Surface & Coatings Technology 433 (2022) 128094

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Surface & Coatings Technology

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

Mechanical, oxidation, and cutting properties of AlCrN/AlTiSiN

nano-multilayer coatings
Baijun Xiao a, *, Teng Fei Zhang b, *, Zhu Guo a, Zhou Li a, Bin Fan a, Ganxin Chen a,
Zhihong Xiong a, Qimin Wang b
a
School of Electromechanical Engineering, Hunan City University, Yiyang 413099, China
b
School of Electromechanical Engineering, Guangdong University of Technology, Guangzhou 510006, China

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

Keywords: The design of multilayered structure is a promising way to tailor the microstructure and properties of the hard
AlCrN/AlTiSiN coating coatings. In this study, AlCrN, AlTiSiN and nano-multilayer AlCrN/AlTiSiN coatings were deposited and their
Nano-multilayer microstructure, mechanical, oxidation and cutting properties were comparatively investigated. The results
Mechanical properties
showed that the AlCrN/AlTiSiN coating, possessing two phase and denser microstructure, showed improved
Oxidation resistance
hardness (39.4 GPa) and adhesion strength, as compared with the AlCrN and AlTiSiN coatings. The AlCrN/
Cutting performance
AlTiSiN coating also exhibited excellent oxidation resistance up to 1000 ◦ C and its oxidation scale was composed
of a thin and dense Al-rich oxide, due to the multilayer structure acted as an effective barrier to block elemental
diffusion to retard the oxidation process. In the turning tests for SKD11, the AlCrN/AlTiSiN coating demonstrated
good tool life (~800 m), which should be attributed to its higher hardness, good adhesion strength and oxidation
resistance, as compared with the monolithic AlCrN and AlTiSiN coatings.

1. Introduction
AlCrN and AlTiSiN nitride coatings are well acknowledged as wear-
resistant coatings for many industrial machining tools due to their
excellent properties [1–6]. The significant advantage of AlCrN coatings
is their good oxidation resistance up to 1000 ◦ C [7], which can form
dense oxide layer composed of Cr- and Al-rich oxide mixture and show
significantly protective effect by retarding outward diffusion of metal
ions and inward diffusion of oxygen at elevated temperatures [8,9].
However, the formation of wurtzite AlN (w-AlN) and N-loss of AlCrN
coatings at high temperatures significantly degrade their thermal sta­
bility, which limits their applications at working temperature over than
900 ◦ C [10,11]. In addition, AlCrN coatings possess relatively low
hardness, which is disadvantage for wear protection. On the other hand,
the AlTiSiN coatings, with AlTiN nano-crystalls embed into amorphous
Si3N4 phase matrix, typically show high hardness (>40 GPa) and good
thermal stability up to 1000 ◦ C [12–15]. The amorphous Si3N4 grain
boundaries in the nc-AlTiSiN/a-Si3N4 nanocomposite structure of AlTi­
SiN coatings can improve their oxidation resistance to a certain extent
[16]. However, the anti-oxidation capacity of AlTiSiN coatings reduces
rapidly as the oxidation temperature increases to more than 900 ◦ C [17].
To meet the increasing demands of coatings with high hardness, high
thermal stability and good oxidation resistance for high-speed cutting
and dry machining technologies [18,19], some novel coating concepts,
such as multicomponent [20–23] and multilayer architecture [24–26],
have been put forward and widely applied to industry. Among them,
multilayer-structured coatings with alternating two or more different
sublayer materials, have attracted increasing interests due to their great
potential for enhancing the comprehensive properties of the coatings,
which is also one simple and reliable method for industrial applications
[27,28].
AlCrN-based multilayer coatings have been widely reported, such as
AlCrN/TiVN [29], AlCrN/TiAlN [30–32], and AlCrN/ZrO2 [33], Espe­
cially, the AlCrN/AlTiSiN multilayer coatings have drawn great atten­
tion, which combines both high hardness and high thermal stability of
AlTiSiN and good oxidation resistance of AlCrN. However, the oxidation
properties and cutting performance of AlCrN/AlTiSiN multilayer coat­
ings have not been well explored. Therefore, in the present work, the
AlCrN and AlTiSiN monolayer coatings, and AlCrN/AlTiSiN multilayer
coating with a modulation period of ~11.6 nm were deposited on both
Al2O3 and carbide substrates. The microstructure, oxidation resistance
and cutting performance of these coatings were comparatively

