Accepted Manuscript

Full Length Article

Biocompatibility study of multi-layered hydroxyapatite coatings synthesized on

Ti-6Al-4V alloys by RF magnetron sputtering for prosthetic-orthopaedic im-
plant applications

Dunya Abdulsahib Hamdi, Zhong-Tao Jiang, Kwangsoo No, M Mahbubur

Rahman, Ping-Chin Lee, Linh Nguyen Thi Truc, Jaegyu Kim, Mohmmednoor
Altarawneh, L. Thair, Thamir Abdul- Jabaar Jumaa, Bogdan Z. Dlugogorski

PII: S0169-4332(18)32293-1
DOI: https://doi.org/10.1016/j.apsusc.2018.08.157
Reference: APSUSC 40194

To appear in: Applied Surface Science

Received Date: 10 January 2018

Revised Date: 26 July 2018
Accepted Date: 19 August 2018

Please cite this article as: D. Abdulsahib Hamdi, Z-T. Jiang, K. No, M. Mahbubur Rahman, P-C. Lee, L. Nguyen
Thi Truc, J. Kim, M. Altarawneh, L. Thair, T. Abdul- Jabaar Jumaa, B.Z. Dlugogorski, Biocompatibility study of
multi-layered hydroxyapatite coatings synthesized on Ti-6Al-4V alloys by RF magnetron sputtering for prosthetic-
orthopaedic implant applications, Applied Surface Science (2018), doi: https://doi.org/10.1016/j.apsusc.
2018.08.157

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 Biocompatibility study of multi-layered hydroxyapatite coatings
synthesized on Ti-6Al-4V alloys by RF magnetron sputtering for
prosthetic-orthopaedic implant applications

Dunya Abdulsahib Hamdi1, Zhong-Tao Jiang2, Kwangsoo No3, M Mahbubur Rahman2,4,

Ping-Chin Lee5, Linh Nguyen Thi Truc6, Jaegyu Kim3 Mohmmednoor Altarawneh2, L.
Thair7, Thamir Abdul- Jabaar Jumaa8, Bogdan Z. Dlugogorski2

1
Department of Prosthetics & Orthotics Engineering, Al Nahrain University, Baghdad, Iraq
2
Surface Analysis & Materials Engineering Research Group, School of Engineering &
Information Technology, Murdoch University, Murdoch, WA 6150, Australia
3
Department of Materials Science and Engineering, Korea Advanced Institute of Science and
Technology, Daejeon, South Korea
4
Department of Physics, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh
5
Faculty of Science and Natural Resources, Universiti Malaysia Sabah, Jalan UMS, 88400,
Kota Kinabalu, Sabah, Malaysia
6
Department of Chemistry, Ho Chi Minh City University of Pedagogy, Viet Nam
7
Research and Nuclear Applications, Ministry of Science and Technology, Baghdad, Iraq
8
Department of Physics, College of Sciences, Al-Nahrain University, Baghdad, Iraq

Abstract
Triple-layered RF magnetron sputtered HAp/Al2 O3/TiO2 coatings synthesized onto Ti-6Al-
4V alloys were studied to improve the surface biocompatibility and corrosion resistance
features. It was seen that the HAp layers played a substantial role in the biocompatibility,
while the intermediate Al2O3/TiO2 layers were used to enhance the corrosion behaviour of the
substrate. XRD results showed an enhanced crystallinity along with the (211) HAp phase
after the simulated body fluid (SBF) immersion experiment. Local electronic and chemical
bonding states of atomic phosphorus and calcium phosphate groups in the coatings, before
and after immersion process, were confirmed via XPS studies. The electrochemical
impedance spectroscopy (EIS) evaluated the corrosion, which indicated a reduction in
capacitance values and a significant improvement of the corrosion resistance of such
coatings; with improved bio-medical properties of Ti alloys.
Keywords: RF magnetron sputtering, hydroxyapatite, Ti-based alloys,
simulated body fluid, electrochemical impedance spectroscopy.

