Surface & Coatings Technology 366 (2019) 355–365

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Surface & Coatings Technology

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

Characterization and corrosion behaviors of TiN/TiAlN multilayer coatings T

by ion source enhanced hybrid arc ion plating
⁎ ⁎
Gui Lia,b, Lin Zhanga, , Fei Caia, Ying Yanga, Qimin Wanga,c, Shihong Zhanga,b,
a
Research Center of Modern Surface & Interface Engineering, Anhui University of Technology, Maanshan 243002, China
b
School of Materials Science and Engineering, Anhui University of Technology, Maanshan 243002, China
c
School of Electromechanical Engineering, Guangdong University of Technology, Guangzhou 510006, China

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

Keywords: TiN/TiAlN multilayer coatings with various bilayer numbers were deposited on AISI 410 martensitic stainless
TiN/TiAlN steel using ion source enhanced hybrid arc ion plating system. The influences of different bilayer numbers on
Multilayer structure, mechanical properties and corrosion behaviors of TiN/TiAlN multilayer coatings were investigated
Mechanical properties comparatively. The as-deposited coatings were predominantly composed of fcc-TiN and solid solution (Ti, Al) N
Corrosion behaviors
phases with (111) preferred orientation, and the growing tendency towards preferential orientation decreased as
the increase of bilayer numbers. With increasing bilayer numbers, microhardness of the coatings was enhanced
gradually for the increased interfaces and refined crystals, reaching a maximum of 3800 HK0.025 at the coating
with 12 bilayers. Multilayer coatings exhibited an abrasive wear mechanism against WC pair, and possessed an
excellent tribological performance in comparison to MSS substrate. According to electrochemical results, the
coating with bilayer number of 12 presented a high free corrosion potential combined with the lowest corrosion
current density, highest polarization resistance, highest protective efficiency and largest charge transfer re-
sistance than that of other bilayer numbers owing to the increased layered interfaces and high structural density.

1. Introduction coatings. On one hand, these kinds of monolayer nitride coatings ex-
hibit inferior fracture and corrosion resistance due to the existence of
Martensitic stainless steels (MSS) have been extensively applied in columnar microstructure and defects like micro-cracks, pinholes, pores
turbine blades, valve parts and stem rods because of good compre- and transient grain boundaries which offer the guided diffusion path-
hensive mechanical properties and moderate corrosion resistance ways for the corrosive medium [8]. On the other hand, different cracks
[1–3]. When utilized as compressor blades in gas turbine engine at the will be easily initiated and expended by impacting of solid particles
marine environment, they are serving under harsh working conditions because of high residual stress existing in monolayer coatings. These
such as numerous solid particles erosion and pervasive corrosion, re- penetrated cracks become a direct pathway for the corrosion media and
sulting in horrible pitting corrosion and even failure. Jasiczek et al. lead to a failure of coatings as well.
have pointed out that pitting corrosion had a critical influence on the In order to overcome above mentioned coating-growth defects,
fatigue and fracture behaviors of MSS compressor blades [4]. These some attempts have been carried out to obtain desirable coatings with
corroded pits trigger plenty of fatigue cracks on the leading edge and higher corrosion resistance, such as designing multilayered coatings.
enforce the propagation of cracks during service operation. The rate of Compared with monolayer coatings, layered interfaces within the
penetration into the metal induced by pitting corrosion is from 10 to multilayered coatings parallel to coating surface can effectively sup-
100 times larger than that by general corrosion. Additionally, since the press the growth of defects, and further strengthen the coatings' ability
compressor blades serve under marine circumstance, the pitting cor- against the corroded media [9–12]. In addition, increasing coating
rosion is greatly reinforced with solid particle impact. thickness is another path to enhance the corrosion resistance of nitride
One effective technique to protect the blades from pitting corrosion coatings. Chou et al. have figured out that the coating density was in-
is to apply physical vapor deposition (PVD) hard nitride coatings, for deed increased with the increase of thickness [13]. However, the in-
instance TiN [5], CrN [6], and TiAlN [7] coatings. However, the ero- creasing thickness will result inevitably in losses in both adhesion
sion-corrosion process easily induces the failure of the monolayer strength and wear resistance and an increase in coating brittleness due

⁎
Corresponding authors.
E-mail addresses: zhanglin_dut@163.com (L. Zhang), tougaoyouxiang206@163.com (S. Zhang).