* Corresponding authors.
E-mail addresses: beijunxiao@163.con (B. Xiao), tfzhang@gdut.edu.cn (T.F. Zhang).

https://doi.org/10.1016/j.surfcoat.2022.128094
Received 27 May 2021; Received in revised form 28 December 2021; Accepted 4 January 2022
Available online 10 January 2022
0257-8972/© 2022 Published by Elsevier B.V.
B. Xiao et al. Surface & Coatings Technology 433 (2022) 128094

Fig. 1. The schematic diagram of the deposited system and coating multilayer sructure.

by rotating the substrate holder between a pairs of Al0.70Cr0.30 and

Table 1
Al0.60Ti0.30Si0.10 targets. The schematic diagram of the deposition sys­
The deposition parameters of the coatings.
tem and position of targets are showed in Fig. 1. The deposition pa­
Process Parameter Value rameters are listed in Table 1. The electron probe microanalysis (EPMA,
Argon-ion etching Temperature (◦ C) 400 JEOL, JXA-8530F, Japan) was used to identify the chemical composi­
Ar pressure (Pa) 0.8 tions of the coatings. The microstructure of the deposited coatings was
Bias voltage (V) 600
investigated by the scanning electron microscope (SEM, FEI, Nano430,
Cathode current (A) 80
Time (min) 30
United States) and transmission electron microscope (TEM, Talos
Coating Coatings AlCrN AlTiSiN AlCrN/ F200S). The X-ray diffraction (XRD, PANalytical, X'pert PRO, Cu Kα
deposition AlTiSiN radiation, λ = 0.154 nm, United States) was used to characterize the
Cathode current (A) 60 75 60 / 75 phase structure of the coatings. The hardness and elastic modulus of the
Time (min) 60 60 120
coatings on cemented carbide substrates were measured by nano­
Temperature (◦ C) 350
Bias voltage (V) 90 indentation (Hysitron, TI950 TriboIndenter, United States). A penetra­
Working pressure 1.2 tion load of 10 mN was used to maintain indentation depth below 10%
(Pa) of the coatings thickness. The scratch tests were performed to evaluate
Rotation speed (rpm) 2.0
the adhesion strength of the coatings with a loading rate of ~200 N/min
and scratch speed of ~6 mm/min by a scratch tester (CSM, RST). The
investigated. maximum load of scratch testing is 100 N. Thermal gravimetric analyzer
(TGA, SETARAM SETSYS EVO 18) was used to investigate the oxidation
2. Experimental details behavior of the coatings, besides, oxidation of coated Al2O3 plates were
conducted at 800, 900 and 1000 ◦ C in the air for 2 h. The heating rate of
AlCrN/AlTiSiN multilayer coating, as well as AlCrN and AlTiSiN the coatings were ~ 10 ◦ C/min, and the cooling rate were ~30 ◦ C/min.
monolithic coatings were prepared on the cemented carbide (WC-6 wt% The cross-sectional morphologies of the coatings were analyzed by the
Co) and Al2O3 substrates by cathodic arc deposition system (MC800, SEM as well as compositional line-scanning using the integrated energy
Hua Sheng Vacuum Coating, China) with DC substrate bias of − 90 V, N2 dispersive X-ray spectroscopy.
(99.9% purity) pressure of 1.2 Pa and deposition temperature of 350 ◦ C. The machining tests were carried out by horizontal turning center
The cemented carbide substrates were used for mechanical property (SMTCL, ETC3650h, China). The SKD11 mold steel (manufactured by
measurements and machining experiments. The Al2O3 plates were used BAO STEEL Group) was used as the workpiece material. For comparing
for coating characterizations of composition, phase structure, micro­ the machining properties of the coated tools with different coatings, the
structure, and oxidation tests. The cemented carbides and Al2O3 plates value of the rotational speed of the turntable was 4000 r/min. The
were cleaned in acetone and ethanol for 15 min, respectively, and cutting speed of the coated tools is 100 m/min. The feed rate of the
loaded on the substrate holder in the vacuum chamber. Prior to depo­ coated tools is 0.2 mm/r, and the depth of cutting is 0.5 mm. The
sition, the cemented carbides and Al2O3 plates were further cleaned with chemical composition and hardness of the SKD11 are listed in Table 2.
an Ar-ion-bombardment process at DC bias of − 600 V and gas pressure The optical microscope (OLYMPUS, SZ61TR, Japan) was used for
of 0.8 Pa in Ar (99.99% purity) atmosphere for 30 min. To enhance the measuring the flank wear values of the coated tools at each interval of
adhesion strength, a CrN interlayer was deposited on the specimens predetermined cutting distance. The surface morphologies of the coated
from Cr arc target (99.9% purity) in nitrogen (99.99% purity) atmo­ tools were investigated by SEM. Meanwhile, the value of 0.3 mm of the
sphere. The AlCrN and AlTiSiN monolithic coatings were prepared from flank wear was used for the failure criterion for the coated tools.
Al0.70Cr0.30 (99.9% purity) and Al0.60Ti0.30Si0.10 (99.9% purity) tar­
gets，respectively. The AlCrN/AlTiSiN multilayer coating was deposited

