Ceramics International 49 (2023) 13405–13413

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Improvement of TiN coating on comprehensive performance of NiTi alloy

braided vascular stent
Song Wang a, *, Yanqi Zhang a, b, Ying Qin c, Junzhe Lu a, Weiqiang Liu a, b
a
Biomechanics and Biotechnology Lab, Research Institute of Tsinghua University in Shenzhen, Shenzhen, 518057, PR China
b
Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, 518055, PR China
c
Biology Engineering, Tianjin University of Science and Technology, Tianjin, 300457, PR China

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

Handling Editor: Dr P. Vincenzini In order to improve the wear and corrosion resistance of Ni–Ti alloy-based braided stent, High-temperature
nitriding technology was used to prepare the TiN coating with different process parameters. Based on the sys­
Keywords: tematic evaluation of nano-mechanical properties, tribological properties, electrochemical corrosion properties,
TiN film nickel ion release properties and cytotoxicity, the feasibility of the application of the TiN coating in braided
Ni–Ti alloy
peripheral vascular stents was explored. The results showed that TiN coating included the TiN layer of about 1
Braided vascular stent
μm and nitrided layer of 50 μm under the process parameters of 800 ◦ C and 1h. The nano hardness and elastic
Tribological property
Electrochemical corrosion modulus for TiN film were 20.50 GPa and 281.66 GPa, respectively. TiN coating can not only significantly reduce
Nickel ion release the friction coefficient in dry sliding and lubrication state, but also greatly reduce the wear rate such as by three
Cytotoxicity orders of magnitude in dry sliding condition. TiN film reduced the icorr value with a reduction amount of 75.1%,
with the value of 8.41 × 10− 8 and 2.09 × 10− 8A/cm2 for NiTi and TiN, respectively. After 28 days of soak
experiment in phosphate buffer solution, the total nickel ion release amount of sample TiN#4 and bare NiTi were
0.094 and 1.452 ng/m, which was reduced by 93.5%. The relative cell proliferation rate results showed that TiN
samples all exceeded 90%, which mean that the cytotoxicity grade was 0. Based on the above results, TiN showed
good nano-mechanical, tribological, electrochemical corrosion, nickel ion release and cytotoxity properties, and
was expected to be used as a protective layer on the surface of Ni–Ti alloy stent.

1. Introduction
Nickel-titanium alloy is widely used in cardiovascular, orthopedic
and dental implant fields because of its good shape memory and
biosafety [1,2]. Compared with the traditional laser engraving stent,
NiTi-based braided vascular stent is not only suitable for complex
vascular diseases, but also has more advantages for the limbs’ blood
vessels because of its flexible braiding characteristics [3–5]. However,
the wire of braided scaffold is very thin, and under the action of human
load and physiological environment, wear and corrosion between the
wires are easy to occur, which not only easily lead to the release of nickel
ions, but also cause destruction of the scaffold’s mechanical strength
[6–9]. Therefore, the modification technology to improve the wear and
corrosion resistance of NiTi alloy wire is urgently needed clinically.
Not only the braided vascular stent has the problem of wear and
corrosion, but also the main problem of implants made of NiTi alloy in
clinic is the release of nickel ions caused by corrosion in physiological
environment or wear in service [10,11]. Nickel ions can cause skin
swelling, inflammation and even DNA damage, which is potentially
toxic to human body [12,13]. Therefore, the wear and corrosion resis­
tance of NiTi alloy has always been a hot issue in engineering research.
With the development of surface modification technology, at present,
carbon-based (such as DLC) and nitrogen-based (such as TiN) anti-wear
and corrosion coatings can be prepared on the surface of materials by
modification technologies such as chemical vapor deposition (CVD) and
physical vapor deposition (PVD) [14–17]. However, for braided stents,
the wire diameter of NiTi alloy is small and presents irregular shape, and
the shape memory function of NiTi alloy is sensitive to temperature.
Therefore, there are not many feasible and cost-effective modification
technologies available in industrial production nowadays. Rapid Ther­
mal Processing (RTP) combined with CVD, namely high-temperature
nitriding technology, could directly and quickly prepare TiN coating
on Ni–Ti alloy wire or stent products. The method showed higher effi­
ciency, simpler process, higher cost performance and was more suitable

* Corresponding author.
E-mail address: wangs@tsinghua-sz.org (S. Wang).