1. Introduction
The studies within the biomaterial field mainly focus on the development of new materials
with mechanical properties similar to the human bone, the surface modification techniques
enabling optimum biocompatibility (which is closely related to their corrosion behaviour in
biological environments) and osseointegration of medical alloy implants [1]. The
osseointegration refers to “the apparent direct attachment or connection of osseous tissue to
an inert, alloplastic material without intervening connective tissue” [2]. Ti and Ti-based
alloys were widely used in implant applications due to superior biocompatibility, high
mechanical stability, and the existence of natural oxide layers, which enhanced the corrosion
resistance of the surface. However, this passivating layer may produce conditions conducive
to accelerated focal corrosion and failure [3]. Surface modification of Ti-based alloys can be
carried out with different techniques, such as: sol–gel, electro-phoretic deposition (EPD),
plasma spray coating process, RF plasma sputtering deposition, and reactive plasma
sputtering processes [4-15]. These techniques are able to enhance the bio-reactivity of
substrates. However, the electro-phoretic deposition and sol-gel techniques resulted in: non-
uniform thickness, large agglomerations and poor biological fixation to the metal substrates.
The plasma spray coating process had high efficiency and high temperature, which produced
a high degree of melting to ceramic powders [16]. Films fabricated via magnetron sputtering
technique are, generally: high-quality, high density, high adhesion, good thickness under
controlled uniformity over a large area and at a relatively low substrate temperature. The
sputtering synthesised films also met the requirements of grain size distributions and higher
degree of crystallinity, which was desired for the desorption ability in body fluids [17]. Thus,
surface modification of Ti alloys was always being actively sought for the improvement of
the performance of biomaterials in biological systems [18]. Ceramic oxides, such as: ZrO2,
Al2O3, TiO2, MgO and non-oxide ceramics, such as: hydroxyapatite (HAp), SiC, ZnS, Si3N4
play vital roles in improving osseointegration properties of the implant materials [19]. HAp
bioceramics have good biocompatibility but weak mechanical strength. So that it cannot be
used as bulk material. The HAp bioceramic coating on biomedical metallic substrates can
significantly increase its mechanical strength for various applications. HAp was found in the
inorganic component of human bone. It possesses higher bio-affinity that can form the bio-
ceramic coatings; and it is bonded directly with bones required for osseointegration of the
implants [17]. The structure, such as the thickness and number of HAp layers, also affects the
quality of implants. Coatings with a single HAp layer had poor mechanical but better bio-
medical properties [20]. For instance, the thermal expansion coefficient of Ti alloys, TiO2,
Al2O3 and HAp materials were 8.7×10-6/K, 7.249×10-6/K, 8.2×10-6/K, and 13.6×10-6/K,
respectively [21]. Thus, the addition of TiO2 onto the substrate was expected to reduce
thermal expansion mismatch between the substrate and coated layers. Al2O3 was chosen as
the second layer between TiO2 and HAp layers because of its thermal expansion coefficient
to be very close to that of TiO2 [22, 23]. A combined low powered ultrasonic irradiation and
low concentration of gelatine, in the synthesis of nano-sized Hap particles, were thoroughly
investigated via ultrasonic method [24]. The use of Al2O3 layer in between the TiO2 and HAp
coatings led to an increase of interfacial bonding strength. Double or triple layers of HAp
coatings introduced a large number of parallel interfaces with the surface, which may deflect
micro-cracks, provide a relatively wide zone of elemental interdiffusion between the substrate
and the top of the bio-coating, and result in the improvement of the adhesion strength.
Biocompatibility represents the interaction between the biological environment and the
material [25]. Ti-based alloys, ceramic oxides, and non-oxide based materials exhibit good
biocompatibility characteristics. This study was aimed at investigating the triple-layered
(HAp/Al2O3/TiO2) thin film coatings deposited onto Ti-based alloys via RF magnetron
sputtering technique. Materials characterizations include structural, surface morphological
information, improved biocompatibility and corrosion performances before and after
immersion in simulated body fluid (SBF which stands for a simulation for the interaction of
human bones with the biological environment) for one month. Furthermore, since HAp
coatings have displayed substantial success as biomaterials for both dental and orthopaedic
implants due to its applauding osteo-conductive, bioactive properties, and in vivo behaviour.
Hence, the presence of HAp coatings was also expected to prolong the lifetime of prostheses.

