Surface & Coatings Technology 397 (2020) 126044

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Surface & Coatings Technology

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Investigation on the corrosion behavior and biocompatibility of Ti-6Al-4V T

implant coated with HA/TiN dual layer for medical applications
⁎
Maryam Kazemia, Shahrokh Ahangarania, , Mohammad Esmailiana, Ali Shanaghib
a
Department of Advanced Materials and Renewable Energy, Iranian Research Organization for Science and Technology (IROST), Tehran, Iran
b
Department of Materials Engineering, Faculty of Engineering, Malayer University, Malayer, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: Ti-6Al-4V alloy has wide applications in the medical industry due to its unique mechanical properties and
Titanium nitride (TiN) biocompatibility. However, in the long-term use of these alloys, the release of aluminum and vanadium can
Hydroxyapatite (HA) result in serious illnesses. For solving these problems, the implant surface modification can be done to improve
Ti-6Al-4V the corrosion and biocompatibility properties. In this study, TiN coating was applied by Plasma-Assisted
PACVD
Chemical Vapour Deposition (PACVD) method along with hydroxyapatite coating (HA) by sol-gel method on Ti-
Sol-gel
Corrosion behavior
6Al-4V substrate surface. Afterwards, X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-
Biocompatibility SEM), Energy-Dispersive X-ray Spectroscopy (EDS), Atomic Force Microscopy (AFM) and potentiodynamic po-
larization and electrochemical impedance tests were used for evaluating the phase, morphology, chemical
composition, surface roughness, and corrosion behavior in the simulated body fluid (SBF), respectively. Results
showed that the surface roughness of HA/TiN, HA, TiN and substrate specimens were the highest to minimum
values with roughness of 30.86 ± 0.5, 25.1 ± 0.42, 20.43 ± 0.14 and 15.1 ± 0.02 nm, respectively, and the HA-
TiN composite coating had the lowest corrosion current density, highest polarization resistance and corrosion
potential. Results of cell viability and proliferation demonstrated that the HA/TiN nanocomposite coating is a
good choice for dental and orthopedic implants due to its corrosion resistance and biocompatibility.

1. Introduction At the present, application of the metal implants such as stainless

The increasing demand for implants resulted in the progress of the
biomaterials field. Hence, the study and research in the field of bio-
materials has increased significantly in recent years [1–3]. The main
characteristic of a biomaterial is its biocompatibility, meaning that they
should not be toxic or carcinogenic and chemically they should not
perform an undesirable reaction with the body fluids. They must also be
mechanically resistant and have a long fatigue life and an appropriate
density. An ideal metallic biomaterial should have a similar elastic
modulus to that of the bone and have a high corrosion resistance,
aseptic loosening, wear, and good bone-bonding ability. Consequently,
a material with good mixture of high strength and a modulus closer to
bone can be applied in implantation to avoid loosening of implants.
Depending on the type of the bone and the direction of measurement,
the bone modulus varies in the magnitude from 4 to 30 Gpa. With
advent of Ti alloys, their lower modulus varying from 110 to 55 GPa
compared to 316 L stainless steel (210 GPa) and chromium cobalt alloys
(240 GPa), which have been used for the past several years is a very
positive factor [4–8].
steels, cobalt−chromium alloys, and titanium alloys is prevalent [9].
Among the available metal implants, the Ti-6Al-4V alloy (ASTM F136)
is characterized by its properties such as partly low elastic modulus
which is near to that of the bone (reduction of stress shielding phe-
nomenon) and high corrosion resistance to the electrochemical reac-
tions of the body due to the formation of passive layer (TiO2).
Naturally, because of the physiological environment of the body on
its surface, lack of allergenic responses, high strength, low density,
complete neutrality to the body environment, high biocompatibility,
low modulus and high capacity for bonding with bone and other tissues,
it has been advantageous over the stainless steel and cobalt alloy in
dental implants and orthopedic applications in recent years [10]. De-
spite the desirable properties, in recent years, the use of these implants
has been limited, which is due to the fact that when the metallic parts of
implants are exposed to body fluids, they become oxidized and generate
corrosion products [3].The poor corrosion properties leads to the re-
leasing of aluminum and vanadium from the implant into the blood-
stream and in the long time the titanium alloys in biomedical appli-
cations causes problems and diseases such as Alzheimer's disease, and

⁎
Corresponding author.
E-mail addresses: maryam_kazemi@alumni.iust.ac.ir (M. Kazemi), sh.ahangarani@gmail.com (S. Ahangarani).

