journal of the mechanical behavior of biomedical materials 134 (2022) 105352

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Journal of the Mechanical Behavior of Biomedical Materials

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

Mechanical behavior and corrosion resistance of sol-gel derived 45S5

bioactive glass coating on Ti6Al4V synthesized by
electrophoretic deposition
I. Azzouz a, b, K. Khlifi a, *, J. Faure b, H. Dhiflaoui a, A. Ben Cheikh Larbi a, H. Benhayoune b
a
Laboratoire de Mécanique, Matériaux et Procédés LR99ES05, Ecole Nationale Supérieure d’Ingénieurs de Tunis, 5 Avenue Taha Hussein, Montfleury, 1008, Université
de Tunis, Tunisia
b
Institut de Thermique, Mécanique et Matériaux (ITheMM), Université de Reims Champagne-Ardenne (URCA), 51100, Reims, France

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

Keywords: The purpose of this work is the synthesis and the characterization of sol-gel derived 45S5 bioactive glass coatings
45S5 bioactive Glass deposited onto Ti6Al4V alloy substrates. This coating aims the improvement of the biocompatibility of metallic
Sol-gel implants for use in dentistry and orthopedy.
Electrophoretic deposition
The 45S5 bioactive glass powder was synthetized by the sol-gel process and the coatings were produced by the
Nanoindentation
Scratch test
electrophoretic deposition technique (EPD). A grinding protocol was developed to reduce the particle size dis­
Corrosion resistance tribution of the sol-gel powder in order to obtain a stable suspension needed for the electrophoretic deposition.
The particle size distribution of the sol-gel powder was determined using Dynamic Light Scattering (DLS).
Different characterization techniques including X-ray diffraction (XRD), Scanning electron microscopy (SEM)
associated to X-ray microanalysis (EDXS), were used to investigate the microstructure and the morphology of the
coatings before and after an optimized thermal treatment. Homogeneous 45S5 bioactive glass coatings were
obtained with no observable defects. However these coatings are functional if they present good mechanical
properties. Thus, a mechanical study using nano-indentation and micro-scratch testing was carried out. The
obtained results showed that well adherent and cohesive coatings were obtained. The Young’s modulus and the
hardness are improved with the thermal treatment. Indeed, they increased from 11 ± 0.54 GPa and 100 ± 4.34
MPa respectively to 28 ± 1.34 GPa and 300 ± 14.21 MPa. The corrosion resistance of the coatings was also
studied. The electrochemical were carried using a Potentiostat-Galvanostat PGZ301 in 3.5% NaCl solution at
37 ◦ C. It was observed that the 45S5 sol–gel derived bioactive glass coatings allowed the enhancement of
corrosion resistance of the implant.

1. Introduction
Metals of orthopedic implants are susceptible to endure the me­
chanical stresses while and post-implantation for long term support and
stability in vivo. Among these metals, titanium and its alloys are
commonly used due to their interesting mechanical properties. How­
ever, a main concern is about the corrosion resistance in physiological
fluids and their lack of bioactivity, i. e, they are not able to bond to living
tissue without cementation or external fixation devices (García et al.,
2004). Moreover, metallic artificial implants are bioinert which could
lead to encapsulation by the formation of fibrous tissues resulting in a
weak bond formation with the bone and failure of the implant. Thus, it is
necessary to coat these metallic implants with bioactive materials
known by their ability to form a strong bond with the bone by forming a
carbonated hydroxyapatite layer which is the inorganic component of
the natural bone. This layer formation arouse both the cellular response
of the surrounding tissues and the surface mechanical properties of the
implant which is of great importance for high load bearing conditions
(Ducheyne and Qiu, 1999) (Łączka et al., 2016). Bioactive glasses have
proved their clinical success in bone repairing applications (Liu and
Miao, 2004) and have been used in many medical applications since
their discovering by Hench (Buddy D. Ratner, Allan S. Hoffman, Fred­
erick J. Schoen, 1996) (Hench and Wilson, 1993). They show the best
bioactive behavior since they can bond to hard and soft tissues in just a
few hours (Schrooten and Helsen, 2000). The bioactive glasses are al­
ways very attractive materials (Bajda et al., 2021). They present the