2. Materials and methods

2.1 Preparation of the triple-layered (HAp/Al2O3 /TiO2) thin film coatings by RF
magnetron sputtering
The Ti alloy (Ti-6Al-4V) GR2 ASTM F136 (Baoji Jinsheng Metal Material Co. Ltd) had the
composition of Ti 89.20%, Al 5.50-6.50%, V 3.50-4.50%, Fe 0.40%, C 0.10%, N 0.05%, O
0.20% and H 0.0125%. Specimens of Ti-6Al-4V alloy, with a circular shape of 20.0 mm
diameter and 1.8 mm thickness, were used as a substrate for HAp coatings. The Ti-6Al-4V
alloy substrates were sand blasted with SiC abrasive papers (120 – 2500μm), and polished
with the Struers-DAP-U system, Denmark. Three types of targets were used: TiO 2 (4~5µm of
particle size with a purity of 99.99%), HAp (2µm particle size, with a purity of 99.90%) and
Al2O3 (1µm of particle size with a purity of 99.99%). The target materials were received from
Vacuum Thin Film Materials (VTM), Korea. The operation frequency of RF magnetron
sputtering device was 13.65 MHz; with the base pressure of 1 × 10-7 Torr and the working
pressure of 5.5 × 10-3 Torr. The layers of TiO2 and Al2O3 were fabricated on Ti-6Al-4V alloy
substrates by TiO2 and Al2O3 targets, respectively. The third layer, HAp, was fabricated on
the top of Al2O3 layer. The sputtering times for the TiO2, Al2O3 and HAp layers were 2 hours,
4 hours and 7 hours, respectively. The fabricated triple-layered (HAp/Al2O3/TiO2) thin film
specimens were annealed at 600 °C for 2 hours, in a vacuum furnace with the base pressure
of 1 × 10-4 Torr, for recrystallization. Heat treatment protocol of such alloys was extensively
reported in earlier studies [26]. Circular shaped specimens of 20 mm diameter and 1.8 mm
thickness were used for the experimental measurements.

2.2 Characterization methods

The crystalline phases of the coatings were identified by X-ray diffraction technique (Rigaku
Ultima JV, Japan) with Cu-Kα radiation (λ = 1.5406 Å). The scan rate was 2° per minute and
the step size was 0.01°.

The surface morphology, cross-sectional examination and thickness of the coatings were
studied by SEM technique (SEM, Hitachi 5-4800, Japan). To avoid electrical charging due to
low electrical conductivity of the coated surfaces (ceramic nature), specimens were initially
covered with a very thin platinum layer in vacuum (BAL-TEC, SCD-005). The elemental and
chemical composition of the coatings were determined by X-ray photoemission spectroscopy
measurement (XPS, Kratos axis ultra DLD) with the monochromatic radiation Al-Kα X-ray
source (hν = 1486.6 eV, 15 kV and 12 mA). The pass energies, for the survey scan and high
resolution measurements, were 160 eV and 20 eV, respectively. CASA-XPS v.2.3.15
software package was employed to analyse the XPS spectra.
2.3 Biocompatibility experiments
The biocompatibility experiment was performed by immersing the triple-layered
(HAp/Al2O3/TiO2) thin film coatings, in SBF, for a month. Table 1 lists the compositions of
the solution. Compositional and other extensive details on SBF have been also cited
elsewhere [27]. The SBF immersing triple-layered (HAp/Al2O3/TiO2) thin film coatings were
then evaluated in an in-vitro test on corrosion, with an alternating current (AC), and
electrochemical impedance spectroscopy (EIS) measurements. The EIS technique provided
precise, error-free kinetic and mechanistic information with a variety of techniques and
output formats (Nyquist plots, see Figure 8 below) which can be used to make a measurement
in low conductivity solutions. During EIS measurement, an alternating voltage was applied to
the corroding metal, and the corresponding impedance (Z) was measured because all the
magnitude and the relative phase angle of voltage and current must be accounted for the
impedance. These measurements were systematically repeated to replicate specimens, for EIS
analyses, in the frequencies range of a few mHz to 100 kHz. A primary advantage of
impedance techniques was that a purely electronic circuit model can be used to represent an
electrochemical system, such as Randles equivalent circuit. The detail information on the
charge transfer phenomena, at the interface between semiconductor and electrolyte, was
discussed using EIS technique via Randles equivalent circuit model [28, 29].