https://doi.org/10.1016/j.ceramint.2022.12.215
Received 16 November 2022; Received in revised form 19 December 2022; Accepted 22 December 2022
Available online 28 December 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
S. Wang et al. Ceramics International 49 (2023) 13405–13413

for batch production. Hence, based on the above advantages, the

high-temperature nitriding technique was chosen to fabricate the TiN
coatings.
In this study, RTP combined with CVD was used to prepare the wear
and corrosion-resistant TiN coating on the surface of NiTi alloy. Then,
the effects of different process parameters on the surface and composi­
tion of the stent materials were systematically studied. Finally, based on
the systematic evaluation of nano-mechanical properties, tribological
properties, electrochemical corrosion properties, nickel ion release
properties and cytotoxicity, the feasibility of the application of the TiN
coating in braided peripheral vascular stents was explored, providing
reference for future product applications.

2. Materials and methods

2.1. Preparation of TiN coatings

Medical NiTi alloy (Jiangyin Lumenous Peier New Material Tech­

nology Co., Ltd.) was selected as the experimental material in this study,
and the composition content was shown in Table 1. As shown in Fig. 1,
the shape of the material included two types: block (20 × 20 × 5 mm, Fig. 1. Block and wire samples before and after coating.
Ra0.02 μm) and wire (φ0.005inch × 1 m), which the latter was mainly
used for the experimental study of nickel ion release.
RTP method was generally used to realize rapid heating of materials Table 2
by high-power heat radiation tube, and its heating rate can reach tens of Technological parameters of TiN films prepared by RTP method.
degrees per second. The operation of surface oxidation or surface No. N2 flow rate Process temperature Process time
nitriding could be quickly realized by introducing reaction gas into the TiN#1 1000sccm 700 C ◦
0.5h
heat treatment, which shows obvious advantages in improving the TiN#2 1000sccm 700 ◦ C 1.0h
production efficiency of products. In the RTP process, the parameters TiN#3 1000sccm 800 ◦ C 0.5h
that affect the film quality include process temperature, process time, TiN#4 1000sccm 800 ◦ C 1.0h
gas flow rate, etc. Generally, the higher the temperature is, the greater
the thickness of the nitrided layer is. However, too high temperature
examinations of the TiN samples were conducted by X-ray diffraction
may lead to coarse grains in the nitrided layer or affect the performance
(D8 ADVANCE made by BRUKER) analysis with Cu-Kα radiation by
of the substrate material. Considering the low cost, convenience and
scanning in the 2θ range 10–90◦ .
mass production capacity of RTP technology, this study selected RTP
technology to prepare TiN coating on NiTi alloy surface.
In order to preliminarily grasp the parameter range of the corre­ 2.3. Nano-mechanical test
sponding influencing factors of RTP process, an L9-3-3 orthogonal
experiment was first designed to explore the optimal process. The The nano-hardness and elastic modulus of the TiN films were
temperature ranges are 600 ◦ C, 700 ◦ C and 800 ◦ C respectively, the time measured by nano-indentation experiment with nano-indentation tester
is 15 min, 30 min and 60 min respectively, and the nitrogen flow (MDTC-EQ-M55-01). When the indentation depth of nano-indentation
parameter ranges are 500 sccm, 1000 sccm and 2000 sccm respectively. experiment exceeded one tenth of the film thickness, the test results
According to the coating color and surface uniformity, it is found that would be affected by the relatively soft NiTi alloy matrix. Hence, this
the N2 gas flow rate has little influence, while mainly the temperature experiment was conducted by controlling the displacement. After the
and the time influence. Therefore, this study further designed and pre­ experiment was controlled to be loaded for 30s, the load was kept for
pared four groups of TiN coatings based on the combination of tem­ 120s, and then unloaded. The loading depth of TiN films was all 100 nm.
perature, time and flow rate as shown in Table 2.
Taking TiN#1 sample as an example, the manufacture process of TiN 2.4. Tribological test
films in detail was as below. (1) Clean and dry the sample with absolute
ethanol. (2) Put the sample into the sample cavity and vacuum. (3) The tribological experiments were carried out by Rtec multifunc­
Introduce nitrogen at a flow rate of 1000sccm for 1 min (4) Rise tem­ tional friction and wear tester (Rtec-5000). The experimental conditions
perature from room temperature to 700 ◦ C within 20s. (5) Keep the were dry sliding (DRY) and newborn calf serum lubrication (NCS),
temperature at 700 ◦ C for 0.5 h at a nitrogen flow rate of 1000sccm. (6) respectively. The parameters were designed with a load of 4 N, sliding
Natural cooling, while keeping the nitrogen flow at 1000sccm. frequency of 2Hz, sliding stroke of 3 mm and duration of 1800s,
respectively. The friction pair was Al2O3 ceramic balls with a diameter
2.2. Characterization of TiN coatings of 6.35 mm. During the experiments, the change of friction coefficient
(COF) with duration was recorded. After the tribological experiments,
The surface morphology and cross section morphology of TiN white light interferometer (Rtec-5000) was used to measure the surface
coating was characterized by SEM (TESCAN MIRA3). Microstructure wear, and SEM was used to study the change of surface morphology and