* Corresponding author.
E-mail address: kaouther.khlifi@ipeiem.utm.tn (K. Khlifi).

https://doi.org/10.1016/j.jmbbm.2022.105352
Received 26 April 2022; Received in revised form 23 June 2022; Accepted 28 June 2022
Available online 1 July 2022
1751-6161/© 2022 Published by Elsevier Ltd.
I. Azzouz et al.
Fig. 1. Flowchart of the grinding protocol.
advantage to have a controlled genetic response (Xynos et al., 2000)
since they have higher bioactivity and increased absorption rates (Lin
et al., 2018). The sol–gel synthesis has been widely used as an appro­
priate method to obtain bioactive glasses with different morphologies,
such as powders, coatings, fibers or 3D porous scaffolds both micro and
nanosized (Zheng and Boccaccini, 2017) (Baino et al., 2016). Bioactive
glasses synthetized by sol gel method present good characteristics of
osteoconduction and osteoinduction (Łączka et al., 2016). Sol-gel pro­
cessing of bioactive glasses, allows the enhancement of bioactive and
biological performance, due to the presence of specific surface areas
(Justyna et al., 2018). They are very interesting materials for tissue
regeneration and tissue engineering. Moreover, the sol gel technique
offers the advantage of obtaining a well-controlled composition and a
high specific surface area and porosity of the produced powder, inducing
their high bioactivity level (Brekke and Toth, 1998) (Fathi and Doost
Mohammadi, 2008). Therefore, the bioactivity of sol-gel derived
bioactive glasses is greater than that of melt-quenched ones (Gallardo
et al., 2001). On the other hand, the bioactive glasses powders can be
used to obtain implants consisting of bioactive coating on titanium alloy.
To obtain these implants, different techniques can be used for applying
the bioactive glass coating onto the titanium substrates, plasma spraying
(López et al. n.d.), flame spraying (Henao et al., 2019), magnetron
sputtering (Mardare et al., 2003). However, the electrophoretic depo­
sition (EPD) presents the advantage to produce films on substrates of
different forms and shapes and allows to control the particles mobility in
suspension through the applied electric field. Thus EPD offers the pos­
sibility to produce homogeneous and densely packed films (Farnoush
et al., 2015) (Khalili et al., 2016) (Corni et al., 2008) (Besra and Liu,
2007). To the authors’ knowledge, no studies have been published about
the nanomechanical, scratch and corrosion behavior of sol-gel derived
45S5 bioactive glass coating on Ti6Al4V synthesized by electrophoretic
deposition. In this study, 45S5 nanopowder was elaborated by the
sol-gel route associated to an optimized grinding protocol. This powder
was used to elaborate 45S5 bioactive glass coatings on the Ti6Al4V
substrate by EPD. The obtained coatings were characterized, respec­
tively, by SEM-EDXS and X-ray diffraction (XRD) for morphological,
chemical, and structural analysis. The electrochemical corrosion
behavior of the 45S5 sol–gel/Ti6Al4V implant was investigated by
potentiodynamic polarization tests in a physiological normal saline
medium at a temperature of 37 ◦ C. The mechanical properties of the
45S5 sol–gel coatings were performed by scratch tests and
nanoindentation.
2. Materials and methods
2.1. Sol-gel synthesis of the 45S5 bioactive glass
The sol–gel process developed in our laboratory to produce bioactive
glasses was used for the synthesis of the 45S5 bioactive glass (J J. Faure
et al., 2015). It consists of three steps: the hydrolysis, the condensation
and the gel drying. The citric acid is used to catalyze the hydrolysis
reactions and the sol-gel reactions were performed within a thermo­
stated reactor to control the reaction temperature. Colloidal solution
with the 45S5 composition (45 wt% SiO2, 24.5 wt% CaO, 24.5 wt%