https://doi.org/10.1016/j.surfcoat.2019.03.027
Received 10 December 2018; Received in revised form 17 February 2019; Accepted 12 March 2019
Available online 20 March 2019
0257-8972/ © 2019 Elsevier B.V. All rights reserved.
G. Li, et al. Surface & Coatings Technology 366 (2019) 355–365

Table 1 enhanced hybrid arc ion plating system using two pure Titanium
Deposition parameters of TiN/TiAlN multilayer coatings. (99.9%) targets and two titanium‑aluminum alloy targets with 30 at.%
Parameters Values Al composition. AISI 410 martensitic stainless steel, manufactured into
a size of 20 mm × 20 mm × 6 mm, was used as the substrate. These
Deposition pressure (Pa) 2.0 steel substrates respectively were ground, polished, and cleaned ultra-
Deposition temperature (°C) 450
sonically in ethanol for 30 min, then blown dry and put on the rotating
Substrate bias (V) −80
N2 flow rate (sccm) 400
substrate holders to which the substrate-to-target distance was keeping
Arc current of Ti targets (A) 140 on 250 mm from the target plane. Prior to deposition, the substrates
Arc current of TiAl targets (A) 150 were preheated to 450 °C and the base pressure was kept below
Bilayer numbers 2 bilayers 4 bilayers 6 bilayers 12 bilayers 1 × 10−3 Pa over 30 min. The substrates were sputter cleaned in Ar
Deposition time of Ti targets 60 30 20 10
plasma at 4.0 Pa pressure with a bias of −400 V for 10 min. Then the
(min)
Deposition time of TiAl targets 30 15 10 5 ion source cleaning was performed to enhance the adhesive strength
(min) between coatings and substrates, which was reported elsewhere [18].
Total deposition time (min) 180 At the cleaning procedure, Ar gas was ionized assisted by using a ro-
tating cathode of Ti target with a shield plate, which would create a
highly efficient argon etching for substrates. During the coating de-
position, four groups of TiN/TiAlN multilayer nitride coatings were
prepared with various bilayer numbers (2, 4, 6, and 12 bilayers) but
similar overall thickness. In each bilayer TiN was deposited firstly, and
then the TiAlN layer. The detail deposition parameters were listed in
Table 1.