https://doi.org/10.1016/j.surfcoat.2020.126044
Received 5 April 2020; Received in revised form 4 June 2020; Accepted 5 June 2020
Available online 07 June 2020
0257-8972/ © 2020 Elsevier B.V. All rights reserved.
M. Kazemi, et al. Surface & Coatings Technology 397 (2020) 126044

tissue inflammation [11,12]. Table 1

Moreover, very low permeability of this alloy, as well as the che- Chemical composition of Ti-6Al-4V alloy.
mical and biological disagreement with the hard tissue, do not allow Al V Cr Cu Fe Mn Mo Nb Sn
the penetration of the living tissue into the implant, which necessitates
a permanent connection between the tissue and the implant, and tear 6.32 4.25 Trace 0.004 0.03 0.004 0.008 0.005 0.002
due to usage and repetitive and expensive surgeries are needed. To
overcome these problems, the implant surface modification is followed
Ni Si Zr Pd Ru C W Ti
to improve the corrosion properties, hardness, biocompatibility and
bioactivity properties of these implants [13–16]. One of these methods 0.005 0.02 0.02 0.01 0.06 0.005 0.01 Base
is the creation of biocompatible and bioactive hydroxyapatite (HA)
coatings with the chemical formula of Ca10 (PO4)6 (OH)2 on the surface
complex geometric shapes) for TiN coating and sol-gel method to create
to enhance the bone growth and prevent the metal ions from being
the hydroxyapatite coating (Due to the properties mentioned above)
released on metal implants [13,17]. There are various methods for
were used. Moreover, microstructures, compounds, phase structures
forming hydroxyapatite coatings that can be applied by Pulsed laser
and corrosion properties with a wide range of characterization methods
deposition [19], sol–gel [18], plasma spray and pulsed laser deposition
including field emission scanning electron microscopy (FE-SEM),
[18] and hydrothermal [16,19] techniques.
atomic force microscopy (AFM), Energy-Dispersive X-ray Spectroscopy
The sol-gel method is one of the most important ceramic coating
(EDS), X-ray diffraction (XRD), potentiodynamic polarization and
methods due to its properties such as high purity, no need for expensive
electrochemical impedance were studied.
equipment, low operating temperature, appropriate thickness and
uniformity, and its advantages in comparison with other methods.
These coatings generally provide a good adhesion to the substrate and 2. Experimental
contain a certain crystalline structure. In addition, by applying different
chemical primers, ceramic coatings with very different properties not 2.1. Materials
only improve the corrosion and oxidation resistance as well as the
photocatalytic properties of the coating but also results in the appro- In this study, Ti-6Al-4V alloy was provided by TIMET Corporation
priate antibacterial properties [20]. Jonauske et al. [21] synthesized which was considered as a substrate. In order to determine the chemical
calcium hydroxyapatite thin film on stainless steel by sol-gel method. composition of this alloy, a spectrophotometric test was used, the re-
The results showed that this method is a suitable to improve the surface sults of which are given in Table 1. Specimens with dimensions of
properties of the coating [21]. Harun et al. [22] investigated the ad- 1 cm × 1 cm were prepared for surface coating process. In order to
hesion of hydroxyapatite base coatings on metal biomaterials by var- remove the surface oxide and improve the quality, the surface of the
ious methods such as sol-gel. Shahid et al. and Asri [23] studied the HA- specimens was prepared by grinding up to 3000 and then deoxidized.
coated aluminum morphology by sol-gel method and electrochemical Afterwards, the specimens polished with 0.3 μm alumina particles and
deposition techniques. Noticeably, the shear stress during the im- then cleaned with methanol solution and dried.
plantation process caused the removing of the HA monolayer coating
from the surface and release of the particles from the implant surface 2.2. The plasma nitriding (PN) process
[24].
As a result, researchers have made extensive efforts to address this According to the literature [31–33], the PN process as a pre-treat-
problem including the formation of the multilayer and bioactive com- ment before deposition of TiN coating on titanium alloy specimen are
posite coatings including Ti/TiN/TiCN, TiN/AlN, TiN/CrN, etc. These shown in Table 2. These parameters are developed during the pre-
approaches with gradual changes in the composition and mechanical liminary experiments and based on other researches [34–36]. Fur-
properties of the coating, led to improvement of the adhesion of the thermore, the nitrogen and hydrogen gas flow rate in the PN process
coating, enhancement of the properties of the implants such as bioac- should be less than 0.3 to prevent the formation of the white layer
tivity, and improved the wear and mechanical properties of the com- [37,38].
posite coating [25]. Titanium nitride (TiN) coatings are widely used in
the medical industry because of their high hardness (2400−2800
Vickers), wear resistance, high corrosion resistance, low friction coef- 2.3. Coating preparation
ficient, non-toxicity and excellent biocompatibility. The bond structure
in TiN is predominantly covalent and this type of structure controls the The PACVD was used to prepare the TiN coating, where, during the
wear and chemical properties of the coating [26,27]. Applying TiN coating process, the parameters including substrate temperature
coating is possible in different ways. For example, Ander and et al., (475 °C), applied voltage (480 V), working cycle (40%), deposition time
applied TiN coating on an implant of titanium based alloy via cathodic for all specimens (2.5 h) and total pressure (3 mbar) were constant. H2,
arc deposition technique and after 4 weeks of immersion, the HA spe- Ar, N2 and TiCl4 vapour were used as gases in the coating process.
cimen was synthesized in a simulated body fluid (SBF) [28]. Kim and Details of the flow rates of each gas are given in Table 3.The gas flow
his colleagues applied HA/TiN multilayer coatings on the titanium rate was obtained based on preliminary experiments and also literature
substrate via the magnetron method and then sintered the HA specimen [39].
for 1 h at 1300 °C [24]. Hong et al., [29] investigated the micro- According to the literatures [40,41], the sol-gel method was used to
structure improvement and wear resistance of titanium alloy by apply the hydroxyapatite coating on the specimen surfaces, the process
creating TiN/rnano crystalline/amorphous composite coating using of which is based on three steps as below:
electro-spark deposition. Cheng et al. [30] heat treated Ti-6Al-4V alloy
surface using Plasma-Assisted Chemical Vapour Deposition (PACVD) Table 2
Parameters used in the PN process.
method for biomedical applications.
The purpose of this study was to investigate the biocompatibility Argon Nitrogen Hydrogen Time Voltage Duty Pressure Temperature
and corrosion properties of HA/TiN multilayer composite coating de- (sccm) (sccm) (sccm) (h) (v) cycle (mbar) (°C)
(%)
posited on Ti-6Al-4V alloy. To this end, the PACVD method (due to its
moderate temperature compared to the CVD methods and to prevent 100 50 200 2 550 33 1.3 490
the return of steel and the creation of uniform and thin coatings on