Table 1
Composition table of medical nickel-titanium alloy.
Wt% Ni C Co Cu Cr Nb Fe N Ti

GB24627-2009 54.5–57.0 ≤0.05 ≤0.05 ≤0.01 ≤0.01 ≤0.025 ≤0.05 ≤0.05 Others
In this Study 55.8 0.0074 <0.003 0.003 <0.003 <0.003 0.004 0.0015 Others

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analyze the wear mechanism.
2.5. Electrochemical corrosion test
The sample was prepared after being treated with potting glue.
Electrochemical corrosion test was studied using electrochemical work
station (Metrohm-Autolab/PGSTAT302 N) with a three-electrode test
system. The inert platinum electrode and Ag/AgCl reference electrode
were used in three-electrode system. The simulated body fluid used in
the experiment was phosphate buffer solution (PBS), and the test system
was placed in a constant temperature water bath at 37 ◦ C. The potential
polarization curve was tested with the scanning rate of 0.2 mV/s and
scanning range from − 0.6V to 1.6V. Thus, two important corrosion
parameters can be obtained by Tafel extrapolation based on polarization
curves: corrosion current density (icorr) and self-corrosion potential
(Ecorr). Generally, if Ecorr value was higher and icorr value was smaller,
the corrosion rate of materials would be lower.
2.6. Nickel ion release test
Nickel ion release experiment was designed and carried out ac­
cording to ASTM F3306 standard using wire sample. The surface-volume
ratio of the sample to the solution was 0.399 cm2/ml, which met the
recommendation of FDA guidance documents that the value should be in
the range of 0.1–1.0 cm2/ml. Each group of samples was soaked for 28
days, and all the solutions were extracted and replaced on the 1st, 2nd,
4th, 7th, 14th, 21st and 28th days respectively. Finally, inductively
coupled plasma emission spectrometer (ICP, Arcos II MV) was used to
detect the ion concentration of the extracted solution.
2.7. Cytotoxicity test
In order to further compare the biocompatibility of several coatings,
cytotoxicity experiments were conducted according to the standard GB/
T 16886.5–2017. After preparing the leaching solution containing
Minimum Eagle’s Medium (MEM) culture medium, each sample was
leached at (37 ± 1)◦ C for 24 h to obtain the leaching solution sample to
be tested. At the same time, well-grown L929 cells were prepared and
diluted at a concentration of 10,000 cells per ml after digestion, and
added into 96-well plates. After 24 h of incubation, the culture solution
Fig. 2. The surface and cross-sectional morphology of TiN coatings: (a) Surface SEM morphology of TiN#1 film, (a1) Cross section of TiN#1 film, (b) Surface SEM
morphology of TiN#2 film, (b1) Cross section of TiN#2 film, (c) Surface SEM morphology of TiN#3 film, (c1) Cross section of TiN#3 film, (d) Surface AFM
morphology of TiN#4 film, (d1) Cross section of TiN#4 film.
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in the wells was sucked out. Then, 100 μl of the samples were added to
each well including leaching solution to be tested, negative control
sample, positive control sample and blank sample, and the culture was
continued for 24 h. Then, the original culture solution was sucked out,
and 50 μl Cell Counting Kit-8 (CCK-8) solution was added into each well,
and cultured for 2 h. Finally, CCK-8 solution was sucked out, 100 μl
isopropanol was added, and the absorbance of the sample at 450 nm
wavelength was measured by microplate meter. Thus, the cell survival
rate could be calculated.
3. Results
3.1. Characterization of TiN coating
3.1.1. Surface morphology
The surface and cross-sectional morphology of TiN coating were
shown in Fig. 2. According to the surface morphology of Fig. 2(a, b, c, d),
TiN coating was grown on NiTi alloy substrate. With the increase of RTP
temperature and time, the compactness and uniformity of the coating
were gradually optimized. The surface of the TiN coating shown in Fig. 2
(d) was compact, and the coated crystal was full and evenly distributed
on the surface.
According to the cross-sectional morphology of Fig. 2(a1, c1, d1), the
thickness of nitrided layer can gradually increase from 27 μm for
TiN#1–50 μm for TiN#4. According to the analysis on the surface TiN
layer in Fig. 2(b1), its thickness was about 1 μm. Therefore, the results
showed that the thickness of TiN layer was about 1 μm, but the thickness
of nitrided layer can reach 50 μm. Based on the above results, TiN#4
showed the best coating surface quality and the largest nitrided layer
thickness.
3.1.2. XRD spectrogram
The XRD spectrogram of TiN films was shown in Fig. 3. From the XRD
spectrum, it can be found that TiN phase and Ni3Ti phase crystals
appeared on the surface of NiTi alloy after RTP treatment. With the
increase of RTP temperature and time, the intensity of the two kinds of
crystals gradually increased. As known, Ni3Ti belongs to Ni-rich phase
structure. Its appearance indicated that more Ti element combined with
N element to form TiN crystal. Because of the high strength and wear
resistance of TiN phase, its appearance can significantly enhance the