2.2. Phase analyses and microstructure

Crystallographic phases and preferential orientations of the as-de-

posited coatings were characterized by a Bruker D8 advance X-ray
diffractometer with Cu K(alpha) radiation under 2θ scan mode varying
from 10° to 90° at a scan speed of 10°/min. Transmission electron mi-
croscopy (TEM, FEI Tecnai G2 F20) was used to further investigate their
microstructures. The chemical composition of these multilayered
structures was precisely obtained by energy dispersive X-ray diffraction
(EDX). Scanning electron microscope (SEM, JSM-6490LV) was as well
utilized for identifying their thickness and surface morphology.
Moreover, surface roughness was measured in quantitative analysis
using an Alpha-Step IQ surface profiler (KLA-Tencor P7).
Fig. 1. XRD patterns of the multilayer TiN/TiAlN coatings.
2.3. Coating adhesion, hardness and wear
to high residual stress. The thickness of coatings must be reasonably
limited (usually no more than 8 μm). To meet a high requirement of The adhesive strength between the multilayer coatings and sub-
intensive wear and corrosion resistance of gas turbine engines com- strates was assessed using a Rockwell tester under a condition with 15 s
pressor blades, the protective coatings are desired to have high adhe- dwelling time and 150 gf loads. Besides, the surface microhardness
sion strength, wear resistance and excellent corrosion resistance [14]. measurements were performed on a Knoop hardness tester with dif-
Some investigations are already carried out. W. Aperador et al. have ferent loads ranging from 25 to 1000 gf. Additionally, tribological
explored the electrochemical property of TiN/TiAlN multilayer coatings properties of these coatings and the substrate were explored in a ball-
deposited using magnetron sputtering technique, and concluded that on-disk tribometer (CSM HT1000, CSM Instruments, Switzerland). The
corrosion resistance of coatings under corrosion-erosion condition was wear counterpart was WC balls with diameter of 6 mm. The wear tests
improved with increasing of bilayer numbers, which in consist with the were carried out at a total time of 3600 s, a rotational speed of 500 r/
research by J.C. Caicedo [15–16]. E. Alat has utilized cathodic arc PVD min, and a load of 5 N under dry sliding condition at room temperature.
to deposit TiN/TiAlN multilayer coatings, while figured out that 8-layer Worn tracks were analyzed using the step profiler and SEM with an
coatings exhibited the best corrosion performance [17]. electron-dispersive spectrometer (EDS) for compositional analysis.
In the present work, a combination of multilayered structure and
thick coating can be used to enhance the wear resistance and corrosion 2.4. Electrochemical analysis
resistance for protecting the MSS compressor blades. Four types of thick
TiN/TiAlN multilayer coatings were deposited on AISI 410 martensitic Corrosion behaviors of the coated specimens were determined via
stainless steel by ion source enhanced hybrid arc ion plating. A com- potentiodynamic polarization examinations and electrochemical im-
parative study was carried out on the effects of bilayer numbers on the pedance spectroscopy (EIS) measurements using a parstat 4000 po-
structure, mechanical properties and corrosion behaviors of multilayer tentiotat/galvanostat EIS analyzer (Princeton Applied Research &
coatings by means of XRD, SEM, TEM, hardness tester, ball-on-disk AMETEK Company) in the 3.5% NaCl solution. Versastudio software
tribometer, and electrochemical measure in 3.5% NaCl solution. and ZSimpWin software were utilized to analyze potentiodynamic po-
larization and EIS data, respectively. A three-electrode system was ap-
plied to the electrochemical tests, which composed of a platinum aux-
2. Materials and methods iliary electrode, a saturated calomel (SCE) reference electrode and a
working electrode (specimen). Specimens were immersed for 1 h in the
2.1. Substrate material and coating deposition electrolyte until the undulation of potential was reduced to below
1 mV/min, and then regarded this potential as the open circuit potential
The TiN/TiAlN multilayer coatings were deposited by ion source (OCP). Tafel polarization curves were measured at a scan speed of

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Fig. 2. Cross-sectional TEM images of the multilayer TiN/TiAlN coating with 12 bilayers: (a) Bright-field image, (b) Dark-field image with inserted elemental
concentration profiles, (c)HRTEM micrograph, and (d) IFFT image and SAED micrographs.

0.5 mV/s and the relating voltage checked between −0.3 and + 0.3 V detected in these coatings. Additionally, the intensity of (Ti, Al) N and
under an exposed region of 1 cm2. Impedance measurement was carried TiN (111) peaks are decreased gradually with increasing the number of
out on a frequency response tester, and the spectrum was recorded at a bilayers, which is related to the decrease of bilayer thickness [11].
frequency region ranging from 0.01 Hz to 100 kHz. A 10 mV sinusoidal Aimed at further investigating the microstructure of as-deposited
amplitude and differential electrometer mode were utilized. Finally, the coatings, TEM analysis was carried out. For obtaining more information
corroded surface morphologies and corrosion products of the multilayer about the interfaces and laminate structures, the multilayered coating
coatings and bare substrate were characterized by SEM and EDS, re- with 12 bilayers is selected. Fig. 2 displays the cross-sectional TEM
spectively. photographs of the picked coatings. It is clearly seen that columnar
grains grow through several bilayers. Whereas several columnar grains
stop growing on the interfaces, and some others start on it, pointed by
3. Results
white arrows in Fig. 2(a). More interfaces provide more opportunities
for nucleation of crystals, which can restrain and block the columnar
3.1. Structure analysis
growth and result in a refinement of the grain size. The dark-field image
exhibits precisely the laminated structure of TiN layers (brighter) and
Fig. 1 presents the XRD patterns of TiN/TiAlN multilayer coatings
TiAlN layers (darker), as given in Fig. 2(b). It is worth to note that the
prepared onto the AISI 410 substrate with different bilayer numbers.
TiAlN sublayers are much thicker than TiN sublayers, which is brought
Except for Fe diffraction peaks from steel substrate, (111), (200), (220),
about a lower melting point of TiAl alloy and a higher arc current of
(311) and (222) diffraction peaks are identified from these coatings. In
TiAl targets than that of Ti targets. The composition of each layer is
this present work, diffraction peaks of the coatings are well in ac-
measured using the TEM line scanning technique and given in the inset
cordance with the standard TiN diffraction peaks. No AlN peak is