2
M. Kazemi, et al. Surface & Coatings Technology 397 (2020) 126044

Table 3 per milliliter were added to wells containing the specimen and control.
Flow rate for different gases used in TiN coating process. After 4 h incubation, the culture medium was replaced with 200 μL of
Specimen N2/Ar Hydrogen (sccm) Titanium chloride (sccm) dimethyl sulfoxide (DMSO) and 10 min was considered for solving the
dye crystals. After 10 min, the 200 μl of solution was removed from
P1 0.4 200 10 each well and placed in a plate with 96 wells. The optical absorption of
P2 0.6 200 10
the wells was read using Elisa Reader device with a 570 nm wavelength
P3 1 200 10
P4 2.3 200 10
[43].
P5 4 200 10
2.5.2. Electrochemical properties
To investigate the electrochemical properties of the coatings and
First step: at first, ethyl acetoacetate with the chemical formula of prototype, a three-electrode cell, including platinum as the counter
C6H10O3 in the amount of 3CC was diluted with 100 CC ethanol as electrode, Saturated Calomel Electrode (SCE) as the reference electrode
organic solvent (C2H5OH) and stirred for 15 min. Then, 7CC and specimens as the working electrode, was used. Corrosion behavior
(C2H5O3PO), 0.4 CC deionized water and 0.3CC nitric acid were of the deposited coatings under different circumstances was in-
added drop-wise to the solution. The initial solution was stirred with vestigated by polarization test with a potentiostat/galvanostat (EG&G
the magnet at ambient temperature for 24 h at a rotational speed of Princeton Applied Research 263A) in SBF solution for 1 h at 37 °C with
1200 rpm to obtain the final cell. a scan rate of +1 mV/s. Also, electrochemical impedance spectroscopy
Second step: The quaternary calcium nitrate as a source of calcium was performed in the range of 10−2–105 Hz with EG&G A263 device in
ion (CaN2O6.4H2O) was diluted with 10 CC ethanol and then 0.2 CC SBF medium at 37 °C and pH 7.4. The data was analyzed using
nitride acid was added to the solution. Finally, the resulting product ZSimpWin software. Using the results of this test, Nyquist and Bode
was stirred for 15 min. plots were drawn and the analysis was performed on these two dia-
Third step: Then, the second cell was added to the first cell and the grams. Then, polarization resistance of specimens was measured using
final cell was stirred for 30 min. Then, 0.3 CC nitric acid was added Eq. (1):
and the final product was strained for 24 h.
βa βc
RP =
2.4. Coating characterizations 2.3. Icorr (βa + βc ) (1)

where, RP is the polarization resistance, βc and βa are the anodic

2.4.1. Phase and structural properties
and cathodic branched Tafel gradients and the Icorr corrosion current
The phase properties of coatings were determined by X-ray dif-
density, respectively [44].To evaluate the repeatability all measure-
fraction (XRD) (X'Pert PRO MPD model manufactured by PANalytical
ments were performed for three times.
company) method with a scanning angle (2θ) of (10°–90°) and a scan-
ning rate of 0.2°/min. The thickness and morphology of coatings were
3. Results and discussion
examined by Field Emission Scanning Electron Microscopy (FESEM-
MIRA2-TSCAN), along with evaluation of chemical composition by
FE-SEM image of Ti-6Al-4V alloy before coating process is shown in
using Energy-Dispersive X-ray Spectroscopy (EDS, SAMx, France).
Fig. 1. The chemical composition analysis of the observed phases is
presented in Table 5. As can be seen from the Fig. 1, the Ti-6Al-4V alloy
2.5. Biocompatibility assessment
is a β+α biphasic alloy with a structure close to β. Analysis of β phase
shows that this phase is distributed on grain boundaries and has more V
To determine the biocompatibility, Simulated Body Fluid (SBF) with
and less Al in comparison with α phase.
a certain concentration of salts was used according to Table 4 [42].
The X-ray diffraction pattern and FE-SEM image of the TiN coated
Firstly, the salts were dissolved in deionized water and the resulting
specimens are illustrated in Fig. 2. As can be seen in the Fig. 2 (a), in
solution was stabilized in a Teflon plant using a combination of tris-
hydroxymethylaminomethane (C4H11NO3) with a concentration of
50 Mm and HCl at pH of 7.25. Then, all specimens (coating and un-
coated) were placed in solution at 37 °C for 14 days and the calcium
concentration changes were measured by atomic absorption ionometric
test (AAS, 3030).