S. Wang et al.
Fig. 3. The XRD spectrogram of TiN coatings.
wear and corrosion resistance of the surface. However, Ni3Ti phase did
not show the strength and physical characteristics of NiTi material,
excessive production would even have an adverse effect on the perfor­
mance of the original stent. Hence, the content of the two crystals
needed to be balanced. When there was no or only a small amount of
Fig. 4. The Nano-mechanical properties of TiN films: (a) Loading and unloading curves of nano-indentation experiment, (b) Nano hardness, (c) Modulus of elasticity,
(d) H/E value.
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Ni3Ti phase, the nitriding process was still insufficient, which may lead
to insufficient compactness of the coating. Taking sample TiN#1 and
sample TiN#2 as examples, they hardly showed Ni3Ti phase based on
Fig. 3. Correspondingly, their surface compactness was insufficient as
shown in Fig. 2(a) and (b). For sample TiN#3, although Ni3Ti phase
appeared on the surface, its content was still too small. Correspondingly,
its compactness was not optimal though it has been improved, as shown
in Fig. 2(c). For sample TiN#4, the content of Ni3Ti phase has reached a
critical value, so the surface morphology shown in Fig. 2(d) showed that
the coating revealed excellent compactness, and the surface grain size
and distribution were relatively uniform. The above results showed that
the film quality could be judged by the Ni3Ti phase content based on
XRD spectrogram and surface morphology based on the SEM analysis.
Hence, Ni3Ti phase has an important function in evaluating the coating
quality.
Based on the results in Figs. 2 and 3, the nitriding temperature and
time should be controlled within a reasonable range in order to obtain
better coating surface quality. In addition, increasing nitriding temper­
ature and time can effectively improve the surface coating effect by
balancing the ratio of TiN phase and Ni3Ti phase crystals. To sum up,
with the increase of temperature and time in RTP gas nitriding, the
nitriding effect was obviously enhanced. It showed the best coating
surface quality for sample TiN#4 in this study.
3.2. Nano-mechanical properties
The Nano-mechanical result of TiN films was shown in Fig. 4. Based
on the loading and unloading curves of nano-indentation experiment in
S. Wang et al.
Fig. 4(a), the loading depth of TiN films was 100 nm. However, the
forces required to load at the same depth were TiN#4, TiN#3, TiN#2
and TiN#1, in descending order, indicating different surface nano
hardness. The Nano hardness and Modulus of elasticity were shown in
Fig. 4(b) and (c), which showed more details of nano mechanical
properties. The nano-hardness of the TiN samples was 16.95 GPa, 17.48
GPa, 19.03 GPa and 20.50 GPa for TiN#1, TiN#2, TiN#3, and TiN#4,
respectively. Compared with the nano hardness of Ni–Ti alloy material
of 4.22 GPa, the hardness of the samples after surface modification was
significantly improved. In terms of the elastic modulus, the value was
68.59 GPa, 230.14 GPa, 233.54 GPa, 267.17 GPa and 281.66 GPa for
NiTi, TiN#1, TiN#2, TiN#3 and TiN#4, respectively. Based on the re­
sults, it can be seen that the nano-hardness and elastic modulus of TiN
films increased significantly with the increase of nitriding temperature
and time.
Generally, the wear resistance of hard materials could be qualita­
tively evaluated by the ratio of nano-hardness to modulus H/E, and the
larger the ratio, the better the wear resistance of materials can be pre­
dicted. Based on the nano-hardness and elastic modulus data, the results
were further calculated as shown in Fig. 4(d), in which the H/E value of
TiN film was 0.074, 0.075, 0.071 and 0.073 for TiN#1, TiN#2, TiN#3
and TiN#4, respectively. The H/E values of four kinds of TiN films were
similar, but they were all higher than that of NiTi alloy substrate
(0.062). Hence, theoretically, four kinds of TiN films could significantly
improve the wear resistance of NiTi substrate.
3.3. Tribological properties
It showed the curve of friction coefficient with time for NiTi and TiN
films in Fig. 5. The results of Fig. 5(a) showed that the COF of NiTi alloy
suddenly become very large (0.7) in the initial stage, and then was kept
fluctuating around 0.7. For four kinds of TiN thin films, the COF
increased sharply within 200s of the beginning of test. This phenomenon
was related to the large surface roughness at the beginning of dry
sliding, which has not been yet formed a stable friction interface. The
difference was that with time, the COF of TiN#1 and TiN#2 gradually
increased to about 0.7 and has been maintained. However, the COF of
TiN#3 and TiN#4 decreased significantly, and was kept between 0.3
and 0.4. The above results showed that the surface of TiN#1 and TiN#2
may have been damaged, and then the friction between the base ma­
terial and the friction pair appeared, which can also be proved by the
COF value. However, coatings for TiN#3 and TiN#4 can avoid wearing