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Fig. 3. Cross-sectional SEM images of the TiN/TiAlN multilayer coatings: (a) 2 bilayers; (b) 4 bilayers; (c) 6 bilayers; (d) 12 bilayers.

of Fig. 2(b). The ratio of Ti:Al is about 4:1 on the TiAlN layer, and cathode targets [19]. The surface roughness Sa of multilayer coatings is
without diffusion of Al element from the TiAlN layer to TiN layer. From approximately 400 nm measured by Step Profilometer.
high resolution transmission electron microscopy (HRTEM) photograph
in Fig. 2(c), it can be seen that the as-deposited coatings have a well- 3.2. Mechanical and tribological properties
crystallized behavior corresponding to the XRD results. The IFFT mi-
crograph precisely ensures a coherent relationship between TiN and The adhesive capabilities of coatings were evaluated using Rockwell
TiAlN sublayers, and the interplanar distance of TiN layer is 0.218 nm C indentation test according to the VDI 3198 norm [20]. Fig. 5 shows
larger than 0.204 nm of TiAlN layer, presented in Fig. 2(d). This pho- Rockwell indents on the coated steel. It can be seen that several radial
tograph also displays different orientations appeared in the TiN/TiAlN cracks only exist around Rockwell crater (HF2) in the case of 12 bi-
interface. layers (other coatings exhibit similar behaviors), indicating that the as-
Fig. 3 presents the cross-sectional SEM morphologies of the multi- deposited coatings possess excellent adhesion strength between the
layer coatings. It can be seen that the coatings' density is improved with coating and substrate [21]. Fig. 6 shows surface microhardness of the
increasing the bilayer numbers. Thicknesses of coatings with bilayer multilayer TiN/TiAlN coatings under different loads. The microhard-
number of 2, 4, 6, and 12 are 7.34 μm, 6.57 μm, 6.83 μm, 6.97 μm, ness of the coatings reduces gradually with the increase of indention
respectively. The typical surface morphologies are given in Fig. 4. It is load because of the substrate effect. With increasing the number of
found that plenty of droplets and particles appear on the surface of bilayers the microhardness of as-deposited coatings increases under the
these coatings originated from the droplets emitted by arc spots in the same load, reaching a maximum of 3800 HK0.025 in the case of coating

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Fig. 4. Surface morphologies of the TiN/TiAlN multilayer coating with bilayer number of 12: (a) SEM image; (b) profile image.

Fig. 5. Rockwell crater in the case of multilayer coatings with bilayer number of 12.

Fig. 6. Microhardness of the multilayer TiN/TiAlN coatings with different loads.

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Fig. 7. Friction coefficients (a) and wear track profiles (b) of the TiN/TiAlN multilayer coatings.

