Applied Surface Science 401 (2017) 172–180

Contents lists available at ScienceDirect

Applied Surface Science

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

Full Length Article

Structural and corrosion characterization of

hydroxyapatite/zirconium nitride-coated AZ91 magnesium alloy by
ion beam sputtering
Seyed Rahim Kiahosseini a,∗ , Abdollah Afshar b , Majid Mojtahedzadeh Larijani c ,
Mardali Yousefpour d
a
Young Researchers and Elite Club, Damghan Branch, Islamic Azad University, Damghan, Iran
b
Department of Material Science and Engineering, Sharif University of Technology, Tehran, Iran
c
Radiation Applications Research School, Nuclear Science and Technology Research Institute, Tehran, Iran
d
Faculty of Materials and Metallurgical Engineering, Semnan University, Semnan, 35131-19111, Iran

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

Article history: The adhesion of hydroxyapatite (HA) as a coating for the AZ91 magnesium alloy substrate can be improved
Received 11 December 2016 by using the sputtering method and an intermediate layer, such as ZrN. In this study, HA coatings were
Received in revised form applied on ZrN intermediate layers at a temperature of 300 ◦ C for 180, 240, 300, 360, and 420 min by
30 December 2016
ion beam sputtering. A profilometer device was used to study the HA coating thickness, which changed
Accepted 3 January 2017
from 2 ␮m for the 180-min deposition to 4.7 ␮m for 420-min deposition. The grazing incidence X-ray
Available online 4 January 2017
diffraction analysis method and the Williamson–Hall analysis were used for structural investigation.
As the deposition time increased, the crystalline size increased from 50 nm to 690 nm. However, given
Keywords:
Structural properties
sufficient time for stress relief on the coating structure, the lattice strain values were close to zero.
Microstrain Energy-dispersive X-ray spectroscopy results showed that the Ca/P ratio ranged from 1.73 to 1.81. The
Adhesion external indentation method was used to evaluate the coating adhesion to the substrate. The slope of
Corrosion curve for applied force changes versus the radius of cracks in the coating (dP/dr) varied in the range
of 0.2–0.07 by the deposition time, indicating that the adhesion increased with the increase in coating
thickness. The potentiodynamic polarization technique was used to study the corrosion behavior. With
increasing deposition time, the corrosion potential of samples did not show a significant change, and the
corrosion potential of all samples (coated and uncoated substrates) was more positive than approximately
55 mV. When the deposition time increased to 360 min, the corrosion current density decreased from
5.5 ␮A/cm2 to 0.33 ␮A/cm2 . After 420 min of deposition, the current density increased to 8.2 ␮A/cm2 .
Scanning electron microscopy images of the HA surface layer after 420 min clearly showed cracks on the
coating surface, which led to the increase in corrosion current density.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Magnesium (Mg) is a lightweight metal industries [1–6], and
its alloys have high strength of approximately 480 GPa/g/cm3 [7].
Mg and its alloys as biomaterials [8,9] are not only nontoxic, they
can also reduce the risks of blood pressure and heart problems.
Mg ion is needed for the body and can be effective in improving
bone tissue [10]. Calcium phosphate also has excellent biocompat-
∗ Corresponding author.
E-mail addresses: rkiahoseyni@yahoo.com, r.kiahosseini@damghaniau.ac.ir
(S.R. Kiahosseini).
ibility with human bones [11]. The substance has rapid biological
response, improves the adhesion between bone and implant, and
is a suitable support material for bone growth [12–14]. The main
ingredient of bones and teeth is hydroxyapatite (HA) in the compo-
sition of Ca5 (po4 )3 OH or Ca10 (po4 )6 (OH)2 [15–17]. HA has chemical
and crystallographic similarity to natural bone mineral compo-
sition; [18] thus, this material is suitable for dental and medical
implants [12,19]. The ideal planting materials are made from this
material. However, calcium phosphate in bulk form is weak and
brittle, making it inappropriate for replacing body parts. For exam-
ple, high stress, which is difficult to tolerate, is applied to the teeth.
As a result, metallic implant materials with adequate strength
should be covered with calcium phosphate to ensure mechanical

http://dx.doi.org/10.1016/j.apsusc.2017.01.022
0169-4332/© 2017 Elsevier B.V. All rights reserved.
 S.R. Kiahosseini et al. / Applied Surface Science 401 (2017) 172–180 173

strength in combination with the biological properties of calcium 5.5

Exprimental Data
phosphate [15]. HA coating improves the corrosion resistance of
5.0 Fitted by Software
implants [20–23]. The plasma spray-coating method is an econom- a
ical method to create HA layers. Results of in vivo coating produced b
4.5
in this way have shown that the HA coating adhesion is not good and
c
can rapidly corrode and experience damage because of its amor-