3. Results and discussion

3.1 XRD analysis of (HAp/Al2O3/TiO2) thin film coatings
The XRD pattern of the triple-layered (HAp/Al2O3/TiO2) thin film coatings, see Fig. 1,
demonstrates that there are two HAp associated phases; other than the calcium phosphate
phase [30-31]. After annealed at 600 C, the formation of a ceramic compound, such as α-
Ca3(PO4)2, can be identified through the (1011), (214), (0210), and (404) reflection planes at
2θ of 25.8, 27.4, 31.0, and 41.1, respectively. The HAp phase can be determined through the
XRD peaks at 25.8, 32.1 and 34.2 for the reflection plans of (002), (112) and (202),
respectively (according to the ICDD database 01-078-2486). Fig. 2 indicates that the triple-
layered (HAp/Al2O3/TiO2) thin film coatings demonstrated a preferential orientation towards
(211) lattice planes, together with a higher degree of crystallinity. This preferred orientation
was evolved from a random orientation to a pure (211) reflection planes, with increasing the
thickness of HAp coatings after immersion in SBF solution for one month. The results were
consistent with the work reported by Shuyan Xu et al. [32]. The calcium phosphorus phase
observed in the range of 25°-43° indicates the degradation of most calcium phosphorus
phase, together with the enhancement of intensity of HAp (211) phase. Titanium peaks, with
lower intensities of (100), (002) and (101) reflection planes, were at 35.4, 38.0 and 40.7,
respectively. This means that the increase of thickness of HAp coating was due to the
biomimetic process during the immersion, in SBF, together with the dissolution of calcium
phosphorus phase, or due to the immersion process enhanced the crystalline density of HAp
layer. The (211) peak of HAp phase at 2θ of 31.7° was due to the preferred orientation, with
higher degree of crystallinity. The SBF immersion of the specimens was intended to attract
ions of Ca and P from the solution growth onto the surface. That means the surface becomes
more biocompatible. This result was in good agreement with the publication of Yong Liu et
al. [33].

3.2 Surface topography and morphology

Fig. 3 (a) shows the cross-sectional SEM image of Ti-6Al-4V alloy substrate, which is
compared to the triple-layered (HAp/Al2O3/TiO2) thin film coatings fabricated by RF
magnetron sputtering, shown in Fig. 3 (b). The thicknesses of TiO2, Al2O3, and HAp layers
were approximately 300 nm, 540 nm, and 390 nm, respectively. Identification of thickness of
the layers is very important for corrosion resistance measurement which blocks the pathways
of active ions damaging the substrates. The surface morphology and particle shapes of HAp
coating were similar to those obtained by Takacs et al. [34]. A small amount of particle
agglomerations and a few porosities were also observed around the surface of the coatings. It
was also assumed that the high annealing temperature caused the favourable orientations
around the crystallographic planes, as explained in the XRD analysis. This can be elucidated
by noting that, the HAp structure had a hcp phase and the Ti-6Al-4V alloy contained a double
phase consisting of a major α-hcp phase and a minor β-bcc phase, thus far, small
agglomerations of the deposited particles can be arisen. The porous surface improved fixation
via the growth of bone into the coatings forming a mechanical interlock alloys [34-35].

Fig. 4 shows the top-view SEM images of the triple-layered (HAp/Al2O3/TiO2) thin film
coatings, before and after immersion in SBF solution for one month. The boundaries were
associated with the oxidation reactions of Al/Al2O3, and Ti/TiO2. These oxide layers partially
compensated for the annealing shrinkage and inhibit the formation of cracks. It was assumed
that the apatite components, such as Ca and P in SBF process, could penetrate the coated
surface through the porosities. As a result, new layers developed with a series of spherical
shaped apatite linked together and well bonded to the coated layers. Since, the concentration
of SBF solution (see Table 1) was similar to one of the human body solutions, and the growth
of dendritic HAp layer on the surface of thin films, after immersion in the SBF solution,
indicates that the surface is highly biocompatible [36]. The dendritic HAp phase had a
uniform layer, which fully covered the original HAp layer.