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Journal of the Mechanical Behavior of Biomedical Materials 134 (2022) 105352
Na2O, 6 wt% P2O5) was prepared by mixing at ambient temperature 25
ml of a 5 mM citric acid solution (C6H8O7, 5 mM), 11.6 ml of tetraethyl
orthosilicate [(TEOS): (Si (OC2H5)4)] and 1 ml of triethyl phosphate
[(TEP): (PO(C2H5)3)]. The hydrolysis step consists of mixing all the so­
lutions by magnetic stirring at 500 rpm until having a clear sol. The
sodium nitrate (NaNO3) and the calcium nitrate tetrahydrate
(CaH8N2O10) powders were poured into the mixed solution with
increasing the magnetic stirring until 600 rpm until their complete
dissolution. After 1 h of stirring, a clear sol was obtained. In the second
step, the sol starts to transform into gel through polycondensation re­
actions. Finally, the gel was aged at 60 ◦ C for 12 h and heat treated at
200 ◦ C for 5h followed by two additional hours at 700 ◦ C to obtain a
dried heap.
2.2. Grinding protocol
The electrophoretic deposition technique (EPD) requires a stable
suspension for the coating elaboration. This condition is satisfied when
the particle size distribution is less than 1 μm. Therefore, a grinding
protocol has been developed and consists in three steps (Fig. 1).
First the dried heap was hand grinded in an agate mortar to obtain
particles with coarse sizes. The second step consists of using a Retch PM
100 planetary ball mill (VERDER, Epagny-sur-Oise, France) for dry
milling the powder using a 4 mm agate balls during 2 h with a rotation
speed (V) of 500 rpm and a ball to powder mass ratio (BPR) of 1. For the
final step a wet milling in isopropanol (2-propanol, 99.5%, Alfa Aesar,
Haverhill, MA, USA) was carried out during 2 h with a rotation speed of
600 rpm and a BPR of 30 to obtain a fine powder.
2.3. Measurement of the particle size distribution
The measurement of the sol-gel derived 45S5 bioactive glass powder
particle size distribution obtained after the dry milling (step 2) and the
wet milling (step 3) was performed with a Nano Series-Malvern (10 mW,
632.8 nm, Red Laser, Ltd., Worcestershire, UK) instrument using dy­
namic light scattering (DLS). This fast technique allows to measure the
size distribution of particles in suspension by using the scattering of light
by diffusing particles. It is mostly used to analyze nanoparticles, emul­
sions, and proteins. It offers the possibility to work with a wide range of
temperatures and concentrations from a small amount of powder (Ste­
tefeld et al., 2016). The particles size is obtained by measuring the
fluctuations in the intensity of the light scattered from a suspension or a
solution. These fluctuations, due to the Brownian motion of particles in
suspension, are strong in the case of small particles, due to a high
diffusion coefficient, and weak in the case of coarse particles. Indeed the
diffusion coefficient is related to the particle radius R by the
Stokes-Einstein equation:
D ​ = ​ kT/6πηR
where k is the Boltzmann’s constant, T the temperature and η the vis­
cosity (in this study; η isopropanol = 2.37 × 10− 3 Pa s) (Tomar et al., 2016).
I. Azzouz et al.
Fig. 2. Electrophoretic deposition process.
2.4. Electrophoretic deposition
The EPD experiments were carried out using a 5 wt% suspension of
the sol-gel 45S5 bioactive glass fine powder obtained after the step 3 of
the grinding protocol. The particles are positively charged in contact
with isopropanol; therefore, cathodic deposition was performed. A two-
electrode cell was used (Fig. 2) and the electrodes were made of
Ti–6Al–4V alloy (CRITT-MDTS) as discs (12 mm in diameter and 4 mm
in thickness). The substrate at the cathode was treated by alumina
projection to increase its roughness and thus to improve the adhesion of