Thickness ( m)
4.0
phous structure [24–27]. Balaceanu et al. [28] suggested that an
intermediate layer between the substrate and the outer layer influ- 3.5
ences the behavior of the main coating adhesion. In the current
3.0
research, the sputtering deposition method is used, because it eas-
d
ily controls the coating thickness and can achieve uniform coating
2.5
with better adhesion [25]. In our previous research, ZrN coating was
e
deposited on AZ91 magnesium alloy by ion beam sputtering, thus 2.0
creating optimal conditions by mechanism of mismatch and inter-
facial micro-strain reduction to ensure good adhesion between ZrN 1.5
150 200 250 300 350 400 450
film and substrate [29].
Sputtering time (min)

Fig. 1. HA coating thickness variations versus sputtering time curve for deposition
at 300 ◦ C. The bars show mean (n = 5) ± SD. Different letters on the bars represent
2. Experimental the significant difference at 5% level of probability.

In this study, an AZ91 magnesium alloy with 10 × 10 × 3 mm3 3. Results and discussion
dimension was used as the substrate. For 1 h, the substrate was
subjected to sanding and degreasing by alcohol and an ultra- The HA coating thickness versus sputtering time is shown in
sonic treatment in a mixture of ethyl alcohol and acetone. The ion Fig. 1. This behavior was extracted using “CurveExpert” software
beam-sputtering method was used for coating deposition. Before with R2 = 0.999. Thickness is expressed as
conducting the HA deposition, ZrN coating was optimized in a lab- t 
oratory by changing such parameters as time, temperature, and T =˛+ , (1)
 + t 
N2/(Ar + N2). Thus, the ZrN intermediate layer with 1 ␮m thick-
ness was deposited on the samples using the following optimal where T is the film thickness;,,␣, and  are constants; and t is the
conditions: initial vacuum of 2.3 × 10−3 Pa, working pressure of sputtering time. At 180 min of deposition, the mobility of atoms
8.5 × 10−3 Pa, deposition time of 120 min at 400 ◦ C, and ionized deposited on the substrate surface has adequate energy to link
gas in N2/(Ar + N2) = %50. HA depositions were then performed on together, and the initial grains for island shape are developed. Given
the ZrN, with initial vacuum of 2.3 × 10−3 Pa, working pressure that the atoms deposited on the surface have considerable energy,
of 1.6 × 10−3 Pa, and deposition times of 180, 240, 300, 360, and a number of them are not stable and can leave the surface. Until
420 min at 300 ◦ C. After the depositions, the HA coating thick- 240 min, the film growth rate is low. Once the thickness and the
nesses were measured using a mechanical Profilometer model formation of stable grains are subjected to 360 min of deposition,
Dektak 3. The crystal structures of the coatings were investigated energetic atoms penetrate and reach the necessary conditions for
by the grazing incidence X-ray diffraction (GIXRD) technique. The growing grains, which can increase the growth rate of the layer. In
energy-dispersive X-ray spectroscopy (EDS) analyzer installed on longer times, growing grains collide, and their growth is limited. In
a scanning electron microscope (SEM) was used for HA coating other words, the potential energy for grain growth is insufficient,
composition analysis. The coating adhesion to the substrate was thus reducing the coating thickness. Logothetidis [31] reported the
evaluated using a Rockwell hardness machine. In this method, reduction of growth rates by increasing the coating thickness for
the slope of curve for applied force changes versus the radius of carbon coatings produced by radio frequency magnetron sputter-
cracks in the coating (dP/dr) is proportional to adhesion. Details ing at different times.
are reported in the paper of Kim [30]. In this way, different forces
and crack on the coating were created using the Rockwell hardness
indenter.
Owing to the differences in the coating elastic modulus and
soft substrates, cracks occurred around the indentation region. The
chart of crack radius (r) versus power (P) can be drawn by measur-
ing the radius of cracks caused by the different forces. The fitted line
slope is inversely related to the film adhesion to the substrate [30].
In the current study, the potentiodynamic polarization method was
used to investigate the corrosion behavior of samples. All studies
were performed in Ringer’s solution. The counter electrode used
was a platinum rod with a diameter of 2 mm and a length of 40 mm;
a saturated calomel electrode was used as the reference electrode.
After 1 h of immersion, potentiodynamic polarization was per-
formed, with 1 mV/s scan rate in the potential range of −100 mV
to +540 mV versus open-circuit potential. After the corrosion test,
the coating surface of samples was observed using a field emission
SEM. ANOVA and Tukey’s Post Hoc tests were used to compare the
means of the thickness and dp/dr behavior of deposited film at 5%
significance level. Fig. 2. Coating cross section from the sample deposited at 300 ◦ C for 300 min.
174 S.R. Kiahosseini et al. / Applied Surface Science 401 (2017) 172–180

Mg HA ZrN PDF2:01-084-0814
420min

360min

300min
Intensity (a.u.)