2.5.1. Assessment of cell viability by tetrazolium assay

MTT assay was carried out to evaluate the proliferation and viability
of osteoblast cells (MG67) on the surface of specimens for three times to
acquired better results. For this purpose, 20 μL of MTT solution at 5 mg

Table 4
Concentration of salts in 1 L solution of SBF [42].
Materials Amount

NaCl 16.07 (gr/l)

NaHCO3 0.71 (gr/l)
KCl 0.45 (gr/l)
K2HPO4·3H2O 0.462 (gr/l)
MgCl2·6H2O 0.622 (gr/l)
1.0 M HCl 78 ml
CaCl2 0.584 (gr/l)
Na2SO4 0.144 (gr/l)
Tris 12.236 (gr/l)
Fig. 1. Field emission scanning electron microscopy (FE-SEM) image of Ti-6Al-
1.0 M HCl ml 5–10
4V alloy.

3
M. Kazemi, et al. Surface & Coatings Technology 397 (2020) 126044

Table 5 a result, when the particles reached the substrate surface they had a
Phase analysis of Ti-6Al-4V specimen. high energy and ultimately formed a nano-fine-grained structure. This
Element (W %) Ti V Al nano-structure cannot analytically diffract characteristic peaks in X-ray
diffraction and can be seen as broad peaks which is representative of
Area A (β) 90.2 5.1 4.7 amorphous materials [45–48].
Area B(α) 90.3 3.1 6.6
Moreover, the low nitrogen to titanium ratio in the system resulted
in an over-saturated structure of titanium. This supersaturated structure
under non-equilibrium conditions disrupted the crystalline order and
two specimens (P1, P2) prepared at lower ratios of N2/Ar, no peak was
resulted in the formation of amorphous structure in the coatings
observed and the quasi-amorphous structure was formed. As the PACVD
[49,50]. As the amount of nitrogen increased, the deposition occurred
system is a deposition system that forms a thin layer on the surface of
during the phase transformation and the particle size of the nitride
the substrate at high speed, sometimes elements and compounds do not
phases reaches the level that was detectable by X-ray diffraction, which
find sufficient time to reach the most stable phase state with the lowest
were evaluated according to the standard phase cards of TiN (00-006-
energy level and form amorphous phase [45–47].
0642).
On the other hand, when the amount of nitrogen in the plasma was
In the P3 specimen, a peak was seen at a diffraction angle of 43.1
low, deposition could not take place and it was almost non-reactive. As
which is alluded to the plane (200) of the Ti2N phase (lattice

Fig. 2. (a) X-ray diffraction pattern of the layer specimens labeled with different percentages of nitrogen to titanium, (b) FESEM image of the coating surface of P3,
P4 and P5 specimens.