the coating. This treatment is followed by dipping in 40% HF for 10 s (to
eliminate alumina residues) and ultrasonic cleaning in acetone (Acetone
technical, Acros Organics, Geel, Belgium), then in distilled water.
The EPD process was carried out at ambient temperature using a
controlled power supply PS 304 Minipac II (APELEX). The two metallic
electrodes were immerged vertically into the EPD cell at a distance of 8
mm. A direct voltage of 30 V and a time of 90s were used and the as-
deposited coatings (called C90) were air dried at room temperature
for 24 h before the thermal treatment in air at 450 ◦ C for 1 h according to
our previous work (Azzouz et al., 2020).
2.5. Scanning electron microscopy and Energy Dispersive X-ray
spectroscopy (SEM-EDXS)
The surface morphology and the chemical composition of the elab­
orated coatings were determined using a field effect scanning electron
microscope (JEOL JSM-5400LV, JEOL, Tokyo, Japan), operating at
0–30 kV associated to an Energy Dispersive X-ray Spectrometer (EDXS).
Fig. 3. Schematic of scratch process and scratch tracks.
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Journal of the Mechanical Behavior of Biomedical Materials 134 (2022) 105352
The X-Ray spectra were obtained with an energy of 15 kV and an
acquisition time of 100s.
2.6. X-ray diffraction (XRD)
The crystalline phase composition of the coatings was determined by
XRD with a DRON-3 diffractometer (Bourevestnik, Saint Petersbourg,
Russia) using a monochromatic copper radiation (CuKα) of wavelength
λ = 0.15406 nm. The X-ray diffraction patterns were registered in a
range of diffraction angles 2θ between 10◦ and 60◦ by steps of 0.04◦ with
an acquisition time of 12 s per step. The crystalline phases were deter­
mined from the powder diffraction files of the International Center for
Diffraction Data (ICDD).
2.7. Scratch test
The adhesion between the coating and the substrate is an essential
parameter for a good performance of the implant. It was evaluated using
the micro-scratch-test method (Fig. 3). A micro-scratch-tester (CSM In­
struments, Peuseux, Switzerland) equipped with a Rockwell HRC
indenter with a tip of 120◦ cone angle and 200 μm radius was used. The
loading speed was 10 mm min− 1 and the track length was 3 mm. The
normal load of the indenter applied onto the coating surface increased
continuously from 0 to 10N with a loading rate of 32.3 N min− 1. For
each, micro-scratch-test experiment five measurements were performed
and two samples per test were used.
2.8. Nanoindentation
Nanomechanical behavior was studied using the nano-indentation
technique developed by CSM Switzerland Instruments (Anton Paar,
Buchs, Switzerland). Tests were conducted using a nano-indenter
equipped with a diamond Berkovich tip under a maximum applied
load of 100 mN. The nanoindentation test consists in indenting a spec­
imen with a very small load using a high precision instrument that re­
cords continuously the applied load and the indenter displacement. Two
samples per test were used. The output obtained from a nanoindentation
test is a graph relating the applied load and the corresponding indenter
displacement during the loading and unloading phases. Nano­
indentation process and typical loading-unloading (P–h) curve (load-
penetration depth curve) are shown in Fig. 4. Load–displacement curves
were obtained by nanoindentation device based on Oliver and Pharr
method (Oliver and Pharr, 1992). During the nano-indentation test, the
penetration depth increased as a function of the applied load. Nano­
indentation was carried out with a maximum load of 50 mN and a
loading rate of 100 mN/min. From the load–penetration curves, elastic
I. Azzouz et al. Journal of the Mechanical Behavior of Biomedical Materials 134 (2022) 105352