240min

180min

AZ91/ZrN

AZ91

20 25 30 35 40 45 50 55 60 65 70 75 80
Fig. 4. Williamson–Hall curves from the XRD of HA coatings deposited at 300 ◦ C and
at different times.
2Theta
(* The curve of the sample deposited for 180 min is not shown given a high slope.)

Fig. 3. XRD patterns of the substrate AZ91, ZrN, and HA coatings deposited at 300 ◦ C
for a) 180, b) 240, c) 300, d) 360, and e) 420 min. 0.8
Experimental
0.7 Fitted Curve
The cross-section image from the coating is shown in Fig. 2, in
which HA is deposited at 300 ◦ C for 300 min. The impossibility of
0.6
separating the grains in these images shows that the grain size is
Crystallite size( m)

very fine and has a compact and uniform distribution.

0.5
Fig. 3 shows the results of GIXRD from coatings created at
different deposition times. According to the PDF2: 01-084-0814 0.4
standard, the dominated peaks are related to the composition of
HA with the hexagonal structure shown in the curve. The crystalline 0.3
structure of the sample deposited for 180 min has a broad peak that
shows the behavior of the nano structure. With increasing time and 0.2
thicker coating, the peak intensity increases, which shows that the
crystallinity is improved. In addition, the peak intensity of the ZrN 0.1
intermediate coating is reduced by increasing the HA thickness.
Fig. 4 shows the results of the X-ray diffraction (XRD) analysis 0.0
of HA coatings using the Williamson–Hall relationship [29,32] to 150 180 210 240 270 300 330 360 390 420 450
determine the grain size and crystal strain (Eq. (2)) as expressed by
Sputtering time (min)
 0.9 2
2
(K) = + 4e2 K2 , (2) Fig. 5. Curve of HA coating crystallite size versus deposition time at 300 ◦ C.
DWH

where K = 2cos ␪␤C /␭, ␤C is the peak full width at half maximum,
␪ is the Bragg angle, ␭ is the wavelength of the radiation Cu K␣
(1.54 Å), K = 2sin ␪/␭, e is the strain of coating network, and DWH
is the average crystallite size. The curve of the sample deposited
for 180 min has a near-infinite slope resulting from the dominated
nano structure in HA coating for this sample. Therefore, the analysis
of this sample is done only to refer to coating with very fine grains,
and the line of the Williamson–Hall method is not shown in Fig. 4.
The lines related to other samples have a positive slope, thereby
demonstrating a tensile strain in the HA crystal lattice.
Fig. 5 shows the changes in crystal size compared with the
HA deposition time. The study conducted using the CurveExpert
software indicates that the relationship between grain size and
deposition time follows the relation D = a + bt + ct2 + dt3 + et4 , where
a, b, c, and d are constants; D is the crystallite size; and t is
the deposition time. The minimum and maximum grain sizes are
approximately 0.06 and 0.6 ␮m that have been created at 180 and
420 min deposition time, respectively. With increasing deposition
time, more particles are deposited on the substrate surface, and
more time is available for atom diffusion for crystal growth on
the surface. Considering that the substrate temperature at 300 ◦ C
is sufficient for atom diffusion to coat grains, deposition time is
expected to have a direct effect on crystal size at constant temper-
ature. According to Eq. (3), the grain size is directly related to the
heat treatment time[33], as expressed by
D − D0 = Kt n , (3)
where D is the average grain size, D0 is the primary grain size, K is a
constant dependent on temperature, t is the time, and n is equal to
the slope of logD-logt curve. Given that the deposition is performed
at temperatures higher than room temperature, we expect that the
grains are coarser with increasing deposition time.
Lin et al. [34] reported that if the ratio of thickness to grain
size is very high, then the grain growth is independent on coat-
ing growth. In the present study, the thickness is approximately
 S.R. Kiahosseini et al. / Applied Surface Science 401 (2017) 172–180 175

5 ␮m compared with the maximu was studied by for NiO-sputtered 0.025

Experimental Data
coating.
Fitted by Software
The lattice microstrain changes versus deposition time are
0.020
shown in Fig. 6. The amounts of network microstrain reduce
to approximately zero by increasing the deposition time. With
increasing deposition time, annealing occurs simultaneously in the