4
M. Kazemi, et al.
parameters: a=0.4140 nm, c=0.8805) [37]. The P4 specimen con-
sisted of a mixture of Ti2N and TiN phases such that the first peak was
seen at the diffraction angle of 36.8° and belonged to the plane (112) of
the Ti2N phase and the second peak to the plane (200) of the TiN phase.
With further increase in the nitrogen content, the coating was com-
pletely nitrified and in the P5 specimen both diffraction peaks are re-
lated to the TiN phase with the card number of 38-1420 (lattice para-
meters: a=0.2417 nm, c=0.2417). As reported by researchers, the
synthesis of Ti2N synthesis often leads to formation of a combination
other compounds, and the pure Ti2N is difficult to achieve and requires
precise and well controlled conditions [51]. In most studies, XRD
analysis shows only the TiN compound [52].
Investigating the width of the peaks and the slope of the diagrams
implies that the microstructures of the coatings were fine-grained and a
wide range of coatings were in the nano-range. The coatings of speci-
mens P1 and P2 had amorphous structure and did not show crystalline
phase by XRD test. From specimen P3 onwards, crystalline structures
began to form and X-ray diffraction patterns were emerged. Thus,
coatings P3, P4, and P5 had Ti2N, Ti2N+TiN and TiN compounds, re-
spectively. The crystallinity value in the specimen P5 was higher than
the other specimens. According to Fig. 2 (b), the microstructure of the
coatings did not change significantly with the change of N2/Ar ratio and
in all specimens the fine grained structure was observed in the form of
pebble grains. The grain size was also increased with increasing the
nitrogen content in the structure.
The XRD pattern for the Ti-6Al-4V alloy at 2θ of 35.40, 38.50,
40.45, 53.30, 63.55, 71.00, 74.90, 76.80, 78.10, 82.50, 84.95 and,
87.50° showed the peaks which are belong to planes of (100), (002),
(103), (200), (112), (201), (004), (202), (101), (102), (110) and, (104)
of the α-phase (JCPDS file #44-1294) with hexagonal structure, re-
spectively. Also, the diffraction angles of 39.45, 57.00, 71.00 and
82.50° correspond to the planes of (200), (211), (220) and (110) of the
β- please (JCPDS file #44-1288) with a cubic structure [45,53].
According to SEM and XRD results of coated specimens, TiN5 spe-
cimen was selected as the main specimen and then HA coating was
applied on this specimen. Fig. 3 shows the morphology, elemental
analysis, and X-ray diffraction pattern of specimens with HA and HA/
TiN coatings. According to Fig. 3 (a), the HA coating had a spherical
morphology and the particles were non-uniformly algebraic. According
to Fig. 3 (b), EDX spectra confirm the presence of calcium and phos-
phorus with a ratio of 1.68 with an approximate ratio of hydroxyapatite
(1.67), indicating the formation of HA coating on the titanium substrate
[54]. According to Fig. 3 (c), it can be seen that the TiN peak intensity
was decreased which confirms that the TiN layer on the Ti-6Al-4V alloy
was coated with a thick layer of HA. It is also seen in Fig. 3 (d) that the
coating had a fine-grained, crack-free structure, and a fine-grained
microstructure.
Fig. 4 shows the results of the AFM test for the uncoated and coated
specimens. According to the Fig. 4, it was found that the HA/TiN, HA,
TiN and substrate specimens had the highest of minimum values with
roughness of 30.86 ± 0.5 nm, 25.1 ± 0.42 nm, 20.43 ± 0.14 nm and
15.1 ± 0.02 nm, respectively. These results confirm that the HA/TiN
coating with higher roughness had a similar structure with bone and
was capable of accelerating the cell growth which provided a good
adhesion to the substrate and prevented the release of toxic elements
(aluminum and vanadium).
3.1. Potentiodynamic polarization behavior
RP is a factor that determines the corrosion resistance of alloys. This
value is inversely correlated with the corrosion current density.
Therefore, its high values indicate the low corrosion rates. It also in-
dicates that the piece is highly resistant to changes in its equilibrium
state, leading to a low rate of aluminum and vanadium ion release and
oxide growth which can result in a decrease of the current density of the
coating and as a result, the corrosion resistance is enhanced, which
5
Surface & Coatings Technology 397 (2020) 126044
confirms the accuracy of the polarization results.
Fig. 5 shows the EIS curves (Bode, Bode phase and Nyquist curve)
for different layers deposited on the titanium substrate after electro-
chemical impedance test in SBF solution at 37 °C. In Table 6, the values
of the EIS parameters, Resistance solution (RS) and polarization re-
sistance (Rp) are reported which are derived from appropriate equiva-
lent electrical circuits using a stationary phase element [55,56]. It can
be seen from Fig. 5 (a) that the semicircular diameter of the deposited
specimens was larger than that of the raw (uncoated) specimen. It is
obvious that the specimen with HA/TiN coating had a larger semicircle
than the other specimens. In general, the larger diameter of semicircles
in the Nyquist diagram indicates a better corrosion protection [57,58].
From the phase Bode diagram in Fig. 5 (b) for all different surfaces, it
can be inferred that the phase angles tend to be approximately 70°. For
the uncoated Ti-6Al-4V alloy surface (natural metal oxide only), up to a
frequency of about 103 Hz, the impedance phase angle remained close
to 80°. In contrast, the impedance phase angle for Ti-6Al-4V alloy
coated with TiN, HA, HA/TiN had two zones with different behavior in
low frequency and high frequency regions due to the existence of dif-
ferent interfaces [56]. By examining the Bode diagram in Fig. 5 (b), it
can be seen that the linear slope of log (Z) (impedance) vs. log (f)
(frequency) was approximately −1, which is characteristic of a high-
capacity layer [59]. As shown in Fig. 5 (b), this behavior is also char-
acterized by a phase angle of about 90°. The chi-square values de-
termined by ZSimpWin software are usually in the order of 10−3, which
means a good agreement for the curve fitted between the measured and
calculated values by using the equivalent circuits [56,59].
According to the Bode graph, the values of Rs (shown in Table 6) for
the uncoated specimen and the specimens coated with TiN, HA and HA/
TiN coatings were 9.43, 23.21, 26.40 and 49.51, respectively. The po-
larization resistance (Rp) of HA/TiN (3.67) > HA (2.97) > TiN
(1.73) > non-coated alloy surface (0.92) in terms of MΩ cm2 showed
the higher phase impedance (Z) and greater Rp, respectively, in which
the HA/TiN coating was thicker and denser. Its high capacity is dis-
played in Fig. 5 (a) [55,56,59]. This thick and dense feature of HA/TiN
film prevents its dissolution and strengthens the barrier properties
during the EIS test and resulted in a higher polarization resistance in the
SBF solution [60]. Therefore, the present study concludes that the
corrosion resistance of Ti-6Al-4V biological alloy can be significantly
improved by coating HA/TiN through a novel deposition method.
Impedance results should be in accordance with the corrosion
physical model. In general, the equivalent electrical circuits used to
analyze the impedance spectrum can be shown in parallel circuits (RC)
with resistance of R, and capacity of C. Semicircular indentation is often
due to surface heterogeneity because of surface roughness, impurities,
defects in the crystal lattice, fractures, distribution of active sites on the
metal surface, deformation of the porous layer, and adsorption of in-
hibitors [61–63]; so, more constant phase element (CPE) is used in
comparison to the conventional capacitors in equivalent electrical cir-
cuits (Fig. 6). Rct and Rf represent the load transfer resistance and the
coating resistance, respectively. CPE also means frequency distribution