Table 2
The chemical constituents and hardness of the SKD11 mold steel.
Workpiece material Chemical composition (wt%) Hardness (HRC)

C Cr Mo Si Mn Ni V

SKD11 1.4–1.6 11.0–13.0 0.7–1.2 ≤0.6 ≤0.6 – 0.15–0.3 62

2
B. Xiao et al. Surface & Coatings Technology 433 (2022) 128094

Fig. 2. The SEM surface and cross-sectional morphology of (a and d) AlCrN, (b and e) AlTiSiN, and (c and f) AlCrN/AlTiSiN coatings.

3. Results and discussion

3.1. Composition and microstructure of the coatings

Based on the EPMA results, the contents of oxygen impurity in our as-
deposited coatings are quite low (about 0.5 at.% ~ 0.7 at.%), which
should be attributed to the residual oxygen impurity in the chamber
during deposition. All the coatings exhibited slightly overstoichiometric
nitrogen content, in range of 51 at.% ~ 53 at.%. To simplify notations,
the elemental compositions of AlCrN, AlTiSiN and AlCrN/AlTiSiN
coatings can be identified as Al0.63Cr0.37N, Al0.65Ti0.29Si0.06N and
Al0.54Cr0.17Ti0.21Si0.08N, respectively. The relatively lower Al concen­
tration in multilayer AlCrN/AlTiSiN coating was considered to be
mainly caused by the re-sputtering effect. Al element has lower atomic
mass than Ti and Cr elements, which could be more easily re-sputtered
from as-deposited surface. Higher density of metallic ion flux was
generated owing to double targets operation during deposition of
AlCrN/AlTiSiN coating, which resulted in enhanced bombardment of
metallic ions and re-sputtering effect of the AlCrN/AlTiSiN coating than
those of the monolayer AlCrN and AlTiSiN coatings. Therefore, Al
element was preferably etched off from the surface of AlCrN/AlTiSiN
coating, leading to lower Al concentration [64]. Fig. 3. XRD patterns of AlCrN, AlTiSiN and AlCrN/AlTiSiN coatings.
The surface and cross-sectional morphologies of as-deposited coat­
ings are shown in Fig. 2. The growth defect of metallic macroparticles sectional images of AlCrN and AlTiSiN (Fig. 2(d and e)) coatings
can be discovered on the surfaces of all coatings due to the characteristic exhibit typical columnar structure. On the other hand, the AlCrN/
of arc deposition. The AlCrN and AlTiSiN monolithic coatings show AlTiSiN coating shows a much denser microstructure (Fig. 2(f)), indi­
higher density of macroparticles, as seen in Fig. 2(a and b), whereas the cating that the alternating deposition of AlCrN and AlTiSiN monolithic
AlCrN/AlTiSiN multilayer coating exhibits less amount of macro­ layers hinder the growth of columnar grains, and reduce internal defects
particles on its surface (Fig. 2(c)). It was inferred that the AlCrN/AlTiSiN of pin-holes and large columnar grain boundaries, resulting in better
coating suffered from stronger re-sputtering effect than the monolayer compactness of AlCrN/AlTiSiN coating. The measured thicknesses of
AlCrN and AlTiSiN coatings due to higher density of metallic ions and AlCrN, AlTiSiN and AlCrN/AlTiSiN multilayer coatings were ~ 3.5, 3.8
enhanced bombardment of metallic ions generated from double targets and 4.1 μm, respectively.
operation during deposition of AlCrN/AlTiSiN coating. Therefore, many XRD patterns of AlCrN, AlTiSiN and AlCrN/AlTiSiN coatings are
micro-droplets would have been etched off from the surface of AlCrN/ shown in Fig. 3. All coatings exhibit a typical face-centered cubic (fcc)
AlTiSiN coating, leading to fewer micro-droplets [65]. The cross- structure. The AlCrN monolithic coating is mainly composed of fcc-CrN