through the surface because of their better surface coating quality.
According to the friction coefficient shown in Fig. 5(b), the lubrica­
tion state can significantly reduce the friction coefficient value.
Fig. 5. The curve of friction coefficient with time: (a) Dry sliding condition, (b)
Newborn bovine serum solution condition.
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However, the COF of NiTi alloy still showed great fluctuation, which
may be related to the severe abrasive wear caused by NiTi alloy particles
produced on the surface. Abrasive particles may significantly affect the
surface contact state, and then affect the change of friction coefficient.
Although the friction coefficients of the four kinds of TiN films were
stable under lubrication, TiN#3 and TiN#4 samples obviously showed
lower friction coefficients than TiN#1 and TiN#2 samples. The above
results showed that the friction coefficients of TiN#3 and TiN#4 were
not only lower but also more stable, which proved that the coating
quality was better.
In order to further compare the tribological performance, the
average friction coefficient and volume wear rate under both dry sliding
and newborn bovine serum solution condition were calculated as shown
in Fig. 6. The results showed that, in dry sliding condition, the average
COF of NiTi alloy was the biggest with the value of 0.7034. However, the
average COF of four kinds of TiN films were all about 0.4 in dry sliding,
indicating greatly reduced by preparing TiN. However, in newborn
bovine serum solution condition, the average COF for four TiN films was
all a little bigger than that for NiTi as shown in Fig. 6 (a). This may be
related to the higher roughness of TiN film caused by crystal growth.
Based on the volume wear rate results in Fig. 6(b), whether in dry
sliding or lubrication state, the four TiN films obviously reduced the
volume wear rate. To be specific, the volume wear rates under dry
sliding were 1.24E-12 and 2.94E-15m3/Nm for NiTi and TiN#4,
respectively. In addition, the volume wear rates under lubrication were
4.94E-14 and 9.73E-16m3/Nm for NiTi and TiN#4, respectively. Hence,
the volume wear rates were reduced by 2–3 orders of magnitude by
sample TiN#4 under both dry sliding and lubrication conditions. In
addition, the TiN#4 showed the lowest volume wear rate under both dry
sliding and lubrication conditions.
In order to further judge the wear depth and contrast with film
thickness, the cross-section wear profiles were also measured. As shown
in Fig. 7, the wear depth reached about 25 μm under dry sliding con­
dition and 5 μm under newborn bovine serum solution condition for
NiTi. However, based on Fig. 7(a), it can be seen that for TiN#1 and
TiN#2 samples, the wear depth under dry sliding was also very large,
reaching 17 and 15 μm, respectively, which also proved the COF result
of Fig. 5. It indicated that the films of TiN#1 and TiN#2 were both worn
through, and then the substrate participated in the dry sliding. However,
TiN#3 and TiN#4 samples showed good wear resistance in dry sliding,
and the wear depth was only 0.58 μm and 0.47 μm, respectively, which
indicated that the coating was still working. According to Fig. 7(b), the
wear depth of four kinds of TiN films under lubrication condition was
smaller, and the values were all below 0.5 μm, indicating that the
coatings were not worn through.
Fig. 6. The average friction coefficient and volume wear rate under both dry
sliding and newborn bovine serum solution condition: (a) Average friction co­
efficient, (b) Volume wear rate.
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Fig. 7. Cross-section wear profiles under both dry sliding and newborn bovine
serum solution condition: (a) Dry sliding condition, (b) Newborn bovine serum
solution condition.
large furrow scratches. The worn surface showed a large number of NiTi
alloy abrasive particles, and the wear mechanism was mainly abrasive
wear and adhesive wear as shown in Fig. 8 (a) and Fig. 8 (a1). However,
in the lubricated state, wear width of NiTi alloy was significantly
reduced, and the degree of abrasive wear and adhesive wear was also
significantly reduced based on Fig. 8 (f) and Fig. 8 (f1).
For samples of TiN#1 and TiN#2, similar to Fig. 8 (a) and Fig. 8 (a1),
large furrow scratches also appeared on the worn morphology under dry
sliding with severe abrasive wear and adhesive wear marks as shown in
Fig. 8(b)(c)(b1) (c1). This result also confirmed that TiN films were worn
through for samples of TiN#1 and TiN#2. For samples of TiN#3 and
TiN#4, wear severity was much lower, and scratches mainly appeared
on the surface with the abrasive wear mechanism. Under lubrication
state, when compared Fig. 8(f) with Fig. 8(g)(h)(i)(j), it can be seen that
the wear width and wear severity were obviously reduced by TiN films.
The dominant wear mechanism was abrasive wear, confirmed by many
thin wear scratches as shown in Fig. 8(g1)(h1)(i1)(j1).
3.4. Electrochemical corrosion performance

