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https://doi.org/10.1007/s11665-019-04427-y 1059-9495/$19.00

Atomic Layer-Deposited Al2O3 Interlayer for Improved

Tribological and Anti-corrosion Properties of TiN Hard
Coating on 316L Stainless Steel
Ji-Zhou Kong, Liang Yin, Yan Xuan, Ai-Dong Li, Qian-Zhi Wang, and Fei Zhou

(Submitted February 18, 2019; in revised form September 30, 2019)

A dense Al2O3 interlayer was inserted into TiN to enhance the tribological and anti-corrosion properties of
TiN hard coating via a hybrid process of magnetron sputtering and atomic layer deposition (ALD). The
influence of the ALD-Al2O3 layer on the microstructure, mechanical, tribological and anti-corrosion
properties of TiN was examined. The TiN-Al2O3 coating exhibits low friction coefficient and specific wear
rate, due to the structure change and columnar refinement caused by the addition of amorphous ALD-
Al2O3 interlay which improves the mechanical properties of hard coating. The improved corrosion prop-
erties of TiN are attributed to the fact that the insulating ALD-Al2O3 used as a sealing layer can prevent the
corrosive chlorine ions migrating into the lower TiN layer and block the charge transport in coatings.
Moreover, raising the insertion position of ALD-Al2O3 layer away from the steel substrate results in a
further increase in the anti-corrosion property of TiN-Al2O3 composite coating.

the substrate and/or inert without any microstructural defect

Keywords atomic layer deposition, Al2O3 interlayer, corrosion,
TiN hard coating, tribological property
1. Introduction
Stainless steel (SS) is an important structural and functional
alloy material for both household and industrial applications. Its
wide application is ascribed to the remarkable combination of
good mechanical properties as well as high corrosion resis-
tance, due to a thin passive layer of chromium oxide-enriched
surface (Ref 1). However, this passive layer could be easily
broken down in the presence of chloride ions, resulting in the
localized corrosion (Ref 2). Corrosion durability can be
prolonged by an appropriate surface coating (Ref 3). The
coating material must be either cathodically protective toward
Ji-Zhou Kong, State Key Laboratory of Mechanics and Control of
Mechanical Structures, Nanjing University of Aeronautics and
Astronautics, No. 29 Yudao Street, Nanjing 210016, China; College
of Mechanical and Electrical Engineering, Nanjing University of
Aeronautics and Astronautics, Nanjing 210016, China; and National
Laboratory of Solid State Microstructures, Materials Science and
Engineering Department, Nanjing University, Nanjing 210093, China;
Liang Yin, College of Mechanical and Electrical Engineering, Nanjing
University of Aeronautics and Astronautics, Nanjing 210016, China;
Yan Xuan, Advanced Analysis and Testing Center, Nanjing Forestry
University, Nanjing 210037, China; Ai-Dong Li, National Laboratory
of Solid State Microstructures, Materials Science and Engineering
Department, Nanjing University, Nanjing 210093, China; and and
Qian-Zhi Wang and Fei Zhou, State Key Laboratory of Mechanics
and Control of Mechanical Structures, Nanjing University of
Aeronautics and Astronautics, No. 29 Yudao Street, Nanjing 210016,
China; and College of Mechanical and Electrical Engineering, Nanjing
University of Aeronautics and Astronautics, Nanjing 210016, China.
Contact e-mails: kongjzh@nuaa.edu.cn and fzhou@nuaa.edu.cn.
(Ref 4).
Several methods including sol–gel (Ref 5), micro-arc
oxidation (MAO) (Ref 6), physical vapor deposition (PVD)
(Ref 7, 8) and chemical vapor deposition (CVD) (Ref 9) are
employed to coat steel/alloy with hard ceramic coating layer.
However, some defects, e.g., pinholes and cracks exist in these
ceramic coatings (Ref 3). For example, the magnetron sputtered
metal nitrides such as TiN and CrN usually suffer from the
intrinsic defects, e.g., columnar structures, pinholes and
discontinuities (Ref 10, 11). When the metal nitride-coated
steels are exposed in a corrosion media, the corrosive
substances such as Cl pass through the possible intrinsic
defects of coatings to corrode the steel substrates (Ref 4). Many
strategies are adopted to overcome above defects and enhance
the anti-corrosion behavior of metal nitride coatings. Doping
with the nonmetal elements such as Si, C and B into metal
nitrides leads to the formation of nanocomposite structure
including an amorphous matrix inlaid with nanosize crystallites
(Ref 12–14). Additionally, the nanolaminated composite coat-
ings exhibit superior mechanical properties and chemical
stability (Ref 15, 16). Unfortunately, the commercial applica-
tions of nanocomposites and nanolaminated multilayer coatings
are sometimes incompetent owing to their un-uniformity of
physical and chemical properties (Ref 11).
Recently, a novel atomic layer deposition (ALD) technique
is explored to deposit ultrathin coatings which are applied in
microelectronics, optoelectronics, catalysis and electrolumines-
cence (Ref 17). Based on the growth mechanism of self-
limiting surface reactions, ALD is capable of depositing dense
and uniform films with low defect, high conformality and well-
controlled thickness on many substrates (Ref 18, 19). It was
commonly used to form oxide films for corrosion protection
(Ref 3, 20, 21). However, the growth of ALD thin films is
relatively slow, and thus the ALD technology is not econom-
ically feasible to deposit thicker layers against erosive loads.
Another advantageous of ALD over other coating techniques is
that it can coat high-aspect-ratio micro/nanostructures without