Fig. 4. Nanoindentation process, typical loading-displacement curve and Oliver and Pharr model.

and plastic deformation energies, surface hardness (H), and young’s

modulus (E) were calculated using integrated software.
The H/E and H3/E2 ratios were determined to predict the coating
performance (Hong et al., 2016). The H/E ratio, called elastic strain to
failure, was used to assess the film resistance to elastic deformation. The
H3/E2 ratio predicts the resistance to plastic deformation and the wear
resistance of the coating.

2.9. Electrochemical test

Prior to each test, the surface dimensions of the samples in contact

with the electrolyte were measured. The electrochemical corrosion
behavior of the 45S5 bioactive glass coated Ti6Al4V alloy was investi­
gated by potentiodynamic polarization and EIS tests in physiological Fig. 5. EDX spectrum of the sol-gel derived bioactive glass powder.
normal saline at a temperature of 37 ◦ C in order to obtain desired
equilibrium. The time of immersion of the specimens in physiological
linear polarization methods. The mean values of the results were
solutions was over 2 h. An electrochemical corrosion polarization test
calculated.
cell was used for in vitro potentiodynamic corrosion tests. A graphite
electrode was used as the counter electrode and a saturated calomel
3. Results and discussion
electrode (SCE) was employed as a reference electrode. The coated ti­
tanium alloy substrate with an exposed area of 1.1304 cm2 was used as
3.1. Characterization of the sol gel derived 45S5 powder
the working electrode. Physiological normal saline (0.9 wt % NaCl) was
used as electrolyte. To evaluate the corrosion behavior the samples were
Fig. 5 shows the EDX spectrum of the bioactive glass powder ob­
dynamically polarized in the physiological solution. Potentiodynamic
tained by sol-gel. One may clearly observe that all elements of the 45S5
polarization curves were determined at 37 ± 1 ◦ C, using a Solartron
1280 B Electrochemical unit interfaced with a computer. The working
electrode was allowed to equilibrate for 10min in NaCl at a pH of 7.35 ±
Table 1
0.05 to reach a suitable stable open circuit potential before starting the
Quantitative analysis of the sol-gel derived powder.
electrochemical tests which explains that the needed minimum time of
Element O (at%) Si (at%) Na (at%) Ca (at%) P (at%)
2 h (Kirkland et al., 2010). Potentiodynamic polarization test was car­
ried out at a scan rate of 1.0 mV/s. The anodic and cathodic polarization Theoretical 55.27 16.25 17.12 9.54 1.82
curves were obtained for each specimen. The corrosion current densities Experimental 60.1 ± 12.8 ± 13.6 ± 12.4 ± 1.20 ±
3.0 0.7 0.7 0.7 0.05
and corrosion potentials were deduced. Tafel curves extrapolation and

4
I. Azzouz et al.
Fig. 6. X-ray diffractogram of the sol gel bioactive glass coating.
are identified such as O, Si, Ca, P and Na.
The quantitative analysis shows that the measured elemental atomic
concentrations are close to the theoretical ones (Table 1).
These results are confirmed by the XRD pattern of Fig. 6 which re­
veals several crystalline peaks corresponding to the silicate phases
Na2Ca2Si3O9 (ICDD PDF #22.1455), Na2Ca3Si6O16 and Na2CaSi2O6
Fig. 7. Particle size distribution of the sol-gel derived 45S5 bioactive glass after A) step 2, B) step 3 of the grinding process.
Fig. 8. Time evolution of the suspension stability of the sol-gel derived powder.
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Journal of the Mechanical Behavior of Biomedical Materials 134 (2022) 105352
characteristic of the sol-gel 45S5 bioactive glass (Siqueira et al., 2011)
(Azzouz et al., 2020).
Among these phases, the combeite Na2Ca2Si3O9 (ICDD PDF
#22.1455) is known to influence the bioactivity of the 45S5 bioactive
glass once implanted in the human body. The formation of this phase is
directly related to the heat treatment at the temperature of 700 ◦ C
during the drying of the sol gel powder (Chen et al., 2006). Previous
studies have shown that the formation of this phase is more pronounced
in the case of the 45S5 synthesized by sol gel compared to the
melt-derived one (Luiz Siqueira et al., 2011) (J. J Faure et al., 2015).
Thus, the behavior of the 45S5 sol-gel derived coating in contact with
physiological environment is influenced in terms of dissolution and
chemical behavior.
On the other hand, Fig. 7 presents the morphology and the particles
size distributions of the 45S5 powder after the step 2 (Fig. 7A) and the
step 3 (Fig. 7B) of the grinding process. It clearly shows that the particles
size is reduced from about 1 to 2 μm to about 800–900 nm. This final
particle size is required to obtain a stable suspension necessary for EPD.
3.2. Morphological, chemical, and structural analysis of the 45S5 coating
obtained by electrophoretic deposition
Fig. 8 shows the time evolution of the 5% weight suspension
I. Azzouz et al. Journal of the Mechanical Behavior of Biomedical Materials 134 (2022) 105352