Microstrain
0.015
deposited layers; as a result, stress relief occurs [35], reducing the
residual strain in the film. According to the research of Wieder,
lattice parameter and microstrain are related to each other by [36] 0.010

D (hkl) = D0 (hkl) + ε (hkl) D0 (hkl) , (4)

0.005
where D0 (hkl) is the (hkl) plane distance in a state without strain
that is equal to the lattice parameter, D(hkl) is the (hkl) plane dis-
tance in the study situation with microstrain, and ε (hkl) is the 0.000
150 180 210 240 270 300 330 360 390 420 450
lattice microstrain for (hkl) planes. Therefore, the lattice param-
eter changes and tends toward standard values by increasing the Sputtering time(min)
deposition time. When the lattice microstrain tends to zero, the HA
crystal lattice parameters are close to the standard structure with- Fig. 6. Lattice microstrain for HA coating versus deposition temperature at 300 ◦ C.

out tension. However, according to the fitted curve by CurveExpert

software, the curve slope at 420 min deposition is positive. This
result suggests that the stress increases in HA coating because of The results of the EDS analysis of HA coatings deposited at 300◦ C
the thickness increment and grain growing interaction with others. for 180 min are shown in Fig. 7. The calcium and phosphorus peaks
This phenomenon can cause cracks in the cover. are visible in this image.

Fig. 7. Results of a) SEM micrograph and b) EDS for HA coatings deposited at 300 ◦ C for 180 min (HV = 15.00 kV).
176 S.R. Kiahosseini et al. / Applied Surface Science 401 (2017) 172–180

Table 1 0.24
Weight percent of calcium and phosphorus ratio in HA coatings created by ion beam
sputtering at 300 ◦ C for different times. 0.22
a a
Deposition time (min) Ca (at.%) P (at.%) Ca/P ratio 0.20
180 14.33 7.90 1.81
240 22.91 12.93 1.77 0.18
300 29.25 16.65 1.76
360 28.56 16.48 1.73
0.16

dP/dr
420 27.62 15.73 1.76
0.14
0.12 b
2600 180 min c
240 min 0.10
2400 180min
300 min 0.08 d
2200 360 min
2000 420 min 300min 0.06
1800 240min
Crack Radius (µm)

0.04
1600 150 200 250 300 350 400 450
420min
1400 360min
Sputtering Time(min)
1200
1000
800
600
400 Fig. 9. dp/dr versus HA coating adhesion at 300 ◦ C for different deposition times. The
200 bars show mean (n = 5) ± SD. Different letters on the bars represent the significant
difference at 5% level of probability.
20 40 60 80 100 120 140 160

Indentation force(kg)
-1.35
Fig. 8. HA coating crack radius curves versus indentation force for 300 ◦ C deposition
temperature at different times.
-1.40

The EDS values obtained from the ZrN/HA coated at different

-1.45
Potential(V. vs. SCE)

times are shown in Table 1. As can be seen, the Ca/P ratio for HA
coatings ranges from 1.73 to 1.81. In sputtering methods, HA coat- AZ91/ZrN
420min
ing with stoichiometric composition is difficult to deposit [37–40]. 360min
-1.50 240min
This phenomenon is a result of two factors: the phosphorus atomic
300min
mass is lower than that of calcium during deposition on AZ91, and
AZ91
the resputtering and vaporization for phosphorus are more signifi- -1.55
cant than those for calcium atoms. However, the sputtering method
is considered because of its uniform coating with better adhesion 180min
compared with other methods. -1.60
The radius of film cracks around the indentation region by a
hardness tester is shown in Fig. 8. The results of the adhesion anal-
-1.65
ysis of HA coatings produced at different deposition times are given -9.5-9.0-8.5-8.0-7.5-7.0-6.5-6.0-5.5-5.0-4.5-4.0-3.5-3.0-2.5-2.0
in Fig. 9. Fig. 8 shows that the dp/dr ratio increases along with
logi(A/cm )
2
increased deposition time. Considering that dp/dr is directly related
to adhesion, the coating adhesion to the substrate is increased with
increasing deposition time. Although the increase in coating thick- Fig. 10. Potentiodynamic polarization curves of the HA/ZrN-coated AZ91 deposited
at 300 ◦ C for different times in Ringer’s solution.
ness reduces film adhesion, various mechanisms, such as chemical
bonding and mechanical locks, can improve adhesion behavior
[41]; therefore, mechanisms should be prioritized. Residual stress
and strain are the most important factors in reducing adhesion The potentiodynamic polarization curves for evaluating the cor-
to the substrate [42]. This contradictory behavior may be caused rosion behavior of the HA/ZrN-coated AZ91 samples in Ringer’s
by the residual strain reduction in the HA coating and resulting solution are shown in Fig. 10. As can be seen, in all cases, no passive
chemical reaction, which leads to the formation of chemical bonds behavior is created.
between HA and ZrN coatings. As shown in Fig. 6, with increasing The results of potentiodynamic polarization curves are shown
deposition time, the microstrain on the HA network is decreased, in Fig. 11. The corrosion potential of samples with increasing depo-
which effectively improves adhesion behavior. The XRD curves sition time does not show significant changes. The potential of
obtained from HA coatings imply that, with increasing deposition coated samples is approximately 55 mV more positive than that
time, the intensity of peaks becomes higher owing to the higher of uncoated substrate, thereby indicating the presence of microp-
coating crystallinity. These results show that at a long deposition orosity and crystallographic defects in coatings. Corrosion potential
time, the particles have sufficient time to migrate to appropriate is a thermodynamic parameter [43,44]. Consequently, these results
sites and form crystalline grains, which can affect the microstrain indicate that corrosion occurs under coatings or on the surface of
in crystals and improve the film adhesion. the AZ91 substrate. Small holes and coating defects act as active
 S.R. Kiahosseini et al. / Applied Surface Science 401 (2017) 172–180 177