Journal of Materials Engineering and Performance

line-of-sight requirement (Ref 22, 23). In recent years, ALD-
oxide layers have been employed to seal hard coatings to
improve their anti-corrosion properties (Ref 23, 24). Neverthe-
less, the ALD-oxide sealing layers with thin thickness on hard
coatings can be easily worm out under the wear-corrosive
working conditions. Wan et al. reported (Ref 11) that the
amorphous Al2O3 interlayer was added into CrN to form the
sandwich-structured CrN-Al2O3-CrN composite coating by
combining PVD and ALD processes. As the insulating and
sealing bifunctional layer, the dense ALD-oxide layer can
inhibit the charge transfer, and prevent the diffusion of
corrosive media. However, the tribological properties as well
as mechanical properties including adhesion of CrN-Al2O3-
CrN are not reported so far. Although CrN shows excellent
mechanical properties and corrosion behavior, TiN coatings
present superior thermal stability and high hardness as well as
its beautiful color (Ref 7, 25). It delivers similar optical
parameters to Au in the visible region. Thus, as a novel
plasmonic material, TiN has a promising candidate for
optoelectronic materials (Ref 26, 27). More importantly, the
TiN-Al2O3-TiN structure can also adopted as the metal–
insulator–metal (MIM) integrated capacitor, which has been
applied in the dynamic random access memory (DRAM)
platforms, radio frequency (RF) integrated circuits and energy
storage devices (Ref 28, 29). So far, the influence of ALD-
Al2O3 on the tribological properties of TiN-Al2O3 composite
coating deposited by PVD/ALD hybrid processes has not been
reported. Therefore, it is important and urgent to investigate the
influence of ALD-Al2O3 interlayer on the microstructure,
tribological and anti-corrosion properties of TiN-Al2O3-TiN
composite coating.
In this work, an amorphous Al2O3 interlayer was inserted
into TiN to form the sandwich-structured TiN-Al2O3-TiN
composite coating by a combination of magnetron sputtering
and ALD technology. The influences of the dense ALD-Al2O3
layer on the microstructure, mechanical, tribological and
electrochemical corrosion properties of TiN-Al2O3-TiN were
evaluated in detail. The related mechanism was also discussed.
2. Experimental
sequence consisted of a 0.5 s TMA precursor dose, followed by
a 10 s N2 purge, then a 1 s H2O dose, and lastly a 10 s N2
purge. The source temperatures of TMA and H2O were kept at
room temperature, while the deposition temperature was
200 C with the Al2O3 growth rate of  1 Å/cycle.
Finally, a magnetron sputtered TiN was deposited on the top
of ALD-Al2O3 layer under the same deposition conditions.
Schematic illustrations of TiN coatings without/with the
inserted ALD-Al2O3 interlayer are shown in Fig. 1.
2.2 Characterization
An x-ray diffractometer (XRD, Bruker D8 Advance) with
Cu Ka radiation was adopted to identify the crystal structure of
the coatings. Surface and cross-sectional morphologies of the
coatings were observed by a scanning electron microscope
(SEM, Zeiss Ultra 55). The roughness of coatings were
measured using a white light interferometer (CCI 3D, Taylor
Hobson). An x-ray photoelectron spectroscopy (XPS, Thermo
K-alpha) with Al Ka radiation was used to analyze ex situ the
components and chemical states of the coatings. All of the
binding energies were calibrated by adventitious C1s peak at
284.6 eV. Mechanical properties of the coatings were investi-
gated by a nanoindentation tester (Elionix ENT-1100a) with
Berkovich indenter mode. To minimize the substrate effect, a
constant penetration depth of 100 nm was conducted using the
continuous stiffness measurement (CSM) mode at room
temperature.
2.3 Tribological Measurements
The wear tests of the coatings were investigated by a ball-
on-disk tribometer with sliding against SiC balls in 3.5 wt.%
NaCl solution at room temperature. The hardness, elastic
modulus, surface roughness and diameter of SiC balls are
22 GPa, 430 GPa, 88.5 nm and 8 mm, respectively. All the
tribological tests were carried out at 0.1 N with a sliding speed
of 0.1 m/s. The friction coefficient was continuously recorded
during testing, and the friction tests were repeated three times to
ensure the reliability of measured results. Meanwhile, the cross-
sectional area of the wear track on the coated disk was observed
by a non-contact white light interferometer (CCI 3D, Taylor
Hobson Ltd.).