3
B. Xiao et al.
Fig. 4. Cross-sectional bright-field (a) TEM and (b) HRTEM images of the as-deposited AlCrN/AlTiSiN multilayer coating with corresponding SAED pattern.
Fig. 5. Mechanical properties of AlTiSiN, AlCrN and AlCrN/AlTiSiN coatings on cemented carbide substrates.
phase and the AlTiSiN monolithic coating is mainly composed of fcc-TiN
phase, with (111), (200), and (220) peaks being identified, respectively.
The AlCrN/AlTiSiN multilayer coating shows diffraction peaks of both
fcc-TiN and fcc-CrN phases. Slight shifting to higher angles of the peaks
might be attributed to the decrease (or release) of the residual stress in
multilayer structure [41,42], which had been widely reported in Ti/TiN
[43] and Mo2N/CrN [44] multilayer coating systems.
The cross-sectional TEM investigations of AlCrN/AlTiSiN multilayer
coating was performed to further analyze its microstructure, as shown in
Fig. 4. TEM bright-filed image of AlCrN/AlTiSiN multilayer coating in
Fig. 4(a) shows a compact nanocrystalline structure. The SAED image
inserted reveals that the AlCrN/AlTiSiN multilayer coating consists of
TiN and CrN phases with (111), (200), (220) diffraction rings being
identified, respectively. This is in good agreement with the XRD results
in Fig. 3. The high resolution TEM image in Fig. 4(b) displays that the
AlCrN/AlTiSiN coating has a nano-multilayer structure with clear in­
terfaces, where alternating bright and dark contrast sublayers are cor­
responding to the AlTiSiN and AlCrN layers, respectively. The
modulation period of AlCrN/AlTiSiN coating is ~11.6 nm, and thickness
of AlCrN and AlTiSiN sublayers are ~4.1 and 7.5 nm, respectively.
Compared with AlCrN and AlTiSiN monolithic coatings, the multilayer
structure in AlCrN/AlTiSiN coating can effectively reduce the internal
defects of pin-holes and macroparticles (seen in Fig. 2) and inhibit the
growth of large columnar grains, leading to grain refinement, which can
result in a pronounced increase in the volume fraction of grain
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Surface & Coatings Technology 433 (2022) 128094
boundaries, and high hardness, good thermal stability can be obtained
[39,40].
3.2. Mechanical properties of the coatings
Hardness and elastic modulus of our coatings are shown in Fig. 5(a).
The hardness values of AlCrN and AlTiSiN monolithic coatings were
~27.8 and 36.1 GPa, respectively, while higher hardness of ~39.4 GPa
of AlCrN/AlTiSiN multilayer coating was obtained. The elastic modulus
of the AlCrN and AlTiSiN monolithic coatings are ~363.5 and ~475
GPa, respectively, while elastic modulus of our AlCrN/AlTiSiN multi­
layer coating is ~491 GPa. According to Koehler theory [45], hardening
effect of multilayer coating can be attributed to the elastic modulus
difference of the matching monolayers. It was considered that the great
elastic modulus difference between AlCrN and AlTiSiN monolayers was
one main factor of higher hardness of the multilayer AlCrN/AlTiSiN
coating. On the other hand, the grain boundaries inside the AlCrN/
AlTiSiN multiyear coating impede dislocation motion and form more
dislocation accumulations at the grain boundaries, which can enhance
the yield strength of the coating material and result in a higher hardness
[46–48]. Besides, the denser microstructure (SEM result) and grain