-1.20
-1.24 Experimental Data
-1.28 Fitted Curve
------ AZ91 Substrate
-1.32
-1.36
-1.40

ECorr(V vs. SCE)

-1.44
-1.48
-1.52
-1.56
-1.60
-1.64
AZ91 Corrosion Potential
-1.68
-1.72
-1.76
-1.80
150 200 250 300 350 400 450
Sputtering Time (min)

Fig. 11. Corrosion potential change curves of the HA/ZrN-coated AZ91 at a HA deposition temperature of 300 ◦ C and different times in Ringer’s solution.

26
24
22
AZ91 Current Density
20
18
icorr(µA/cm2)

16
14
AZ91/ZrN Current Density
12
10
8
6 Experimental Data
Fitted by Software
4
2
0
150 200 250 300 350 400 450

Sputtering Time(min)

Fig. 12. Corrosion current density change curves of the HA/ZrN-coated AZ91 at a HA deposition temperature of 300 ◦ C and different times in Ringer’s solution.

routes, through which the corrosive solution can pass through and
reach the substrate surface. The corrosion potential of coated sam-
ples becomes very close to the corrosion potential of the uncoated
AZ91.
Fig. 12 shows that the corrosion current density decreases
by increasing the deposition time to 360 min, thereby indicating
improvement in corrosion behavior. According to the results of
the corrosion potential, the reduced corrosion current density until
360 min is a result of the increased thickness and reduced defects in
the HA layer. In 420-min deposition, the corrosion current density
increases again.
The SEM of corrosion areas is shown in Fig. 13. The corrosion
rate of the sample treated for 180 min by HA coating is higher than
the corrosion rates of other samples. In this sample, owing to the
lack of coating uniformity, corrosion occurs in the areas where cov-
erage is weaker. Other areas are damaged as a result of the solution
penetrating the weaker areas in the intersection of the coating and
substrate. Generally, the compact and uniform coatings have more
resistance to corrosive agents [45]. For other samples, the corro-
sion rate is reduced by increasing the thickness and uniformity of
coating after a 360-min deposition. However, when the sample is
deposited for 420 min, corrosion occurs in preferential pathways.
This path can come in the form of microcracks, grain boundaries,
and pathways grown under internal tension. Fig. 13-e shows the
cracks that can be clearly observed on the surface can increase the
corrosion current density.
Meanwhile, Fig. 14 shows the optical microscope image from
the AZ91 surface after etching in Nital solution for 5 s. Investiga-
tions carried out using the “ImageJ” software show that the average
grain size of the AZ91 is approximately 40 ␮m, which is larger than
the gradation shown in Fig. 13, which is approximately 4 ␮m. The
images in Fig. 13 do not show the AZ91 grains, although they indi-
cate the coating surface that has gone through corrosive agents at
the grain boundaries and preferred routes.
4. Conclusion
ZrN coating with a thickness of 1 ␮m was created on an
AZ91alloy, and HA coating was then created at a temperature of
300 ◦ C for 180, 240, 300, 360, and 420 min by ion beam sputtering.
178 S.R. Kiahosseini et al. / Applied Surface Science 401 (2017) 172–180

Fig. 13. Scanning electron microscopy images of HA coatings corroded surface deposited at 300◦ C for different deposition times, a) 180 min, b) 240 min, c) 300 min d) 360 min
and e) 420 min.