2.1 Preparation of TiN-Based Composite Coatings

TiN hard coatings were deposited on 316L SS substrates and
Si wafers via unbalanced magnetron sputtering technique in
mixed Ar and N2 gases with the corresponding flow rates of 15
and 2 sccm. Before deposition, Si (100) and well-polished
316L SS substrates were cleaned ultrasonically in deionizer
water and ethanol, and then dried. Thereafter, the substrates
were handled with Ar+ plasma etching at a bias voltage of
500 V for 30 min. A pure Ti target (99.99 wt.%) was used to
deposit TiN layer at the target power of 125 W. During
deposition, the work gas pressure, substrate temperature and
bias voltage were maintained at 0.23 Pa, 200 C, and 60 V,
respectively. The deposition time was adjusted to control the
thickness of the TiN layer.
A dense Al2O3 interlayer about 10 nm was deposited on
TiN coating via Picosun SUNALE R-150B ALD reactor
using trimethylaluminum (TMA, (99.9999%)) and H2O.
Ultrahigh purity N2 (99.999%) was used as both the reactant
carrier and purging gas. Each typical ALD-Al2O3 deposition Fig. 1 Schematic illustration of the cross-sectional structure of the
TiN and TiN-Al2O3 coating

Journal of Materials Engineering and Performance

2.4 Electrochemical Measurements which includes a saturated Ag/AgCl reference electrode, a
coated sample as the working electrode and a platinum wire as
The electrochemical corrosion behavior of the coatings was
the counter electrode. The potentiodynamic polarization curves
conducted in 3.5 wt.% NaCl solution at room temperature.
were performed at a sweep rate of 20 mV min1 from 1 to
Prior to tests, the coated samples were covered by silicon
1 V versus Ag/AgCl.
rubber with a working region of 1 9 1 cm2. The electrochem-
ical measurements were measured by using CHI 660E electro-
chemical workstation in a traditional three-electrode system,
3. Results and Discussion

3.1 Crystal Structure and Surface Morphology

XRD patterns of TiN and TiN-Al2O3 composite coatings are
shown in Fig. 2. It can be obviously identified that the main
diffraction patterns in the coatings belong to a typically face-
centered cubic (fcc) structured TiN (JCPDS No. 087-0633)
with some characteristic peaks of (111), (200) and (220) planes.
In addition, the pure TiN displays (111) preferred orientation,
due to this plane possesses the lowest surface energy in the fcc
structure. There are no peaks referring to ALD-Al2O3 owing to
its amorphous phase. It is interesting to note that the preferred
orientation of TiN transforms to (200) and (220) from the
original (111) orientation after the addition of the ALD-Al2O3
interlayer. As was reported (Ref 11), the insertion of the ALD-
Al2O3 interlayer would result in the columnar refinement of
PVD-CrN coating, which could suppress the large columnar
crystal growth. Meanwhile, more nucleation sites would be
formed on the modified surface during depositing the TiN layer.
It is said that TiN with (200) preferred orientation could deliver
Fig. 2 XRD patterns of the pure TiN and TiN-Al2O3 composite better mechanical behavior and lower residual stress (Ref 30,
coating 31). Meanwhile, the block of columnar structure and refinement