refinement (TEM result) can also benefits for higher hardness of our
multilayer coating [46].
The H/E* and H3/E*2 (where E* = E/(1-ʋ2)) values are presented in
Fig. 5(b). The H/E* plays an important role for evaluating plasticity and
B. Xiao et al.
Fig. 6. SEM images of scratch tracks of the AlTiSiN, AlCrN and AlCrN/AlTi­
SiN coatings.
toughness properties of the coatings (e.g. the cracking and abrasive
wear). The H/E* values of AlCrN, AlTiSiN and AlCrN/AlTiSiN coatings
are 0.08, 0.085 and 0.10, respectively, which demonstrates that higher
H/E* value of the coating can be achieved by a multilayer structure. The
H3/E*2 ratio is typically related with the plastic deformation resistance
of the coatings. The H3/E*2 ratios of these coatings shows the same trend
with the H/E* values. The enhanced H/E* and H3/E*2 values of AlCrN/
AlTiSiN coating can be attributed to the nano-multilayered structure
with large amount of interfaces, which can impede the propagation of
cracks and dislocations and effectively improve the toughness and
plastic deformation resistance of AlCrN/AlTiSiN coating [49,50].
Fig. 6 shows the optical morphologies of scratch tracks of our AlCrN,
AlTiSiN and AlCrN/AlTiSiN coatings, where the critical adhesion
strength (edge chipping LC2 and massive delamination LC3) of the
coatings are evaluated. In present work, the LC2 stage corresponds to the
Fig. 7. The thermogravimetric curves of AlTiSiN, AlCrN and AlCrN/AlTiSiN coatings at oxidation temperatures of 800, 900, and 1000 ◦ C in air.
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Surface & Coatings Technology 433 (2022) 128094
sign of adhesion failure of the coatings, which is defined as adhesion
strength of the coatings [52–54]. The LC2 values of our AlCrN, AlTiSiN
and AlCrN/AlTiSiN coatings are ~74.5, 82.3 and 84.3 N, respectively,
indicating that the multilayer structure has slightly improved the
adhesion strength of the coating.
3.3. Oxidation resistance of the coatings
The oxidation resistance of the coating plays an important role for
the cutting performance of the coated tools. Fig. 7 shows thermogravi­
metric curves of AlCrN, AlTiSiN and AlCrN/AlTiSiN coatings between
800 ◦ C and 1000 ◦ C in air for 2 h. The mass gains of AlTiSiN coatings
significantly increase compared with those of AlCrN and AlCrN/AlTiSiN
coatings after isothermal oxidation at all temperatures. The mass gains
of AlCrN and AlCrN/AlTiSiN coatings are parabolically related to
oxidation time from 800 ◦ C to 1000 ◦ C, whereas the thermogravimetric
curve of AlTiSiN coating consists of two different stages at 1000 ◦ C. In
stage Ia, the mass gain of AlTiSiN coating increases linearly during the
oxidation reaction. In stage Ib, mass gain of AlTiSiN coating shows a
parabolic relationship as a function of oxidation time, due to the
oxidation diffusion process. The parabolic oxidation rate of the coating
can be expressed as:
(Δm)2
= kt + c (1)
S
where t is oxidation time, Δm is mass change, S is the surface area of the
specimen, and k and c are constants.
The diagram of (Δm/S)2 versus time is shown in Fig. 8, where
parabolic diffusion control law can perfectly describe the oxidation
behavior of the coatings. The coefficient values of determination (R2) is
in the range of 0.98–0.99, indicating good fitness of the test dates for all