The particles accumulated on the surface increased with increas-
ing deposition time. The coating thickness therefore changed from
2 ␮m to 4.7 ␮m. However, the three-dimensional grain growth
reduced the growth rate. The structural study conducted using
GIXRD indicated that the HA had a hexagonal structure. The
Williamson–Hall analysis of the results showed that the crystallite
size increased from 50 nm to 690 nm, and that the lattice micros-
train was reduced to nearly zero with increasing deposition time.
The deposition at 300 ◦ C might lead to stress relief and least net-
work strain of crystals with increasing sputtering time. Owing to
the mobility of atoms at 300 ◦ C, particles might also escape from
the surface.
Meanwhile, the EDS results showed that the Ca/P ratio ranged
from 1.7 to 1.8, which was less than the HA stoichiometric amount
 S.R. Kiahosseini et al. / Applied Surface Science 401 (2017) 172–180
Fig. 14. Optical microscope image from AZ91 grains after etching in Nital solution
for 5 s.
of 1.67. With the particle mobility, increased stress relief, and
reduced microstrain on the network by increasing the coating time,
the ratio of dP/dr as a measure of comparison for the coating
adhesion ranged from 0.2 to 0.07, indicating improvement in sub-
strate adhesion. Increased adhesion until 360 min deposition time
effectively improved the corrosion behavior. At a longer time, the
corrosion potential in all samples became 55 mV more positive than
that for AZ91, because of the increase in the layer thickness and
the formation of cracks. Nevertheless, the corrosion current den-
sity for samples deposited for 360 min reduced from 5.5 ␮A/cm2 to
0.33 ␮A/cm2 , and that for samples deposited for 420 min increased
to 8.2 ␮A/cm2 .
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2017.01.
022.
References
[1] R.-c. Zeng, Y. Hu, F. Zhang, Y.-d. Huang, Z.-l. Wang, S.-q. Li, E.-h. Han, Corrosion
resistance of cerium-doped zinc calcium phosphate chemical conversion
coatings on AZ31 magnesium alloy, Trans. Nonferrous Met. Soc. China 26
(2016) 472–483.
[2] D. Shen, H. Ma, C. Guo, J. Cai, G. Li, D. He, Q. Yang, Effect of cerium and
lanthanum additives on plasma electrolytic oxidation of AZ31 magnesium
alloy, J. Rare Earths 31 (2013) 1208–1213.
[3] C.H. Chang, C.M. Lee, J.P. Chu, P.K. Liaw, S.C.J. Jang, Fatigue property
improvements of ZK60 magnesium alloy: Effects of thin film metallic glass,
Thin Solid Films 616 (2016) 431–436.
[4] W. Jin, G. Wu, P. Li, P.K. Chu, Improved corrosion resistance of Mg-Y-RE alloy
coated with niobium nitride, Thin Solid Films 572 (2014) 85–90.
[5] X. Li, X. Liu, S. Wu, K.W.K. Yeung, Y. Zheng, P.K. Chu, Design of magnesium
alloys with controllable degradation for biomedical implants: from bulk to
surface, Acta Biomater. (2016) (in press).
[6] J. Zhang, H. Huang, C. Yang, Effects of hot ring forging on microstructure,
texture and mechanical properties of AZ31 magnesium alloy, Mater. Sci. Eng.
A 679 (2017) 20–27.
[7] S.R. Kiahosseini, A. Afshar, M.M. Larijani, M. Yousefpour, Electrochemical
evaluation of hydroxyapatite/ZrN coated magnesium biodegradable alloy in
ringer solution as a simulated body fluid, J. Chem. Health Risks 5 (2015) 45–53.
[8] J. Hu, G. Shaokang, C. Zhang, C. Ren, C. Wen, Z. Zeng, L. Peng, Corrosion
protection of AZ31 magnesium alloy by a TiO2 coating prepared by LPD
method, Surf. Coat. Technol. 203 (2009) 2017–2020.
[9] J. Hu, C. Zhang, B. Cui, K. Bai, S. Guan, L. Wang, S. Zhu, In vitro degradation of
AZ31 magnesium alloy coated with nano TiO2 film by sol–gel method, Appl.
Surf. Sci. 257 (2011) 8772–8777.