Fig. 3 SEM images of the pure TiN and TiN-Al2O3 composite coatings: (a) S1, (b) S2, (c) S3 and (d) S4

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Fig. 4 XPS spectra of the coatings: (a) Ti 2p, (b) N 1 s and (c) O 1 s for S2 and (d) O 1 s for TiN covered with ALD-Al2O3. Inset in d is
XPS spectrum of Al 2p
of grains can efficiently improve the structural density of
coatings, which ought to benefit to strengthen the corrosion
resistance of multilayer coatings (Ref 32).
The influences of the inserted ALD-Al2O3 layer on the
surface morphologies of TiN coatings were further investigated.
As shown in Fig. 3(a), the TiN coating deposited via magnetron
sputtering exhibits columnar structure with the average width of
approximately 200 nm, agreed well with the previous reports
(Ref 33). By contrast, the insertion of Al2O3 interlayer leads to
an obviously decreasing column width of the TiN coating.
Thus, we can consider that the addition of the Al2O3 interlayer
results in the columnar refinement of TiN, which has a critical
influence on microstructure and improved mechanical proper-
ties of the metal nitride coating (Ref 11). Based on the Hall–
Petch relationship, columnar refinement makes a critical effect
on strengthening hard coatings. Decreasing column width
caused by the addition of Al2O3 layer would also affect the
roughness of coatings. The roughness of TiN is 33.6 nm. The
insertion of ALD layer causes the declining roughness of the
TiN-Al2O3 composite coating. The decreased roughness is also
ascribed to the columnar refinement due to the addition of the
ALD-Al2O3 inserted layer. Among the TiN-Al2O3 composite
coatings, the sample of S2 has the lowest roughness of
16.5 nm.
Figure 4(a), (b) and (c) shows the XPS spectra of S2
deposited on silicon (100) substrate. As shown in Fig. 4(a), the
Ti 2p3/2 XPS spectrum of the coating is illustrated. After
deconvolution, this spectrum can be fitted into three peaks. The
binding energy at 455.5 eV corresponds to Ti-N bond for TiN
(Ref 34), and the peak located at 456.1 eV refers to the N-Ti-O
bond. N1s XPS spectra are shown in Fig. 4(b). The binding
energy of 396.5 eV is assigned to Ti-N bond for TiN (Ref 35),
while the peaks at 398.3 and 402.0 V are attributed to the N-Ti-
O bond of TiNxOy and nitrogen oxygen adsorbed species (NOx
or Ti-NOx) (Ref 36), respectively. Only one O1s peak exists in
Fig. 4(c), corresponding to the N-Ti-O bond of TiNxOy.
However, there is no peak in the Al 2p region. To further
confirm the existence of Al2O3 interlayer in TiN-Al2O3
composite coatings, TiN directly covered with ALD-Al2O3
layer was used to analyze the chemical states of elements. The
existence of Al2O3 interlayer in the TiN-Al2O3 composite
coating is verified by the peak of O 1s at 530.6 eV as well as Al
2p at 74.4 eV (inset of Fig. 4d), respectively.
3.2 Mechanical Properties
Figure 5(a) shows the hardness (H) and elastic modulus (E)
of coatings tested by the nanoindentation. As given in Table 1,
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H and E of the TiN coating are 8.5 and 165.3 GPa, respectively.
After insertion of an ALD-Al2O3 layer, the H and E values of
the TiN-Al2O3 composite coatings obviously increase. As
discussed above, the addition of Al2O3 interlayer results in
decreasing the column size of TiN coating, which could
improve the hardness of hard coating. Meanwhile, the dense
Al2O3 interlayer can seal its lower defective coating, suppress
the defect proliferation and block the dislocation motion in TiN
layer during the indentation, due to the excellent conformality
over large areas with high-aspect-ratio conformity for ALD
technology. As shown in Fig. 2, the addition of the ALD-Al2O3
interlayer results in the preferred orientation of TiN transforms
from the original (111) to (200) and (220) orientation, which
could deliver better mechanical behavior and lower residual
stress. Thus, the enhanced mechanical properties can be
attributed to the structure densification and decreased crystallite
size. It is interesting that the values of H and E for the ALD-
Fig. 5 Mechanical properties (a) and critical loads (b) of pure TiN
and TiN-Al2O3 composite coating. Inset is the scratch test result of
S2
Table 1 Mechanical properties and surface roughness of the pure TiN and TiN-Al2O3 composite coatings
Coatings Hardness, GPa Elastic modulus, GPa
S1 8.46 165.34
S2 13.65 203.40
S3 11.57 181.04
S4 10.72 178.29
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Al2O3 inserted TiN coating decreases when the insertion
position of ALD-Al2O3 is close to the 316L stainless steel
substrate. S2 exhibits the maximum H, and E values of 13.7
and 203.4 GPa, respectively. As it is known, the plasticity index
of H/E refers to the elastic strain to failure. While the value of
H3/E2 is proportional to the plastic deformation resistance,
which is correlated with the relative wear resistance to a certain
extent. Higher H/E and H3/E2 of the composite coatings indi-
cate a greater wear resistance of the TiN coating after the
addition of ALD-Al2O3 interlayer.
It is worth noting that the adhesion property of coating
with the substrate is one of the important mechanical proper-
ties. Figure 5(b) illustrates the critical loads of crack initiations
(Lc), which were evaluated by the scratch tests. We can see that
the composite coatings deliver larger Lc than that of the pure
TiN coating. Meanwhile, the value of Lc shows an ascending
trend with raising the insertion position of ALD-Al2O3.
According to the definition of Lc, we can speculate that the
addition of ALD-Al2O3 improves the crack resistance of TiN
coating, just as we expected.
3.3 Tribological Properties
Figure 6 shows the friction behavior of TiN and TiN-Al2O3
coatings sliding against SiC balls in 3.5 wt.% NaCl solution.
As shown in Fig. 6, the friction coefficient of TiN increases
gradually and then reaches a steady value of about 0.54. After
the addition of ALD-Al2O3 interlayer, the friction coefficients
of TiN-Al2O3 composite coatings show a descent tendency. In
contrast, a low friction coefficient for the sample S2 is obtained
in the whole sliding friction. Figure 7 shows the mean-steady
friction coefficients and specific wear rates of different
Fig. 6 Friction behavior of coatings sliding against SiC balls in
3.5 wt.% NaCl solution
H/E H3/E2 Roughness, nm
0.0512 0.0221 33.6
0.0671 0.0615 16.5
0.0639 0.0473 20.3
0.0601 0.0388 26.7