B. Xiao et al.
Fig. 8. The plots of (Δm/A)2 versus time of AlTiSiN, AlCrN and AlCrN/AlTiSiN coatings during isothermal oxidation at temperatures between 800 ◦ C and 1000 ◦ C.
Best fitting straight lines gave with the coefficient of determination R2.
Fig. 9. The arrhenius plots of AlTiSiN, AlCrN and AlCrN/AlTiSiN coatings
during isothermal oxidation at temperatures between 800 ◦ C and 1000 ◦ C.
straight lines. The oxidation activation energy of our coatings can be
expressed in Arrhenius Eq. (2):
Ea
LnK = LnA −
RT
where K is oxidation rate constant, A is pre-exponential constant, T, R
and Ea are absolute temperature, gas constant and activation energy,
respectively.
Fig. 9 shows the linear fitted lines of LnK versus 1000/T for AlCrN,
AlTiSiN and AlCrN/AlTiSiN coatings. The activation energies of AlCrN,
AlTiSiN and AlCrN/AlTiSiN coatings are extrapolated to be 135.1, 49.3
Surface & Coatings Technology 433 (2022) 128094
and 107.8 kJ/mol− 1, respectively, exhibiting that less reaction potential
with oxygen of the AlCrN/AlTiSiN multilayer coating by inserting AlCrN
sublayers into the AlTiSiN coating. According to Gibbs free energy
evaluation, Al2O3 can be preferentially formed as compared with TiO2
during the oxidation of AlTiSiN coating at 800 ◦ C [36]. However, it
cannot form a dense Al2O3 scale on the surface of AlTiSiN coating during
the initial oxidation stage, which causes inward diffusion of oxygen and
form a porous TiO2 in the immediate sublayer. Former researches show
that the formation rate of TiO2 is faster than that of Al2O3 at oxidation
temperature above 900 ◦ C [37,38], and TiO2 remarkably generates
beneath the Al2O3 scale over 900 ◦ C. Under compress stress, Al2O3 scale
will be further cracked by TiO2 oxide, which expedites outward diffu­
sion of Ti and generates more porous TiO2 oxide on the surface of
AlTiSiN coating. These factors obviously increase the mass gains of
AlTiSiN coatings. For AlCrN/AlTiSiN multilayer coatings, many in­
terfaces exist inside the coatings to effectively retard inward diffusion of
oxygen and block outward diffusion of metallic ions, which significantly
improves oxidation resistance of the coatings. In addition, the multilayer
structure also hinders columnar crystal growth and forms a dense
microstructure, which further retards inward diffusion of oxygen [38].
To further investigate oxidation behavior of the coatings, isothermal
oxidation was performed at 900 ◦ C and 1000 ◦ C in air for 2 h. Fig. 10
shows SEM cross-sectional images of AlTiSiN, AlCrN and AlCrN/AlTiSiN
coatings after oxidation at 900 ◦ C. The AlTiSiN coating remains a coarse
(Al, Ti)-rich oxide scale with a thickness of ~0.38 μm (Fig. 10(c)),
(2)
Whereas AlCrN/AlTiSiN and AlCrN coatings show dense and well-
bonded oxide scales with thicknesses of ~0.2 and 0.16 μm, respec­
tively, as shown in Fig. 10 (a and b). The oxide scales of AlTiSiN and
AlCrN/AlTiSiN coatings are measured by the EDS line-scanning. The
strong Ti and O signals on the surface of the AlTiSiN coating indicate
outward/inward diffusion of Ti and O elements during oxidation at
900 ◦ C (Fig. 10(e)). For AlCrN/AlTiSiN multilayer coating (Fig. 10(d)),
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B. Xiao et al. Surface & Coatings Technology 433 (2022) 128094