It is known that the main aims of surface modification of medical alloys are: to protect the
surface against corrosion, which needs a porosity free surface in order to reduce the active ion
attachment to the base metal, and to create a rough and porous surface, in order to enhance
the tissue-implant bonding. From the electrochemical view point, the introduced TiO2 and
Al2O3 layers lead to the formation of the bonding layer, which blocked the pathway of active
ions to attack the substrate materials. Thus, the triple-layered (HAp/Al2O3/TiO2) thin film
coating structure is able to increase the biocompatibility, while TiO2 and Al2O3 layers
enhance the corrosion behaviour of the substrate materials.

3.3 XPS Analysis

3.3.1 XPS analysis of annealed coatings before immersing in SBF
High resolution XPS spectra and the corresponding de-convolution curves of the triple-
layered (HAp/Al2O3/TiO2) thin film coatings are shown in Fig. 5 and the corresponding peak
positions and relative percentage due to different chemical bonding states are listed in Table
2. Fig. 5 shows that the deconvolution of C1s spectrum consisted of three components. The
first peak at 284.58 eV is due to the external adventitious hydrocarbon C-H due to pump oil
or contamination from air. The second one at binding energy of 285.63 eV is assigned to be
C-O or C=C bonds. The last one at 286.82 eV can be due to C-P environment. These results
are in good agreement with the NIST XPS database and other reports [36-38]. The de-
convolution of O1s spectrum (Fig. 5(b)) consist of three sub-peaks: (1) the first and second
peaks at 529.20 eV was attributed to Ca=O bonding, the peak at 531.70 eV was due to C=O
bonding states, and (2) the third peak detected at 533.04 eV was associated within P2O5
phase. These observations were well consistent with the NIST XPS database and previous
reports [39-40]. The deconvolution of P2p spectrum (see Fig. 5 (c)) consisted of three sub
peaks: the first peak at a binding energy of 132.0 eV and the second one at that of 133.3 eV
were recognized to the CaHPO4 phase. However, the third peak seen at 134.5 eV could be
allocated to anhydrous monocalcium phosphate Ca(H2PO4)2 phase. All these peaks were
attributed to the pyrophosphate groups. Fig. 5 (c) is the deconvolution of Ca2p XPS spectra:
(1) the first and second components (at 346.7 and 347.7 eV) are due to Ca-P chemical
environments, and (2) the third and fourth components (at 349.87 and 351.25 eV) are due to
Ca-O bonding states. The two peaks of Ca2p3/2 observed at binding energies of 346.7 and
347.7eV are associated with possible chemical phosphate materials (CPM). Many different
materials, containing Ca, also gave a similar binding energy of Ca2p because different
oxidation states of Ca in those materials were similar to those of Ca3(PO4)2,
Ca10(PO4)6(OH)2) phases.

3.3.2 XPS analysis of the triple-layered (HAp/Al2 O3/TiO2) thin film coatings after
immersion in SBF for one month
XPS spectra of the triple-layered (HAp/Al2O3/TiO2) thin film coatings after immersed in SBF
solution, for one month, are shown in Fig. 6 and the peak positions of key elements are listed
in Table 3. In Fig. 6 (a), the C1s spectrum can be de-convoluted to three sub-peaks. The first
and second peaks at 283.38 and 284.91 eV relate to the chemical states of carbon arising due
to the external adventitious of carbon atoms, while the remaining peak, at 288.02 eV,
assigned to a NaC2H3O2 phase. It can be assumed that sodium atoms acted as reagent
contaminants in SBF. It is also considered that after the immersion the appearance of the
NaC2H3O2 phase and an increasing of amount of carbon components, come from SBF and the
atmosphere. The results were in good agreement with the NIST XPS database and the work
done by other groups [37-38]. The O1s spectrum in Fig. 6 (b) was deconvoluted into three
components at binding energies of 529.77, 531.65, and 533.28 eV. The two components were
attributed to Ca=O bonding and the peak seen at 533.28 eV was due to the P2O5 phase. The
Ca2p spectrum (Fig. 6 (c)) could be resolved into four components at 344.39, 347.22,
350.14, and 351.48 eV. The first component seen at 344.39 eV corresponded to the
contribution of calcium element. The remaining peaks at 347.22, 350.14 and 351.48 eV were
assigned to Ca-P bonding, which was reported by Ren-Jei Chung et al. [37]. It was also
realized that more signals belonging to the calcium phosphate groups were detected after the
SBF immersion. This was also confirmed by SEM studies, shown in Fig. 4. The Fig. 6.d
showed that the de-convolution of P2p spectrum consisted of three sub-peaks at 130.37,
132.8, and 133.51 eV. The signals at binding energies of 130.37 and 133.51 eV were
assigned to (C6H5)2PCH2P(C6H5)2 and Ca(H2PO4)2 phases, respectively; whereas the peak
detected at 132.45 eV belonged to atomic phosphorus with the maximum intensity. These
observations were consistent with the NIST XPS database and some earlier reports [40, 41].