Fig. 7 Mean steady friction coefficients (a) and specific wear rates
(b) of tribopairs 3.5 wt.% NaCl solution
Fig. 8 Optical cross-sectional profiles of wear tracks in coatings:
(a) S1, (b) S2, (c) S3 and (d) S4
tribopairs. The friction coefficient and specific wear rate of TiN
are 0.46 and 1.26 9 105 mm3/Nm, respectively. Compared
with the pure TiN coating, the mean-steady friction coefficients
and wear rates of composite coatings decrease. Thus, it can be
demonstrated that the amorphous Al2O3 interlayer deposited by
ALD technology could improve the wear resistance of TiN
sputtered by magnetron sputtering on 316L SS. The addition of
ALD-Al2O3 interlayer results in the refinement of grains, which
could efficiently improve the structural density and mechanical
properties of hard coatings. Among the coatings, S2 exhibits
the lowest friction coefficient of 0.36 and specific wear rate of
1.65 9 106 mm3/Nm, in good agreement with above expec-
tation based on the results of H/E and H3/E2. Additionally, the
corresponding specific wear rate of SiC mating ball is
3.45 9 107 mm3/Nm, lower than those of other samples.
Figure 8 shows the cross-sectional profiles of wear tracks in the
coatings measured by optical profilometer. Compared with pure
TiN coating, the shallow scratches with low width exhibit on
the wear tracks of TiN-Al2O3 composite coatings. A low depth
is about 0.11 lm for the wear tracks of S2 coating, lower than
the thickness of its upper TiN layer. By comparison, the
maximum depth of scratches increased to 0.26 lm for TiN
coating. Therefore, we can conclude that after the addition of
ALD-Al2O3 interlayer, TiN-Al2O3 coatings exhibit superior
friction behavior.
The SEM images and EDS analysis of wear tracks for
coatings are shown in Fig. 9. There are some shallow scratch
lines on the wear track, where some wear debris exists. Thus,
the wear mechanism is dominated by abrasive wear when
sliding against SiC ball. Additionally, the corrosion traces are
obviously observed on the wear tracks, indicating that the
friction accelerates corrosion. By contrast, the wear scar of S2
coating is relatively smooth, which is attributed to the
tribochemical wear. As shown in Fig. 9(d), there is a small
amount of O element observed on the wear track of S2.
According to the previous reports (Ref 7, 25), the hydration
reaction of TiN coating could take place in aqueous environ-
ment, resulting in the formation of TiOx as the lubrication (Ref
25). As discussed above, the addition of ALD-Al2O3 interlayer
results in the transformation from the preferred orientation
(111) of fcc-TiN coating (Fig. 2) with the lowest surface energy
to (200) and (220) orientation. Thus, we estimate that the
transformed orientation may benefit the friction-induced hydra-
tion of TiN. The above discussion about the wear tracks for
coatings indicates that the TiN coatings with ALD-Al2O3
interlayer exhibit the excellent friction and wear properties as
sliding against SiC ball in 3.5 wt.% NaCl solution.
3.4 Corrosion Properties
Figure 10 shows the Tafel plots of as-deposited coatings
after 60 min immersion in 3.5 wt.% NaCl solution. Each
sample shows the behavior of spontaneous passivation then
pitting corrosion. The pitting corrosion potential (Ep) for bare
316L SS substrate is about 80 mV. Compared with the pure
TiN coating, the Ep values of composite coatings show a shift
toward the positive side, indicating better anti-corrosion for the
substrate supplied by the composite coatings. As given in
Table 2, the corrosion current density (Icorr) of the coatings
decreases when compared with the bare substrate, implying that
the coatings prevent the substrate from corrosion with the
chosen corrosive medium. By adding an ALD-Al2O3 interlayer,
a further decrease in Icorr is obtained, as compared with that of
the pure TiN coating, implying the significantly improved
corrosion resistances of coatings result from the insertion of
ALD-Al2O3 layer. The electrochemical porosity (P) of the
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Fig. 9 SEM images and the corresponding EDS analysis of wear track: (a, c) S1 and (b, d) S2