at double layer capacity and Rs is the solution resistance. In fact, such a
deviation from the shape of the perfect circles is due to the hetero-
geneity of the electrode surface. The CPE is used instead of the capa-
citive element to make a more accurate fit with the experimental data.
Moreover, the double layer capacity and coverage capacity are calcu-
lated from Eq. (2) [64–66]:
C = (Y0 × R1 − n)1/ n (2)
C represents the capacity of the double layer or coating capacity, Y0
is the admittance of the CPE (in Sn Ω−1 cm−2), R is the load transfer
resistance or coating resistance, and n is the constant experimental
power associated with surface heterogeneity.
The results of the Table 6 show that the load transfer resistance
increases from non-coated specimen to TiN coated specimen, HA
coating and HA/TiN coating, respectively, which indicates an
M. Kazemi, et al.
Fig. 3. (a) FE-SEM image, (b) EDS analysis of HA-coated alloy, (c) FE-SEM image, (d) XRD of HA/TiN coated alloy.
improvement of the corrosion protection performance. Increasing the
load transfer resistance can increase the tendency of the current to pass
through the capacitor in the circuit.
The polarization diagram of Ti-6Al-4V alloy and various coatings
measured in SBF solution at 37 °C are plotted in Fig. 7. Table 7 shows
the obtained electrochemical parameters in the Simulated Body Solu-
tion (SBF). These values were obtained from polarization curves and
Tafel plots using linear sections of both the cathodic and anodic bran-
ches of the curves [67]. The more adherent the more protective layer is
and the less defects, the less oxygen and metal ions penetration can be
seen, and therefore the current density, which indicates the rate of
corrosion, will be decreased. The corrosion current density of HA/TiN,
HA, TiN coatings and initial titanium specimens were 0.06, 0.12, 0.27
and 1.17 (μA/cm2), respectively, in which HA/TiN coatings had a lower
value than other specimens. Also, the lowest values of I300mV (0.57 μA/
cm2) and Ipass (0.34 μA/cm2) belonged to the HA/TiN composite spe-
cimen and these values were increased for HA coating, TiN coating and
initial titanium specimen, respectively [55,56]. The mechanism of in-
creased corrosion resistance of the TiN-coated substrate can be attrib-
uted to the very low electrical conductivity of these coatings, which
partially prevents the electron transfer from the metal substrate (anode)
to electrolyte (cathode). However, one of the reasons for the decrease in
corrosion resistance by increasing the voltage of the uncoated specimen
6
Surface & Coatings Technology 397 (2020) 126044
compared to the coated specimen can be due to the decrease in the
thickness of the protective coatings, as the increased thickness can
cause defects and porosity in the coating and reduction of coating de-
fects helps to increase its corrosion resistance. On the other hand, in-
creasing the thickness of the HA/TiN layer reduces the electric field
(E=V/d) and consequently decreases the electrical flux (φ=ʃE.dA)
which reduces the corrosion current density, hence the typical corro-
sion current density HA/TiN coating will be less than that of the sub-
strate because of its greater thickness than other specimens. Therefore,
the corrosion resistance of Ti-6Al-4V bio-medical alloy could be im-
proved by forming the HA/TiN composite coatings using novel de-
position methods. The increased corrosion resistance of this type of
dense coating can be attributed to the natural oxide layers such as
Nb2O5, ZrO2, TiO and TiO2 that are formed naturally on the surface
[68–70].
3.2. Assessment of biological behavior in the simulated body fluid (SBF)
The biodegradation and bioactivity of the coatings were measured
in a simulated body fluid and under physiological conditions of the
human body containing a pH of 7.4 at 37 °C. Fig. 8 illustrates the re-
lationship between changes in calcium ion concentration in the simu-
lated body fluid and the type of coatings during different immersion
M. Kazemi, et al.
Fig. 4. AFM test results of (a) substrate, (b) TiN coated, (c) coated with HA, and (d) coated with HA/TiN.
times. Increasing the immersion time of the specimens in simulated
body fluid showed an increasing trend of calcium ion. The rate of in-
crease in calcium ion in the simulated body fluid was dependent on the
type of coating. As is evident, the concentration of calcium in the si-
mulated body solution was higher in the HA/TiN coating specimen.
As can be seen, the concentration of calcium ions in the simulated
solution in the HA/TiN composite specimen was increased as compared
to the TiN and the substrate specimen. On the specimens, the dissolu-
tion of the specimens and the absorption of calcium ions on the spe-
cimen surfaces were increased simultaneously. In fact, the calcium ion
concentration was controlled by both the release of calcium from the
specimen and the formation of apatite [71]. When the specimens are
placed in a simulated body fluid, both dissolution of the specimens and
deposition of the new apatite layer on the specimen surface, occur si-
multaneously [72]. The dissolution and deposition behavior of apatite
are two major factors that control the bioactivity of apatite. It was
found that the formation of hydroxyapatite coating increased the dis-
solution rate of the coating as a result of the increased calcium ion
concentration leading to localized super saturation, which is beneficial
and useful in germination and growth of new apatite crystals. In ad-
dition, with increasing the solubility of the specimens, more germina-
tion sites for new apatite crystals are created. As a result, higher de-
position rates will be obtained in specimens with higher dissolution
rates. The rate of apatite formation determines the bioactivity of the
specimens. The higher rate of apatite formation led to the higher
bioactivity of the specimens.
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Surface & Coatings Technology 397 (2020) 126044
3.3. Evaluation of biological behavior through MTT test
Fig. 9 shows the optical microscopy images of cell growth behavior
and initial adhesion on the surface of primary titanium specimens, TiN
coating, HA coating, HA/TiN composite coating after the MTT test. As
can be seen, the number of cells on the surface of the coated specimens
was higher than that of the original titanium specimen. The attachment
of cells to the surface of the biomaterial is one of the biological prop-
erties of the biomaterial that indicates its biocompatibility. Therefore,
coating specimens had a better bioactive surface in cell growth and
proliferation than the original titanium specimens. In other words, the
coated specimens had a more positive biological effect. As can be seen
in Figs. 9 (c), (d) of the coated specimen, more cells were proliferating,
whereas in the initial titanium specimen, the conditions were different
and the number was smaller. By applying the coating on this titanium,
its biocompatibility was increased due to the biocompatibility of these
coatings and the release of toxic elements from the alloy into the cell
environment was prevented. The results of the cytotoxicity test showed
that the coating of the TiN, HA and HA/TiN composite on this alloy
could make this material a better biocompatible material.
Fig. 10 shows the MTT test results indicating the biocompatibility of
each specimen. According to Fig. 10, the highest biocompatibility (cell
viability and proliferation) was for the HA/TiN specimen and the lowest
amount was obtained for the primary titanium alloy.
In order to obtain the number of cells, the numbers were read ac-
cording to the relationship of 3 and numbers of each specimen were
M. Kazemi, et al. Surface & Coatings Technology 397 (2020) 126044