Fig. 9. SEM micrographs and EDS analysis of sol-gel derived coatings before (a, b, c) and after (d, e, f) thermal treatment.

obtained with the optimal 45S5 sol-gel powder in isopropanol. One may
observe that the suspension presents an excellent stability over 1 h
which is preserved up to 7 h. This suspension was then suitable for the
coating deposition by EPD.
The surface morphology of the coating obtained after EPD at 30V
during 90s is presented on Fig. 9. Before thermal treatment (Fig. 9 a, b) a
homogeneous coating with a cracks network is visible. The cracks for­
mation is mainly due to the evaporation of the isopropanol trapped
within the coating during air drying (Azzouz et al., 2020) (Lucas-Girot
et al., 2011). The high magnification micrograph of this surface reveals
that the coating is highly dense and formed by the agglomeration of
sub-micrometric particles. The corresponding EDX spectrum (Fig. 9 c)
shows all elements of the sol-gel 45S5 bioactive glass with elemental
atomic percentages close to that of the initial powder. After thermal
treatment (Fig. 9 d, e, f), the homogeneity and the chemical composition
of the coating were conserved despite a slight increase of the cracks
network. This crack network is due to the mechanism of the layer
growth. Indeed, from a certain thickness, cracks formation starts around
domes formed by powder agglomeration evaporation of the solvent
helps to expand these cracks. One can also note the improvement of the
compactness and density of the coating which is a main factor for the
mechanical performance.

3.3. Nanomechanical behavior of the sol-gel derived 45S5 bioactive glass

Fig. 10 shows the nanoindentation results of the gel-derived 45S5

Fig. 10. Nanoindentation results: Load-Penetration depth curves and the
values of H/E and H3/E2 indexes for the as-deposited and the heat-
treated coating.
bioactive glass coating before and after thermal treatment. The output of
the nanoindentation tests is the graphs showing the evolution of the
normal force as a function of the penetration depth.
According to the load-penetration depth curves. The gel-derived
45S5 bioactive glass coating showed a plastic behavior. Exploitation
of these curves, using the Oliver-Pharr model allows to estimate the

Table 2
Mechanical properties of the coatings before and after heat treatment.
Coating H (MPa) E (GPa) hmax (μm) hr (μm) We/Wt (%) Wp/Wt (%)