Table 2 Corrosion properties obtained from the Tafel

curves in 3.5 wt.% NaCl solution
Coatings Ecorr, mV Ep, mV Icorr, lA cm22 P, %

316L SS  145 70 2.45 …

S1  283 15 1.06 43
S2  351 95 0.29 9
S3  432 80 0.41 17
S4  493 100 0.63 29

rapidly, indicating that the Al2O3 interlayer significantly

improves the anti-corrosion capability of the TiN coating.
Meanwhile, the porosity decreases as raising the insertion
position of ALD-Al2O3 layer away from the steel substrate and
Fig. 10 Tafel curves of coatings in 3.5 wt.% NaCl solution S2 delivers the lowest porosity.
Figure 11 presents the surface morphologies of the coatings
coated 316L SS can be estimated according to the following after potentiodynamic test in 3.5 wt.% NaCl solution. For the
equation (Ref 2). bare 316L SS, there are many pits with several micrometers in
diameter in Fig. 11(a). As was reported, macroparticles,
Icorr droplets and growth defects probably formed during the PVD
P¼ 0
 100% ðEq 1Þ
Icorr process. The corrosion was proved to selectively occur at such
0 growth defect sites (Ref 35). As shown in Fig. 11(b), there are
where Icorr is the corrosion current density of the bare 316L SS, some corrosion pits with much smaller diameter appeared on
and Is is the corrosion current density of coatings. The porosity the surface of TiN coating, owing to the existence of some
of the pure TiN is only 43%. After inserting the Al2O3 micropores. Some previous reports (Ref 32, 37) confirmed that
interlayer, the porosity of the composite coatings decreases