Fig. 5. (a) Nyquist diagram obtained from the impedance test for coated and uncoated specimens in SBF solution, (b) Bode and (c) Bode phase of EIS diagram for
different layers deposited on Ti-6Al-4V after impedance test in SBF solution At 37 °C.

8
M. Kazemi, et al. Surface & Coatings Technology 397 (2020) 126044

Table 6
The electrochemical parameters obtained from the impedance diagrams for the coated titanium and uncoated specimens, these values are the mean of three
replications and in accordance with ( ± ) the standard deviation.
Specimen RS (Ω·cm2) CPEf Rf nf CPEdl Rct ndl RP
(μF·cm−2·sn-1) (kΩ·cm2) (μF·cm−2·sn-1) (kΩ·cm2) (MΩ·cm2)

Non-coated 9.43 ± 0.7 – – – 176.3 8.9 ± 0.7 0.75 ± 0.01 0.92 ± 0.8
TiN-coated 23.21 ± 0.9 15.2 0.05 ± 0.01 0.74 ± 0.01 216 18.6 ± 0.9 0.73 ± 0.02 1.73 ± 0.11
HA-coated 26.40 ± 14 0.42 0.07 ± 0.01 0.81 ± 0.02 234.4 55.3 ± 14 0.66 ± 0.02 2.97 ± 0.13
HA/TiN-coated 49.51 ± 23.8 0.32 0.41 ± 0.01 0.63 ± 0.01 908 177.7 ± 23.8 0.75 ± 0.01 3.67 ± 0.15

Fig. 6. Equivalent electrical circuits used in order to modeling the data measured in the EIS diagram a) un-coated sample and b) coated sample.