The potentiodynamic polarization curves of NiTi and TiN films under

The wear morphology of NiTi and TiN films under both dry sliding phosphate buffer solution were shown in Fig. 9. The corrosion potential
and newborn bovine serum solution condition was shown in Fig. 8. In (Ecorr) and the corrosion current density (icorr) were determined from the
dry sliding environment, the surface wear of NiTi alloy was serious, with polarization curves using Tafel extrapolation method. Based on the

Fig. 8. Wear morphology of NiTi and TiN films under both dry sliding and newborn bovine serum solution condition: (a) NiTi, DRY, (b) TiN#1, DRY, (c) TiN#2,
DRY, (d) TiN#3, DRY, (e) TiN#4, DRY, (f) NiTi, NCS, (g) TiN#1, NCS, (h) TiN#2, NCS, (i) TiN#3, NCS, (j) TiN#4, NCS.

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Fig. 9. Potentiodynamic polarization curves of NiTi and TiN films under
phosphate buffer solution.
analyses, the Ecorr value was − 0.374, − 0.262, − 0.226, − 0.367 and
− 0.313V for NiTi, TiN#1, TiN#2, TiN#3 and TiN#4, respectively. The
icorr value was 8.41 × 10− 8, 2.90 × 10− 8, 1.80 × 10− 8, 7.01 × 10− 9 and
2.09 × 10− 8 A/cm2 for NiTi, TiN#1, TiN#2, TiN#3 and TiN#4,
respectively. Compared the corrosion potential between NiTi and TiN
films, it can be seen that four TiN films all increased the value, indicating
stronger electrochemical corrosion resistance. Similarly, compared the
corrosion current density between NiTi and TiN films, TiN films also
decreased the values. To be specific, the corrosion current density was
reduced by 75.1% compared TiN#4 sample with NiTi. As known, if
Ecorr was higher and icorr was smaller, the corrosion rate of materials
would be lower. Hence, these results suggested an improvement in
electrochemical corrosion resistance by TiN films.
3.5. Nickel ion release performance
For Ni–Ti alloy-based vascular stents, the release amount of nickel
ions was an important index of stent safety. The curves of nickel ion
release rate and total nickel ion release with time were shown in Fig. 10.
According to Fig. 10(a), the maximum nickel ion release rate of all
samples appeared on the first day, and then gradually decreased. And
Fig. 10. Curves of nickel ion release rate (a) and total nickel ion release (b)
with time.
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the release rate of nickel ions after the 14th day was significantly lower
than that of the first and second days. Among them, bare NiTi released
the largest amount on the first day, nickel ion release rate was 0.842 ng/
m/d, followed by polished NiTi, with a value of 0.589 ng/m/d. Four TiN
films can all significantly reduce the release rate of nickel ions based on
Fig. 10(a). According to Fig. 10(b), after 28 days of experiment, the total
release amount of bare NiTi can reach 1.452 ng/m. However, the total
nickel ion release value was 0.143, 0.121, 0.119 and 0.094 ng/m for
TiN#1, TiN#2, TiN#3 and TiN#4, respectively. Therefore, TiN films can
significantly reduce both nickel ion release rate and total nickel ion
release. To be specific, the total nickel ion release was reduced by 93.5%
compared TiN#4 sample with bare NiTi.
3.6. Cytotoxicity
According to the national standard GB/T 16886.5, the cytotoxicity
test results by CCK-8 method of NiTi stent and coated samples were
shown in Fig. 11. The results showed that NiTi alloy did not indicate
high toxicity with grade 0 and 99.21% for the relative cell proliferation
rate. Hence, there will be no adverse reaction after implantation due to
the release of nickel ions or nickel-containing wear particles without
serious wear and corrosion. For samples coated with TiN, the results of
relative cell proliferation rate of all samples exceeded 90%, which mean
that the cytotoxicity grade was 0. For samples TiN#1 and TiN#2, the
cell proliferation rate even exceeded 100%, indicating that the effect of
promoting cell proliferation was better than that of the blank group. This
result was mainly due to two aspects. Firstly, for samples TiN#1 and