Journal of Materials Engineering and Performance


Fig. 11 SEM images after the polarization of (a) 316L SS, (b) TiN
and (c) TiN-Al2O3-coated samples
the oxide products were dominated by the titanium compounds
in the corroded area of TiN. The addition of ALD coating could
reduce corrosion current density, due to the sealing of pinholes.
Even after the complete removal, the corrosion current density
of worn hybrid PVD/ALD coatings is still less than half, as
compared with the CrN coating without any wear (Ref 38).
Compared with the TiN coating, it is obvious that the TiN-
Al2O3 coating (S2) shows a few pitting failures after the
potentiodynamic test, indicating that the oxidation reaction is
reduced. As discussed above, the addition of ALD-Al2O3
Fig. 12 Schematic diagram for the possible corrosion mechanism
of TiN-Al2O3 composite coating
interlayer would result in the block of columnar structure and
refinement of grains, which could efficiently improve the
structural density of coatings, benefit to strengthen the corro-
sion resistance of multilayer coatings. Therefore, we can
conclude that the TiN-Al2O3 coating delivers the enhanced
anti-corrosion behavior, in well agreement with the above
polarization analysis.
According to the analysis of microstructure and corrosion
behavior, the schematic illustration for improved anti-corrosion
behavior of the TiN coating after ALD-Al2O3 insertion on 316L
stainless steel is shown in Fig. 12. Because of the line transfer
of vapor flux for magnetron sputtering (Ref 11), the metal
nitrides usually deliver some intrinsic defects such as pinholes,
which could seriously deteriorate the anti-corrosion behavior of
coatings. For example, as exposed in the corrosion environ-
ment, pinholes extended through the coating can accelerate the
corrosion of the substrate. The special growth mechanism of
ALD leads to the dense films that are excellent conformality,
uniformity with a low defect density, on surfaces even on
challenging 3D morphologies. Thus, ALD-deposited coatings
can cover the pinholes, even the pinholes are extremely deep
with high-aspect-ratio (Ref 23). Such improved anti-corrosion
properties of the TiN-Al2O3 composite coatings are ascribed to
two main reasons. The ALD-Al2O3 layer with poor electrical
conductivity can improve the corrosion resistance of the
coating and prevent the charge transfer, leading to the decrease
in the corrosion current. On the other hand, the dense Al2O3
layer acts as a sealing layer to obstruct the diffusion of
corrosive medium through the defects in coatings, e.g.,
pinholes, and protect the metal substrates.
When the friction tests were performed in an aggressive
solution such as seawater and 3.5 wt.% NaCl solution, the
interaction of wear and corrosion led to an irreversible
deterioration of materials as a result of the simultaneous
interactions between physic-chemical and mechanical pro-
cesses. It is well-known that a passive layer of few nanometers
thick would be formed on the coatings, when immersed in
aqueous solutions (Ref 38). This passive layer is protective in
the presence of corrosive electrolytes. However, it easily breaks
down in the sliding condition. The corrosive species in the
aggressive electrolyte can easily penetrate into coatings even
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the substrate. Thus, it can be seen in wear accelerates corrosion.
Acting as a sealing interlayer, the dense ALD-Al2O3 layer can
hinder the corrosive species from penetrating into the bottom
layer of the composite coating, resulting in improved anti-
corrosion properties of the composite coating. Even after the
complete removal of the ALD coatings, the corrosion current
density of worn hybrid PVD/ALD is still less than that of CrN
coating without any wear (Ref 23).
4. Conclusions
In summary, TiN-Al2O3 composite coatings were deposited
by combining PVD and ALD techniques. By inserting a dense
ALD-Al2O3 interlayer, the grain size and surface roughness of
the TiN coatings decrease. The improved tribological properties
can be ascribed to the addition of ALD-Al2O3 layer with few
defects, which results in the change of crystal structure and
improves the mechanical properties of hard coating. Addition-
ally, the insulating Al2O3 interlayer can block the charge
transport in coatings, and decrease the corrosion current
density. Meanwhile, the dense ALD-Al2O3 layer with high-
aspect-ratio conformity used as a sealing layer can also inhibit
the diffusion of corrosive media through the defects, e.g.,
pinholes to corrode the substrates. Thus, the TiN-Al2O3 coating
exhibits superior anti-corrosion properties. Moreover, when the
insertion position of Al2O3 interlayer is near the surface of
coating, a further improvement in the tribological and anti-
corrosion properties of TiN-Al2O3 composite coating can be
obtained.
Acknowledgments
This work is financially supported by ‘‘the Fundamental
Research Funds for the Central Universities’’, No. NS2017030.
We would like to acknowledge it for the financial support.
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