Fig. 7. Specimen polarization diagrams of Ti-6Al-4V alloy and various coatings in SBF solution.

inserted into the X unknown equation derived from the standard slope
equation of cell count and the cell number of each specimen was de-
termined. The calculations are given in Fig. 11.
Y = 22405/62025X–6300/33903 R2 = 0.985
Fig. 11 shows the cell viability in the specimens after 3 days of
culture. As can be seen, the results of this figure are consistent with the
results of the microscopic images of cells and an increase in the bio-
compatibility of the primary titanium alloy after HA, TiN coating as
well as HA/TiN coatings, is observed. According to ISO-10993 Standard
Part 5 [73–75], if the cell viability is above 70% compared to the
(3)
substrate, it can be said that the specimens are non-toxic and bio-
compatible. According to the Fig. 11, biocompatibility of HA/TiN
composite coatings was greater than that of the HA, TiN coatings and

9
M. Kazemi, et al. Surface & Coatings Technology 397 (2020) 126044

Table 7
Electrochemical parameters obtained from the anodic polarization test for different layers deposited on Ti-6Al-4V alloy. These values are the mean of three re-
plications (N=3) and in accordance with ( ± ) the standard deviation for specimens with dimensions of 1 cm × 1 cm.
Treatment Corrosion potential corrosion current density Current density at 300 mV Current density at the passive region
Ecorr(mV) Icorr(μA/cm2) I300mV(μA/cm2) Ipass(μA/cm2)

Non-coated −608 ± 8.609 1.17 ± 0.005 3.71 ± 0.026 3.74 ± 0.018

TiN-coated −469 ± 5.110 0.27 ± 0.004 2.39 ± 0.029 2.46 ± 0. 012
HA-coated −480 ± 4.136 0.12 ± 0.008 0.71 ± 0.003 0.60 ± 0.004
HA/TiN-coated −149 ± 5.110 0.06 ± 0.002 0.57 ± 0.001 0.34 ± 0.004

Fig. 8. Trend of changes in calcium ion content in simulated body fluid during immersion for uncoated, TiN-coated and HA/TiN coated specimens.

Fig. 9. Optical microscopy images of the scatter and shape of cells in the vicinity of the primary titanium alloy specimen. (a) Primary titanium alloy. (b) TiN coating
(c) HA coating (d) HA/TiN coating.

substrate. In general, the biocompatibility of an alloy is influenced by
several factors such as corrosion resistance in the body environment
and the rate of releasing the elements, as well as the non-toxicity of the
constituents of the alloy.
In line with the results and investigations provided, the steps that
can be taken in the next work will be as follows: perform the in-vivo
experiments, and investigation the wear behavior and adhesion
strength by which the coatings can be examined more accurately. Also,
in this paper, the effect of pH, calcination temperature and aging time
on the applied coatings have not been investigated. For future work, the

10
M. Kazemi, et al.
Fig. 10. MTT test results for MG-67 cells after 3 days of culture on the specimens with Standard deviation bars.
Fig. 11. Cell viability of Ti-6Al-4V, TiN coating, HA coating, and HA/TiN nanostructured coating with Standard deviation bars.
effect of adding other nanoparticles (for example, silver or Sic nano-
particles) on different properties of the coating will be investigated, and
the effect of antibacterial properties of the coating using different
methods including bacterial culture will be studied, and the wetting
amount of the hydroxyapatite composite coating will be perused.
4. Conclusion
The purpose of the present study was to investigate the bio-
compatibility and corrosion properties of HA/TiN multilayer composite
coating deposited on Ti-6Al-4V alloy using different analytical methods
(FE-SEM, AFM, EDS, XRD, potentiodynamic polarization and electro-
chemical impedance), in which the PACVD method was used to coat
TiN and sol-gel method was applied to create the hydroxyapatite
coating, and the following results were obtained:
• X-ray diffraction studies showed that the phase structure of the
coatings is changed with increasing the N2/Ar ratio from amorphous
to single phase Ti2N, then a combination of TiN and Ti2N biphasic is
created and finally reaches the TiN stoichiometric structure (N2/
Ar=4) and the specimen containing TiN single-phase compounds
performed better than other specimens.
• EDX results confirmed the presence of calcium and phosphorus in
the HA coating with a ratio of 1.68 which is close to a stoichiometric
ratio (Ca/P=1.67).
• The FE-SEM results indicated that the HA/TiN coating had a finer,
non-cracking structure than the other coatings, and this fine-grained
microstructure led to a high adhesion strength of the coating to the
substrate.
11
Surface & Coatings Technology 397 (2020) 126044
• AFM results demonstrated that the HA/TiN coating with higher
roughness had a similar structure with bone and was capable of
accelerating the growth compared with HA, TiN and substrate spe-
cimens, respectively.
• The corrosion parameter from the potentiodynamic polarization
curves signified that the corrosion resistance (Ecorr, Icorr, I300 and
Ipass) was lower for HA/TiN coatings in comparison with other
specimens. As well, HA/TiN coating had a higher Rp than other
specimens.
• Finally, raising the immersion time in SBF solution led to an increase
in the amount of calcium ion on the surface of HA/TiN. Also, the
results of biomass evaluation by MTT test displayed that the highest
biocompatibility (surviving cell) belonged to HA/TiN coating and
the lowest amount of primary titanium alloy.
CRediT authorship contribution statement
Maryam Kazemi: Investigation, Writing - original draft, Writing
review & editing.Shahrokh Ahangarani: Conceptualization,
Funding acquisition, Investigation, Project administration, Writing -
review & editing. Mohammad Esmailian: Investigation. Ali
Shanaghi: investigation, Writing - original draft.
Declaration of competing interest
The authors declare that there is no conflict of interests regarding
the publication of this paper.
M. Kazemi, et al.
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