As deposited 100 ± 4.34 11 ± 0.54 4.67 4.51 7 93

Heat treated 300 ± 14.21 28 ± 1.34 3.15 3.06 3 97

6
I. Azzouz et al.
Fig. 11. Scratch test study of the as-deposited coating for a maximum load of 5N.
Hardness H and Young’s modulus E as shown in Fig. 4.
Table 2 presents the calculated parameters obtained from the load
displacement curves based on the Oliver-Pharr approach (Oliver and
Pharr, 1992):
A residual penetration depth hr was obtained after the complete
removal of the indenter. The maximum depth of penetration hmax moved
from 4.67 μm for the as-deposited C90 coating to 3.15 μm for the heat
treated one which indicates an improvement of the coating’s hardness.
Indeed, the hardness increased from H = 100 ± 4.34 MPa for the as-
deposited coating to H = 300 ± 14.21 MPa for the heat treated one
and the Young’s modulus from E = 11 ± 0.54 GPa to E = 28 ± 1.34 GPa
for the treated one which is beneficial for reducing the mismatch be­
tween the implant and the supporting bone ((Takemoto et al., 2005)
(Kasten et al., 2005)). This strong increasing of H and E can be explained
by the improvement of the coating compactness and the reduction of its
porosity due to the adopted heat treatment protocol. Such results were
obtained by R. Moriche et al. (R. Moriche et al., 2021). Indeed these
authors found an elastic module of about 25 GPa for 45S5 commercial
bioactive glasses deposited on titanium substrates.
The obtained values of H/E and H3/E2 are represented on the his­
togram of Fig. 10 and the ratios We/Wtot and Wp/Wtot are given in
Table 2. These results confirm the plastic behavior of the 45S5 sol-gel
bioactive glass coating both before and after the heat treatment.
Furthermore, all these results showed that the heat treatment
enhanced the mechanical properties (H and E) as well as the H/E and
H3/E2 ratios, which reveals a good resistance to elastic/plastic
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Journal of the Mechanical Behavior of Biomedical Materials 134 (2022) 105352
deformation and predicts a good wear resistance. It can be concluded
that the heat treatment of the 45S5 sol gel bioactive glass coating in­
duces an important rise of its mechanical properties as well as the
resistance to elastic and plastic deformation. This can be explained by
the high density and homogeneity of the coating obtained after heat
treatment.
3.4. Scratch analysis
Both quantitative and qualitative analyses were carried out. The
graphs representing the variation in the friction force and penetration
depth as a function of the normal load, were superposed to the corre­
sponding optical microscope images of the scratch tracks of the 45S5 sol-
gel derived bioactive glass coatings obtained before and after heat
treatment. Thus the critical loads values were deduced.
Figs. 11 and 12 present the results of the scratch test performed on
the as deposited and heat-treated coating for a maximum load of 5 N. In
both cases, the friction force and the penetration depth increase linearly
with the normal load. No total removal of the coating was observed
which indicated the compactness and the good adhesion of the coating
to the substrate. The maximum load of 5 N was not sufficient for a total
removal of the film but it was adequate to reveal the phenomenon
occurring at the transition loads LC1 and LC2. Their corresponding values
extracted from the curves of Figs. 11 and 12 are given in Table 3. On may
clearly observe that the first critical load LC1 increases from 1.5 ± 0.06 N
for the as-deposited coating to 2.1 ± 0.12 N for the heat treated one. The
I. Azzouz et al.
Fig. 12. Scratch test study of the heat-treated coating for a maximum load of 5N.
Table 3
Critical loads obtained by scratch test of the 45S5 coating before and after heat
treatment for a maximum load of 5N.
Critical forces (N) LC1 L C2
As deposited 1.5 ± 0.06 2.7 ± 1.33
Treated sample 2.1 ± 0.12 3.9 ± 1.94
first delamination corresponding to LC2 increased from 2.7 ± 1.33 N
before heat treatment to 3.9 ± 1.94 N after thermal treatment indicating
an improvement of the coating compactness. These critical load values
are of the same order of magnitude as in our previous work on 45S5
commercial bioactive glass coatings which confirms the positive effect
of the heat treatment on scratch resistance.
On the other hand, to determine the required force to totally remove
the film, the normal load was increased to 10 N. Fig. 13 present the
obtained results. The friction force and the penetration depth increase
linearly by increasing the normal load. Before heat treatment (A), a total
removal of the coating was observed at LC3 = 6 ± 0.33 N. After heat
treatment (B), no total removal of the coating was observed. These re­
sults clearly indicate the good cohesive and adhesive properties of the
coating obtained after heat treatment.
Based on the scratch results (Fig. 13), a possible wear mechanism of
Journal of the Mechanical Behavior of Biomedical Materials 134 (2022) 105352
the 45S5 sol-gel coating is shown in the schematic diagram of Fig. 14.
Three failure mechanisms can be proposed:
- Cohesive failure, at the LC1 critical load, corresponding to the
L C3 appearance of the first cracks.
– - Adhesive failure, at the LC2 critical load, which corresponds to the
– presence of cavities inducing a local delamination of the coating.
- Adhesive failure at the LC3 critical load, corresponding to the total
removal of the coating (over than 50%).
3.5. Corrosion behavior
The electrochemical corrosion tests were carried out in a 3.5 wt %
NaCl solution. The typical potentiodynamic polarization curves ob­
tained in this saline solution for the bare titanium alloy and for the 45S5
sol-gel bioactive glass coated titanium alloy before and after heat
treatment are shown in Fig. 15. These curves were selected for presen­
tation because the extracted values of the corrosion current densities
and of the corrosion potentials were the nearest to the mean values of
the tested specimens.
The corrosion potential Ecorr and the corrosion current density Icorr
are determined from the potentiodynamic polarization curves by the
Tafel extrapolation method (Shi et al., 2010). These results associated to
the cathodic and anodic Tafel slopes (βc, βa) and to the polarization
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I. Azzouz et al. Journal of the Mechanical Behavior of Biomedical Materials 134 (2022) 105352