[10] C. Wen, S. Guan, L. Peng, C. Ren, X. Wang, Z. Hu, Characterization and
degradation behavior of AZ31 alloy surface modified by bone-like
179
hydroxyapatite for implant applications, Appl. Surf. Sci. 255 (2009)
6433–6438.
[11] H. Tang, Y. Han, T. Wu, W. Tao, X. Jian, Y. Wu, F. Xu, Synthesis and properties
of hydroxyapatite-containing coating on AZ31 magnesium alloy by micro-arc
oxidation, Appl. Surf. Sci. 400 (2016) 391–404.
[12] H. Li, Z.X. Li, H. Li, Y.Z. Wu, Q. Wei, Characterization of plasma sprayed
hydroxyapatite/ZrO2 graded coating, Mater. Des. 30 (2009) 3920–3924.
[13] Q. Yuan, T.D. Golden, Electrochemical study of hydroxyapatite coatings on
stainless steel substrates, Thin Solid Films 518 (2009) 55–60.
[14] C. Vasilescu, S.I. Drob, J. Hmeljak, A. Coer, J.M.C. Moreno, Long-term corrosion
behavior and biocompatibility testing of titanium-based alloy covered with
nano-crystalline hydroxyapatite, Mater. Corros. 66 (2015) 562–572.
[15] B. Leoı́n, A. Jansen, Thin Calcium Phosphate Coatings for Medical Implants,
Springer, New York, 2009.
[16] M. Mirak, M. Alizadeh, M. Ghaffari, M.N. Ashtiani, Characterization,
mechanical properties and corrosion resistance of biocompatible Zn-HA/TiO2
nanocomposite coatings, J. Mech. Behav. Biomed. Mater. 62 (2016) 282–290.
[17] R. Chelariu, D. Mareci, G. Bolat, C.A. Peptu, D. Cailean, Electrochemical
characterization of surface modification for Ti6Al7Nb implants with
hydroxyapatite–zirconia nanoparticles synthesis by ultrasound irradiations,
Mater. Corros. 66 (2015) 573–578.
[18] Y. Liu, S. Kim, J.A. McLeod, J. Li, X. Guo, T.-K. Sham, L. Liu, The effect of crystal
structure of TiO2 nanotubes on the formation of calcium phosphate coatings
during biomimetic deposition, Appl. Surf. Sci. 396 (2016) 1212–1219.
[19] M. Yousefpour, A. Afshar, X. Yang, X. Li, B. Yang, Y. Wu, J. Chen, X. Zhang,
Nano-crystalline growth of electrochemically deposited apatite coating on
pure titanium, J. Electroanal. Chem. 589 (2006) 96–105.
[20] Z.C. Yan, Z.R. Cheng, L.C. Long, G.J. Cheng, Comparison of calsium phosphate
coating on Mg-Al and Mg-Ca alloy and their corrosion behavior in Hank’s
solution, Surf. Coat. Technol. 24 (2010) 3636–3640.
[21] M.A. Surmenev, R.A. Surmenev, Microstructure characterization and corrosion
behaviour of a nano-hydroxyapatite coating deposited on AZ31 magnesium
alloy using radio frequency magnetron sputtering, Vacuum 117 (2015) 60–62.
[22] A.M. Ribeiro, A.C. Alves, F.S. Silva, F. Toptan, Electrochemical characterization
of hot pressed CoCrMo–HAP biocomposite in a physiological solution, Mater.
Corros. 66 (2015) 790–795.
[23] L.-L. Chen, Y.-H. Gu, F. Chen, W. Yue, H.-D. Wang, L. Zhang, Influence of HA in
the electrolyte on the properties and corrosion behavior of MAO Ca/P coating,
Mater. Corros. 67 (2016) 702–709.
[24] M. Javidi, S. Javadpour, M.E. Bahrololoom, J. Ma, Electrophoretic deposition of
natural hydroxyapatite on medical grade 316L stainless steel, Mater. Sci. Eng.
28 (2008) 1509–1515.
[25] G. Socola, A.M. Macoveib, F. Miroiua, N. Stefana, L. Dutaa, G. Dorciomana, I.N.
Mihailescua, S.M. Petrescub, G.E. Stanc, D.A. Marcovc, A. Chiriacd, I. Poeata,
Hydroxyapatite thin films synthesized by pulsed laser deposition and
magnetron sputtering on PMMA substrates for medical applications, Mater.
Sci. Eng. B 169 (2010) 159–168.
[26] L. Song, L. Gan, Y.F. Xiao, Y. Wu, F. Wu, Z.W. Gu, Antibacterial
hydroxyapatite/chitosan complex coatings with superior osteoblastic cell
response, Mater. Lett. 65 (2011) 974–977.
[27] Q.-G. Fu, C.-G. Gu, H.-J. Li, Y.-H. Chu, J.-H. Lu, L.-L. Zhang, Microstructure and
mechanical properties of SiC nanowires reinforced hydroxyapatite coating on