Table 2 to substrate by means of diffusion and penetration through the defects

Wear volume and wear rate of the TiN/TiAlN multilayer coatings. on the coatings [22]. With increasing the number of bilayers, the dif-
Specimens Wear volume Wv(m3) Wear rate K (m3/N⋅m)
fusion time is increased. This can be explained that the interfaces play a
significant role in restraining the transport of electrolytes. After the
Substrate 1.26E-11 1.34E-14 solution arrived at inner steel, a drastic decrease of OCP values is de-
2 bilayers 0.49E-11 5.16E-15 tected, and all of the coatings' potential is shifted towards the cathodic
4 bilayers 0.33E-11 3.51E-15
6 bilayers 0.62E-11 6.57E-15
direction. The last one is the equilibrium period for substantiating that
12 bilayers 0.58E-11 6.11E-15 the surface of the coatings has reached a steady condition, and its
equilibrium value is close to the free corrosion potential which derived
from Tafel extrapolation [23].
with bilayer number of 12. Fig. 10 presents the potentiodynamic polarization curves of the
Friction coefficient of coated and uncoated specimens against WC multilayered coatings in a 3.5% NaCl solution. Their related corrosion
ball as a function of sliding time is presented in Fig. 7(a). The specimen potential Ecorr(mV) and current density Icorr(μA/cm2) are evaluated
of 4 bilayers possesses the highest value of friction coefficient (ap- using an intersection of extrapolation method at the Tafel curve's strong
proximately 0.7) almost in similar with the uncoated one. Fig. 7(b) polarization zone. The protective efficiency P (%) of these specimens
shows wear track profilers of coated and uncoated specimens. Depth of can be estimated by Eq. (2).
wear tracks of coated specimens is about 2–3 μm much less than the
0
coating thickness, indicating that the overlapped coatings is not worn- P = (1 − Icorr / Icorr ) × 100% (2)
out. The wear rate was calculated using the Eq. (1) according to the
wear track profilers and given in Table 2 [10] where Icorr and Icorr0 are represented by the corrosion current density of
the coatings and substrate, respectively [24]. Their corresponding va-
WV
K= lues of Ecorr and Icorr (listed on Table 3) convey that free corrosion po-
L × sd (1)
tentials of these coated specimens are shifted to a nobler direction with
3
where L is the load (N), Wv is the wear volume (m ), s is the distance corrosion current densities to lower. As can be seen in the Table 3, the
per circle, and d is the number of circles. It is found that all coatings corrosion current density is decreased and polarization resistance in-
show lower wear rate than substrate specimen, and the lowest wear rate creased with increasing bilayer numbers. The coating with bilayer
of K = 3.51 × 10−15 m3/N·m is obtained in the coating with 4 bilayers. number of 12 possesses the lowest corrosion current density of 2.08 μA/
Fig. 8 shows SEM observation on the wear track surfaces after being cm2and the largest polarization resistance of 2.32 × 104 Ω·cm2. The
tested against WC ball. In the case of steel substrate, shallow craters are protective efficiency of the multilayer coatings, 2 bilayers, 4 bilayers, 6
observed on the wear scar in Fig. 8(a). Its wear track surface consists bilayers and 12 bilayers, is about 84.11%, 86.19%, 88.37% and 91.25%
mostly of O element checked by EDS. Meanwhile, a large amount of W respectively.
element is transferred and adhered onto the substrate surface from WC The Nyquist plots of multilayer coatings and substrate were de-
ball. The typical ploughing and plastic deformation following the termined using EIS technique, as shown in Fig. 11. For these multilayer
sliding direction appear on the worn surfaces of coatings, shown in coatings, their semicircles of impedance curves intend to broaden by
Fig. 8(b~d). After checking the composition of worn surface, there is no adding the bilayer numbers, countering to their relating corrosion rates.
evidence of transformation of the WC ball material onto the wear track The simulated equivalent circuit for the substrate and the four types of
with small amounts of O and C elements. multilayer coatings are clearly displayed in Fig. 12(a) and (b) respec-
tively, in which Rs represents the electrolyte resistance from the
3.3. Electrochemical behaviors working to reference electrodes. Cc/1 and Rp stand for the capacitance
and the charger transfer resistance of coatings owing to the existence of
Open Circuit Potential (OCP) measured with the immersion time corroded ionic convection defects across the coating or oxide films on
became a simple qualitative method to explore the corrosion behavior the substrate surface. Cd1 is the double electric layer capacitance re-
of material. Fig. 9 provides the OCP spectra of the multilayer coatings lated to the electrochemical progress occurring in the interface of
and substrate. As it shown, the coatings maintain a nobler potential substrate/solution, whilst Rt also expresses its related charger transfer
than the uncoated stainless substrate. The OCP spectra of the coatings resistance. Fig. 13 presents the bode plots (lg|Z| vs lgf) and (phase angle
can be divided into three periods. The first period, regarded as diffusion vs lgf) of as-deposited coatings and substrate. The impedance at the
time, is the duration for transiting of electrolytes from coatings surface high-frequency region is corresponded to the resistance of the solution,

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Fig. 8. SEM images of the wear track surfaces of the TiN/TiAlN multilayer coatings: (a) substrate, (b) 2 bilayers, (c) 4 bilayers, and (d) 12 bilayers.