3.4 In vitro corrosion investigation via EIS measurements

The Nyquist plots of Ti-6Al-4V original alloy and the triple-layered (HAp/Al2O3/TiO2) thin
film coatings, after being immersed in SBF, were used to investigate the passive behaviour
(see Fig. 7). EIS method was used to evaluate the corrosion parameters of the coating. An
equivalent electronic circuit model (Randle’s circuit, Fig. 8), of the electrochemical system,
was applied and the impedance data (see Table 4) was obtained by fitting the experimental
data to an appropriately proposed circuit model. These results were acquired after the
application of open circuit stability of the passive film, in SBF solutions, which depicts the
corrosion model (see Fig. 8(a)). The simulated Randle’s circuit consisted of the polarization
resistance (R2), in parallel with the capacitance of the coating (C2), and in series with the
resistance of solution (R1). R1 was defined the uncompensated resistance of the electrolyte
between the working and the reference electrodes; R2 represented the polarization resistance
or the charge transfer resistance at the working electrode/electrolyte interface, related to the
rate of corrosion reactions at the passive domain. (C2) was the specific double-layer
capacitance at the working electrode/electrolyte interface. M was an external resistance added
to the equivalent Randle’s circuit, for the section of triple-layered (HAp/Al2O3/TiO2) thin
film coatings, see Fig. 8(b). These values of the capacitive behaviour of the surfaces are
shown in Table 4 (the impedance value is the reciprocal of the capacitance). The surface of
Ti-6Al-4V alloy was well covered by TiO2+Al2O3 double-layered coating which blocked all
the natural oxide porosities and resisted the active ions such as Cl- and O+ to transfer from the
solution to the substrate. That led to the low capacitance and high impedance of the surface.
The limitation of the current study was relevant in vivo tests due to the time restriction.
However, it is worthwhile to carry out such experiments for future study

4. Conclusions
The triple-layered (HAp/Al2O3/TiO2) thin film coatings deposited onto the surface of Ti alloy
by RF magnetron sputtering technique were investigated for their structural and
morphological formations, improved biocompatibility and corrosion performances. The
existence of the intermediate Al2O3/TiO2 layers supported the enhancement of adhesion
between HAp coating and the substrate because of the similar structure and thermal
expansion of TiO2, Al2O3 components to those of Ti-6Al-4V alloys. The triple-layered
(HAp/Al2O3/TiO2) thin film coatings had a high crystallinity, and a wide variety of
preferential directions. XPS results confirmed the existence of Ca=O bonding, calcium
phosphate phase and atomic phosphorus, contained in the coating immersed in SBF solutions.
EIS results indicated that the multi-layered (Al2O3 /TiO2) coatings had a substantial reduction
in capacitance values, which revealed the improvement of corrosion parameters of the
coatings. As a result, HAp layers played a substantial role of the biocompatibility of the
surface, while the intermediate Al2O3/TiO2 layers were used to enhance the corrosion
behaviour of the substrate material which blocked the pathway of active ions from the
environment onto the surface of Ti-6Al-4V alloys.

Acknowledgements
Dunia would like to thank the Ministry of Higher Education and Scientific Research of Iraq
for their funding and scholarship and the Engineering Faculty at Al Nahrain University for
providing with their logistic and other supports. M Mahbubur Rahman is grateful to
Jahangirnagar University for their support.

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Figure 1. XRD pattern of the triple-layered (HAp/Al2O3/TiO2) thin film coatings before
immersion in SBF solution.
Figure 2. XRD patterns of the triple-layered (HAp/Al2O3/TiO2) thin film coatings after
immersion in SBF solution for a one month.
Figure 3. The cross-sectional SEM image of (a) Ti-6Al-4V original alloys, and (b) triple-
layered (HAp/Al2O3/TiO2) thin film coatings.