carbon/carbon composites, Mater. Sci. Eng. A 563 (2013) 133–137.
[28] M. Balaceanu, V. Braic, M. Braic, A. Kiss, C.N. Zoita, A. Vladescu, P. Drob, C.
Vasilescu, D. Dudu, O. Muresanu, Structural, mechanical and corrosion
properties of TiOxNy/ZrOxNy multilayer coatings, Surf. Coat. Technol. 202
(2008) 2384–2388.
[29] S.R. Kiahosseini, A. Afshar, M.M. Larijani, M. Yousefpour, Adhesion,
microstrain, and corrosion behavior of ZrN-coated AZ91 alloy as a function of
temperature, J. Mater. Res. 28 (2013) 2709–2714.
[30] J.-J. Kim, J.-h. Jeong, K.-R. Lee, D. Kwon, A new indentation cracking method
for evaluating interfacial adhesion energy of hard films, Thin Solid Films 441
(2003) 172–179.
[31] S. Logothetidis, Surface and interface properties of amorphous carbon layers
on rigid and flexible substrates, Thin Solid Films 482 (2005).
[32] M. Kalita, K. Deka, J. Das, N. Hazarika, P. Dey, R. Das, S. Paul, T. Sarmah, B.
Sarma, X-ray diffraction line profile analysis of chemically synthesized lead
sulphide nanocrystals, Mater. Lett. 87 (2012) 84–86.
[33] F.X. Gil, D. Rodriguez, J.A. Planell, Grain growth kinetics of pure titanium,
Scripta Metall. Mater. 33 (1995) 1361–1366.
[34] S.-S. Lin, J.-L. Huang, S. ajgalik, Effects of substrate temperature on the
properties of heavily Al-doped ZnO films by simultaneous r.f. and d.c.
magnetron sputtering, Surf. Coat. Technol. 190 (2005) 39–47.
[35] H.-L. Chen, Y.-M. Lu, W.-S. Hwang, Effect of film thickness on structural and
electrical properties of sputter-deposited nickel oxide films, Mater. Trans. 46
(2005) 872–879.
[36] T. Wieder, WVM: A computer program for the determination of lattice
parameters and strains in thin films, Comput. Phys. Commun. 96 (1996)
53–60.
[37] T.F. Stoica, C. Morosanu, A. Slav, T. Stoica, P. Osiceanu, C. Anastasescu, M.
Gartner, M. Zaharesc, Hydroxyapatite films obtained by sol–gel and
sputtering, Thin Solid Films 516 (2008) 8112–8116.
[38] K.v. Dijk, H.G. Schaeken, C.M. Maree, l. Verhoeven, l. Wolke, F.H.P.M.
Habraken, l. Jansen, Influence of Ar pressure on r.f. magnetron-sputtered
Ca5 (PO4 )3 OH layers, Surf. Coat. Technol. 76-77 (1995) 206–210.
180 S.R. Kiahosseini et al. / Applied Surface Science 401 (2017) 172–180
[39] V. Nelea, C. Morosanu, M. Iliescu, I.N. Mihailescu, Hydroxyapatite thin films
grown by pulsed laser deposition and radio-frequency magnetron sputtering:
comparative study, Appl. Surf. Sci. 228 (2004) 346–356.
[40] A. Vladescu, S.C. Padmanabhan, F.A. Azem, M. Braic, I. Titorencu, I. Birlikd, M.A.
Morris, V. Braic, Mechanical properties and biocompatibility of the sputtered
Ti doped hydroxyapatite, J. Mech. Behav. Biomed. Mater. 63 (2016) 314–325.
[41] R.J. Narayan, W. Wei, C. Jin, M. Andara, A. Agarwal, R.A. Gerhardt, C.-C. Shih,
C.-M. Shih, S.-J. Lin, Y.-Y.S. e, R. Ramamurti, R.N. Singh, Microstructural and
biological properties of nanocrystalline diamond coatings, Diamond Relat.
Mater. 15 (2006) 1935–1940.
[42] S.V. Kamat, V. Puri, R.K. Puri, The effect of film thickness on the structural
properties of vacuum evaporated poly(3-methylthiophene) thin films, ISRN
Polym. Sci. 2012 (2012) 1–8.
[43] J.-H. Huang, F.-Y. Ouyang, G.-P. Yu, Effect of film thickness and Ti interlayer on
the structure and properties of nanocrystalline TiN thin films on AISI D2 steel,
Surf. Coat. Technol. 201 (2007) 7043–7053.
[44] W.-J. Chou, G.-P. Yu, J.-H. Huang, Corrosion behavior of TiN-coated 304
stainless steel, Corros. Sci. 43 (2001) 2023–2035.
[45] J. Hu, L. Yang, G. Cao, Y. Yun, G. Yuan, Q. Yue, G. Shao, On the oxidation
behavior of (Zr,Nb)2Fe under simulated nuclear reactor conditions, Corros.
Sci. 112 (2016) 718–723.