while at the low frequency to total resistance. It is found that the extremely thinner and easier to be broken than the coating.
coating with bilayer number of 12 possess the highest charge transfer Pitting corrosion is always occurred at the sites of grain boundaries
resistance, as testified in Fig. 13(a). The plots show two time constants and inclusions, which not only appears on the outmost surface of ma-
representing the capacitive response of double layer and coatings in terial, but penetrates into inner part [25]. Fig. 14 depicts the corrosion
Fig. 13(b). One time constant in higher frequencies stands for the cor- morphology of MSS after checking the Tafel and EIS properties. As can
rosive reaction in the electrolyte/coating interface for coated specimens be seen that there are several corroded sites existed on the surface,
and the electrolyte/oxide film interface for uncoated one, and another which might trigger the development of stress corrosion cracks and
time constant at lower frequencies for the electrolyte/substrate inter- then result in the degradation of components. However, after depos-
face. The related fitting-well value for each element in the equivalent iting the coatings, pitting corrosion issues can be restrained efficiently.
circuit obtained using Zview software is given in Table 4. As can be The corroded surface morphologies of coatings after polarization re-
concluded, the resistance of charge transfer is sharply enhanced and the action are shown in Fig. 15. There are some corrosion pores appeared
capacitance decreased with the addition of bilayer numbers. What's on the coating surface owing to the existence of some micro-pores and
more, the Rp and C1 of the substrate are much lower than that of these particles. Some particles are peeling off because of the attacks by
coatings, because the oxide film overlapped on the substrate surface is electrode and current. From EDS analysis of corroded area, it can be

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Fig. 11. Electrochemical impedance spectroscopy (EIS) of the TiN/TiAlN

Fig. 9. Open circuit potential evaluation with the immersion time of the mul- multilayer coatings in 3.5% NaCl solution.
tilayer coatings and substrate in 3.5% NaCl solution.
atoms to establish the fcc-TiN phase, and the Al atoms are solitude into
TiN phase to form solid solution fcc- (Ti,Al)N phase[27,28]. These
coatings display (111) preferred orientation due to this plane possesses
the lowest surface energy in the fcc structure, which is considered as a
typical characteristic for the coatings deposited by arc ion plating
technique [29]. The block of columnar structure and refinement of
grains can efficiently improve the structural density of coatings, which
ought to be benefited for strengthening the hardness and corrosion
resistance of multilayer coatings. No obvious difference are observed in
SAED patterns among TiN layer, interface, and TiAlN layer, while some
extra diffraction spots appeared in TiAlN layer might be induced by the
solution of Al atoms. The Al atoms can not only provide a solution
strengthening, but be useful for a great wear and corrosion resistance.
Some previous reports have pointed out that the presence of Al atoms
could be benefit for the wear resistance because of the formation of
Al2O3, and its ability to resist wear is much higher than that of TiN or
TiO2 [30]. When soaking in the electrode, Al atoms can form a very
dense and strong adhesive Al2O3 passive film to improve the corrosion
resistance [28].
The as-deposited multilayer coatings exhibit a high adhesive
Fig. 10. Potentiodynamic polarization of the TiN/TiAlN multilayer coatings in
strength, and their surface hardness is improved with increasing bilayer
3.5% NaCl solution.
numbers. According to previous reports, the variation of hardness can
be illustrated conventionally by grain refinement, widen interfaces of
Table 3 layers and more random-oriented microstructure in the crystallographic
Potentiodynamic polarization data of the TiN/TiAlN multilayer coatings in
direction [31,32]. In terms of the finer crystal structure, an improve-
3.5 wt% NaCl solution.
ment of microhardness can be corresponding with Hell-Petch relation-
Specimens Ecorr (mV) Icorr (μA/ βa(V/dec) βc (V/dec) Rp (Ω·cm2) P (%) ships [33]. M.K. Samani has pointed out that the multilayer deposition
cm2) prevented the growing of columnar structure and refines the crystal-
Substrate −435.07 23.83 0.147 0.408 1.97E03 –
lographic grains [31].The interfaces with some random orientations, as
2 bilayers −312.54 3.78 0.231 0.271 1.43E04 84.11 some barriers, impede the extension of crack or dislocation when im-
4 bilayers −200.52 3.28 0.192 0.342 1.63E04 86.19 planting of some hard objects [34].
6 bilayers −306.03 2.77 0.212 0.253 1.81E04 88.37 The frcition coefficient curves of these specimens can be char-
12 bilayers −280.05 2.08 0.618 0.335 2.32E04 91.25
acterized by two stages: friction coefficient increases harshly at the first
period (before 200 s) as a result of the contact stress variations and the
roughness of the surface, after that a steady state with lower friction
seen that oxide products of the oxidation-reduction reaction are
coefficient is followed [31]. The reduction of friction coefficient before
dominated by the titanium and aluminum compounds without that of
reaching a plateau probably relates to wear away the particles or pits on
the inner substrate.
the contacted plane. The multilayer coatings exhibit narrower and
shallower wear scars than substrate, indicating the tribological beha-
4. Discussion
vior of martensitic stainless steel is enhanced by applying TiN/TiAlN
multilayer coatings. From the EDS analysis of wear tracks, the typical
All the detected diffraction peaks of multilayer coatings should
oxidation wear and adhesive wear can be used to explain the tribolo-
belong to TiN or solid solution (Ti, Al) N phases. The bonding energy of
gical behavior for uncoated surface, while the abrasive wear is main
TiN (ΔH nitride = −305.6 kJ/mol) is lower than AlN (−241.6 kJ/mol)
wear mechanism for these ceramic coatings.
in Ti, Al and N system, as reported by R. Mientus et al. [26]. Therefore,
The coatings' OCP values are nobler in comparison with the
during the deposition procedure N atoms are primarily reacted with Ti