TiN#2, the surface roughness was very large according to Fig. 2(a) and
(b), which was easy to induce cell proliferation, and then the prolifer­
ation rate result was good. Secondly, TiN and NiTi alloy material showed
no cytotoxicity and would not inhibit cell proliferation. Therefore, the
cell proliferation rates of many TiN samples were all over 100%. As a
conclusion, the surface of NiTi alloy modified by TiN showed no cyto­
toxicity and good biosafety.
4. Discussions
TiN is suitable for medical surface functional coating because of its
good wear resistance, corrosion resistance and biological safety, and is
widely used in medical implants such as artificial knee joint. At present,
a large number of preparation methods have been reported for preparing
TiN coating or Ni-based nanocoating, such as PVD, CVD, ion implanta­
tion, arc ion plating and pulsed high energy density plasma [14–17]. In
order to improve the bonding strength or some other properties, carbon
Fig. 11. Cytotoxicity test results by CCK-8 method.
S. Wang et al.
nitride film and TiN–TiO2 composite film are also used in the coating
preparation process. However, although there are many preparation
techniques and improvement methods to improve the properties of TiN,
most of the current preparation methods tend to be complicated.
Therefore, RTP combined with CVD was proposed in this study, which
can directly and quickly prepare TiN coating on Ni–Ti alloy wire or stent
products. Moreover, in the study of various properties, it was found that
the prepared TiN coating indicated excellent properties of
nano-mechanics, tribology, electrochemical corrosion, nickel ion release
and cytotoxicity.
In terms of nano hardness and elastic modulus, taking sample TiN#4
as an example, the value was 20.50 GPa and 281.66 GPa, respectively. In
Y. Cheng’s study [18], the average value of hardness and modulus was
29.21 GPa and 276.55 GPa for TiN coating prepared by PIIID method
with a voltage of 20 kV. At this time, the H/E value was 0.105 while was
0.073 in our study. Based on the above comparison, it can be seen that
the H/E value was a little higher than that in this study, indicating a
better wear resistance in theory. However, their study did not carry out
tribological test. In addition, the thickness reached 2.92 ± 0.29 μm [19],
which may be too big for nickel-titanium wire for stent.
In terms of the tribological properties, the volume wear rates under
dry sliding were 1.24E-12 and 2.94E-15m3/Nm for NiTi and TiN#4,
respectively. In addition, the volume wear rates under lubrication were
4.94E-14 and 9.73E-16m3/Nm for NiTi and TiN#4, respectively. Hence,
the volume wear rates were reduced by 2–3 orders of magnitude for
sample TiN#4 under both dry sliding and lubrication conditions. Simi­
larly, there were other reports to prove the wear-resistant modification
effect of DLC coating on NiTi alloy substrate [20–22]. In H.C. Man’s
research [20], the wear rates of the grid-nitrided samples and the
UHMWPE counter-body in the wear pair were both significantly
reduced. The decrease in wear rates can be attributed to the combination
of a hard TiN grid and a soft NiTi substrate. In this study, the analysis of
the wear profile and morphology of the coating also proved that only a
few furrows appeared on the surface of sample TiN#4, and the wear
depth was much lower than the thickness of the coating, which can
protect the surface.
In terms of the performance of electrochemical corrosion, the icorr
value was 8.41 × 10− 8 and 2.09 × 10− 8 A/cm2 for NiTi and TiN#4, with
a reduction by 75.1% compared TiN#4 sample with NiTi. Similarly, the
literature also reported the improvement of electrochemical corrosion
resistance for TiN coating [23–25]. In Justyna Witkowska’s research
[23], Ti(ON)+a-CNH type composite layers were produced on NiTi alloy
in a hybrid process combining oxidation in low-temperature plasma and
Radio Frequency Chemical Vapor Deposition process (RFCVD). They
found that the Ti(ON) layer produced was heterogeneous, nonetheless