Fig. 13. Scratch tracks of the A) as deposited and B) heat treated coating for a maximum load of 10N.

resistance (Rp) are shown in Table 4. These parameters are essential to

Fig. 14. Damage mechanisms during scratch test.
investigate the kinetics of the corrosion resistance. The polarization
resistance (Rp) was calculated with the Stern–Geary equation (1)
(G-Berasategui et al., 2015):
Rp = βaβc / (2.303 (βa + βc)Icorr)
As it can be seen in Table 4 and according to Fig. 15, the uncoated
titanium alloy possesses a high corrosion current density Icorr = 2.53
μA/cm2 indicating a low corrosion resistance when immersed into the
normal saline solution. However, for the coated titanium alloy, he
corrosion current density decreases to Icorr = 1.54 μA/cm2 before heat
treatment and to 0.28 μA/cm2 after heat treatment indicating a strong
improvement of the corrosion resistance. These results are confirmed by
the evolution of the corrosion potential Ecorr. Which exhibits a shift to­
wards the nobler values when the titanium alloy is coated by the 45S5
sol-gel bioactive glass. This shift is more important when the implant is
thermally treated.

4. Conclusion

In this work, a 45S5 sol-gel derived coating was elaborated by

Fig. 15. Tafel polarization curves.
electrophoretic deposition on the Ti6Al4V substrate. For this purpose,
an original grinding protocol of the sol-gel powder associated to an
optimized thermal treatment of the coating were developed. SEM-EDXS
and XRD analysis showed that the obtained 45S5 coating is compact and
homogeneous without modification of the 45S5 powder composition.
Nanoindentation and scratch test methods revealed the good cohesion
and adhesion of the 45S5 sol-gel derived coating obtained after thermal
treatment. Moreover, analysis of the corrosion results confirms that the
coating act as a protective layer and improve the corrosion resistance of
the substrate which was much more improved by the thermal treatment.
In conclusion, a new implant for biomedical applications has been
synthetized with improved mechanical properties and corrosion
resistance.

Funding

This research was funded by the Tunisian Ministry of Research and

9
I. Azzouz et al.
Table 4
Mean values of corrosion current densities and corrosion potentials in normal saline solution at 37 ◦ C.
Material Ecorr (mV) Icorr (μA/cm2)
Ti6Al4V alloy − 338.62 2.53
As deposited 45S5 coating − 306.62 1.54
Heat treated 45S5 coating − 287.62 0.28
by the PHC UTIQUE project N◦ 44054ZE.
CRediT authorship contribution statement
I. Azzouz: Investigation. K. Khlifi: Methodology, Investigation. J.
Faure: Validation, Supervision, Investigation, Conceptualization. H.
Dhiflaoui: Methodology. A. Ben Cheikh Larbi: Supervision. H. Ben­
hayoune: Validation, Supervision, Investigation, Conceptualization.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgments
The authors would like to thank Hassane Oudadesse and Bertrand
Lefeuvre from RennesUniversity for their help concerning DLS
experiments.
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