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Fig. 12. Equivalent circuits for (a) substrate and (b)

TiN/TiAlN multilayer coatings system.

Fig. 13. Nyquist diagram (a) and bode plots (b) of the coatings and substrate in 3.5% NaCl solution.

Table 4 substrate, indicating that the origination of corrosion in these coatings

Parameters extracted from the EIS data of TiN/TiAlN multilayer coatings cor- is much difficult. Thus, the multilayer coatings exhibit a higher with-
roded in 3.5 wt% NaCl solution. standing for corrosive media. Normally, corrosion resistance is corre-
Specimens Rs (Ω·cm2) Cc (F/cm2) Rc (Ω·cm2) Cd1(F/cm2) Rt (Ω·cm2) lated to the corrosion rate which has a positive connection with po-
larization resistance or charge transfer resistance but negative with
2 bilayers 29.02 3.71E-05 5554 9.34E-05 1.03E04 corrosion current density. Based on Tafel and EIS results, the corrosion
4 bilayers 24.47 4.39E-05 5348 9.28E-05 1.51E04
resistance of TiN/TiAlN multilayer coatings develops continually as the
6 bilayers 23.56 4.43E-05 5714 6.92E-05 2.24E04
12 bilayers 25.96 3.52E-05 5514 5.75E-05 6.18E04 increase of bilayer numbers. Anti-corrosion capability of multilayer
Substrate Rs (Ω·cm2) C1(F/cm2) Ro (Ω·cm2) Cd1(F/cm2) Rt (Ω·cm2) coatings increases with bilayer numbers, which might be owing to the
32.43 1.16 E-04 134.90 2.72E-04 2.61E03 improvement of structure density and number of interfaces. The
structural density of coatings is improved by reducing the growth-

Fig. 14. SEM and EDS observation of the substrate after corrosion tests.

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Fig. 15. The corroded surface morphologies of coatings after polarization reaction: (a) 2 bilayers, (b) 4 bilayers, (c) 6 bilayers, and (d) 12 bilayers.

defects like droplets and suppressing the columnar structure, which can results clarified that the coatings with 12 bilayers possessed the
restrain the permeation of corroded media and then improve the anti- lowest corrosion current density, highest protective efficiency, and
corrosion ability. The laminated structure provides more interfaces largest polarization resistance and charge transfer resistance. The
with several random orientations inward coatings, can still be useful for corrosion resistance is improved with increasing the bilayer num-
restraining the transformation of charge in electrochemical tests. From bers, which was attributed to the dense microstructures and inter-
the results of bode plots, resistance loop does not appear at the phase facial barriers.
angle in very low-frequency region, indicating no diffusive behavior
occurred because of the short immense time [35]. According to Oli- Acknowledgment
veira's reports, the material surface in contact with corrosion electrolyte
is more stable when appearing a higher phase angle and broader range This study was sponsored by the National Science Foundation of
of frequencies [22]. That is to say, the multilayered coated specimens China (Grant no. 51522502) and Anhui Provincial Key Research and
with 12 bilayers hold more stable properties and higher corrosion re- Development Program (Grant no. 1804b06020370).
sistance in comparison with other coated ones when soaking in the
artificial 3.5% NaCl aqueous solution. This might also be attributed to References
the high structural density and more interfaces.
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