and it increased the corrosion resistance of the material (the value of the
corrosion potential is up from − 275mV to − 130mV). Y. Cheng’s study
[24] has prepared multilayer TiN/Ti coatings by filtered cathodic arc ion
plating technique and confirmed that this coating can effectively
improve the corrosion resistant property of NiTi alloy for the application
of cardiac occluders.
In terms of the performance of nickel ion release rate, after 28 days of
experiment, the total release amount of bare NiTi can reach 1.452 ng/m.
However, the total nickel ion release value was only 0.094 ng/m for
sample TiN#4, which was reduced by 93.5%. In Milad Badr’s work [26],
the NiTi alloy was oxynitrided in a fluidized bed reactor to attain an
in-situ TiN–TiO2 protective composite layer. It was found that concen­
tration of the released Ni ions decreased from 0.070 (bare NiTi) mg/l to
0.028 mg/l (treated for 8 h) after oxynitriding treatment. Hence, the
above studies also confirmed that TiN coating showed great nickel ion
release resistance.
In terms of the performance of cytotoxicity, the results of relative cell
proliferation rate of TiN samples all exceeded 90%, which mean that the
cytotoxicity grade was 0. That is to say, TiN coating showed no cyto­
toxicity and good biosafety. Lots of similar research also indicated this
conclusion. For example, Shi Jin’s SEM results showed that TiN coating
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Ceramics International 49 (2023) 13405–13413
could enhance the cell attachment, spreading and proliferation on NiTi-
SMA [27]. Raluca Ion et al. [28] investigated the benefits of nitriding the
NiTi shape memory alloy for vascular stent applications. Results from
cell experiments indicated that, compared to untreated NiTi, a superfi­
cial gas nitriding treatment enhanced the adhesion of human umbilical
vein endothelial cells (HUVECs), cell spreading and proliferation. In
addition, the blood compatibilities of NiTi alloy can be also improved
effectively by the deposition of hard films. In comparison with TiN and
DLC film, CNx film had the best surface modification effects covering the
minimum haemolysis ratio and the best anticoagulation property [29].
The excellent biocompatibility of TiN may be related to the surface
roughness [30] and material characteristics [31]. Dayun Yang’s work
[31] showed that TiN coating not only effectively prevented release of
Ni ions from NiTi alloy, but also promoted actin cytoskeleton and focal
adhesion formation, increased energy metabolism, enhanced regulation
of inflammation, and promoted amino acid metabolism.
5. Conclusions
(1) TiN coating was prepared on NiTi with the TiN layer of about 1
μm and nitrided layer of 50 μm by RTP method with the tem­
perature of 800 ◦ C and time of 1h.
(2) The nano hardness and elastic modulus for TiN film were 20.50
GPa and 281.66 GPa, respectively.
(3) TiN coating can not only significantly reduce the friction coeffi­
cient in dry sliding and lubrication state, but also greatly reduce
the wear rate such as by three orders of magnitude in dry sliding
condition.
(4) TiN film reduced the icorr value with a reduction amount of
75.1%, with the value of 8.41 × 10− 8 and 2.09 × 10− 8A/cm2 for
NiTi and TiN, respectively.
(5) After 28 days of soak experiment in phosphate buffer solution,
the total nickel ion release amount of sample TiN#4 and bare
NiTi were 0.094 and 1.452 ng/m, which was reduced by 93.5%.
(6) The relative cell proliferation rate results showed that TiN sam­
ples all exceeded 90%, which mean that the cytotoxicity grade
was 0.
(7) TiN showed good nano-mechanical, tribological, electrochemical
corrosion, nickel ion release and cytotoxity properties, and was
expected to be used as a protective layer on the surface of Ni–Ti
alloy stent.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper..
Acknowledgment
This project was supported by the Guangdong Basic and Applied
Basic Research Foundation (Grant No. 2020B1515120082).
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