Figure 4. Top-view SEM images of the triple-layered (HAp/Al2O3/TiO2) thin film coatings
(a) before, and (b) after immersion in SBF solution for one month.
Figure 5. XPS spectra and their deconvolution curves of the triple-layered (HAp/Al2O3/TiO2)
thin film coatings: (a) C1s, (b) O1s, (c) P2p, and (d) Ca2p photoelectron lines before
immersion in SBF solution for one month.
Figure 6. XPS spectra and their deconvolution curves of the triple-layered
(HAp/Al2O3/TiO2) thin film coatings after immersion in SBF solution for one month: (a)
C1s, (b) O1s, (c) Ca2p3/2, and (d) P2p photoelectron lines.

dgsa
Figure 7. Nyquist plots of Ti-6Al-4V original alloys and triple-layered
(HAp/Al2O3/TiO2) thin film coatings after immersion in SBF solution for one month.
 (a) (b)

Figure 8. Randle’s circuit of (a) Ti-6Al-4V original alloys, and (b) the triple-layered
(HAp/Al2O3/TiO2) thin film coatings after immersion in SBF for one month.
Table 1. The concentration of SBF.

Ion Concentration (mM)

Na+ 142.5
K+ 5.0
Mg2+ 1.5
Ca2+ 2.6
Cl- 148.7
HCO3- 4.2
HPO42- 1.0
SO42- 0.5
Table 2. Electronic bonding states of the triple-layered (HAp/Al2O3/TiO2) thin film coatings
fabricated by RF magnetron sputtering as acquired from XPS studies (before immersion in
SBF).

Bonding Binding Percentages of

Photoelectron lines FWHM (eV)
states energy (eV) component (%)
CH 284.58 1.20 30.0
C1s C-O /C=C 285.63 1.20 41.2
CP 286.82 2.30 29.0
CaO 529.50 2.5 9.1
O1s CaO 531.73 2.50 26.2
P2O5 533.04 2.50 64.7
Ca-P 346.2 2.22 21.4
Ca2p3/2 CaO 349.87 2.01 9.9
CaO 351.25 2.09 19.7
P 132.00 2.35 23.4
P2p CaHPO4 133.28 1.56 31.59
Ca(H2PO4)2 134.49 1.89 45.03
 Table 3. Electronic bonding states of the triple-layered (HAp/Al2O3/TiO2) thin film coatings
fabricated by RF magnetron sputtering as acquired from XPS studies (after immersion in
SBF).

Bonding Binding FWHM

Photoelectron Percentages of
states/possible
lines energy (eV) (eV) component (%)
chemical environments
Carbides (C-Ca) 283.38 2.00 19.4
C1s C-H or C-C 284.91 1.88 42.4
NaC2H3O2 288.02 2.68 38.2
Ca=O 529.77 1.99 9.1
Ca=O 533.28 2.50 26.2
O1s O=P bonding states in
531.65 2.50 64.7
P2O5
Metal Ca 344.93 2.35 8.5
Ca=O 350.14 2.50 27.8
Ca2p3/2 Ca=O 351.84 2.50 15.2
Ca=O 347.22 2.43 48.5
P-CH2 bonds in
130.37 1.90 15.4
(C6H5)2PCH2P(C6H5)2
P2p
Elemental P 132.45 2.00 57.4
Ca(H2PO4)2 133.51 1.76 27.3

Table 4. The equivalent circuit parameters of Ti-6Al-4V original alloy and the triple-layered
(HAp/Al2O3/TiO2) thin film coatings after immersing in SBF.

Samples R1 (Ohm) R2 (Ohm) C (Farad) M (Ohm)

Ti-6Al-4V 4023 402325 1.574×10-6 …
The triple-layered
60.57 26300 1.33×10-10 449366
coating
 Highlights

 Triple-layered HAp/Al2O3/TiO2 coatings were synthesized via RF magnetron

sputtering method.
 Biocompatibility and corrosion resistance features of HAp coatings were studied.
 XRD, SEM, XPS, and EIS methods were employed for the characterizations of HAp
coatings.
 Biocompatibility and corrosion performances before and after immersion in
simulated body fluid (SBF) solution were analysed.
 Deconvolution of XPS spectra provide us with surface chemical bonding states of
triple-layered HAp/Al2O3/TiO2 coatings.