Fig. 10. The cross-sectional SEM morphologies of (a) AlCrN, (b) AlCrN/AlTiSiN, and (c) AlTiSiN coatings at 900 ◦ C for 2 h and the corresponding EDS line-scanning
of (d) AlCrN/AlTiSiN and (e) AlTiSiN coatings.

Fig. 11. The cross-sectional SEM morphologies of (a) AlCrN, (b) AlCrN/AlTiSiN, and (c) AlTiSiN coatings at 1000 ◦ C for 2 h and the corresponding EDS line-scanning
of (d) AlCrN/AlTiSiN and (e) AlTiSiN coatings.

7
B. Xiao et al.
Fig. 12. Cross-sectional SEM image of AlTiSiN coating oxidized at 1000 ◦ C for 2 h and the corresponding EDS mapping.
Fig. 13. Cross-sectional SEM image of AlCrN/AlTiSiN coating oxidized at 1000 ◦ C for 2 h and the corresponding EDS mapping.
no strong Cr and Ti signals are observed, and O signal shows a sharp
decrease at the interface of oxide scale and remained nitride coating,
indicating that nano-multilayered structure effectively retards inward/
outward diffusion of oxygen /metallic ions, respectively. Up to 1000 ◦ C,
AlCrN/AlTiSiN multilayer coating still keeps a dense structure with an
oxide scale thickness of ~0.28 μm (Fig. 11(b)), and AlCrN coating also
shows a dense structure with an oxide scale thickness of ~0.26 μm
(Fig. 11(a)). The oxidation resistance of AlCrN/AlTiSiN multilayer
coating was comparable to AlCrN coating. However, AlTiSiN coating
exhibits a loose oxide scale of ~0.5 μm (Fig. 11(c)). By EDS line-
scanning analysis, the oxide scale of AlCrN/AlTiSiN coating mainly
consists of Al-rich oxide (Fig. 11(d)), while the oxide scale of AlTiSiN
coating is composed of (Al, Ti)-rich oxide (Fig. 11(e)).
The elemental diffusion behavior of our coatings was further inves­
tigated by EDS mapping. Figs. 12 and 13 show the cross-sectional EDS
mapping of AlTiSiN and AlCrN/AlTiSiN coatings oxidized at 1000 ◦ C in
air for 2 h. The high concentration Al, Ti and O elements on the surface
of AlTiSiN coating are observed, indicating that inward diffusion of O
and outward diffusion of Al and Ti ions significantly occur during
oxidation (Fig. 12(b-d)). However, a thin and dense oxidation scale is
formed on the surface of AlCrN/AlTiSiN coating, as shown in Fig. 13(a).
Relatively low concentration Ti and Cr elements on the surface of the
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Surface & Coatings Technology 433 (2022) 128094
AlCrN/AlTiSiN coating are observed, indicating that less outward
diffusion of Ti and Cr occurs for the multilayered coating (seen Fig. 13(c
and e)). Low content of oxygen can be detected in the inner layer of the
coating, which reveals that the inward diffusion of oxygen is effectively
retarded (Fig. 13(d)).
As mentioned above, For the AlTiSiN coating, Ti ions diffuse rapidly
into the surface of AlTiSiN coating and exhibit a faster formation rate of
TiO2 at high oxidation temperatures, as compared with Al2O3 [38],
which destroys the formation of the protective Al2O3 layer on the surface
of the AlTiSiN coating and leads to generate a porous (Al, Ti)-rich oxide
scale on the surface of AlTiSiN coating [38,55–57]. For the AlCrN/
AlTiSiN multilayer coating, the interfaces between the sublayers act as
good barriers to block the inward diffusion of oxygen and outward
diffusion of metallic ions such as Ti, which significantly improves the
oxidation resistance of the multilayer coatings [56]. In addition, less
straight column boundaries inside AlCrN/AlTiSiN multilayer coating
also decreases diffusion pathways for oxygen and metallic ions and
promote the better oxidation resistance of AlCrN/AlTiSiN coatings
[57–62]. These results are in good agreement with the above thermog­
ravimetric tests.
B. Xiao et al.
Fig. 14. The flank wears of the coatings as a function of cutting length.
3.4. Cutting performance of the coated tools
To evaluate the machining performance of the AlCrN-, AlTiSiN- and
AlCrN/AlTiSiN- coated tools, the turning tests were performed on
SKD11cold mold steel at cutting parameters given in Table 2. The ex­
periments have been repeated three time. During the cutting tests, the
flank wear values of the different coated tools are periodically measured
with an optical microscope. Tool life would be recorded after the flank
wear reached over 0.3 mm. The uncoated tools are also tested for the
reference. Fig. 14 presents the flank wear values of the coated tools with
different coatings versus the cutting length. Clearly, the flank wear
trends for all coated tools are obviously different. The flank wear of all
tools are significant in the initial stage. With increasing cutting length,
Fig. 15. SEM morphologies of wear morphology and elemental map for the coated tool with AlCrN coating (the cutting length for 400 m).
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Surface & Coatings Technology 433 (2022) 128094
the flank wear of the coated tools with AlCrN and AlTiSiN coatings
obviously accelerated, whereas the flank wear of the coated tools with
AlCrN/AlTiSiN coating are steady followed. It is clear that the
descending sort of the flank wear values for all coated tools are un­
coated, AlCrN, AlTiSiN and AlCrN/AlTiSiN coatings with the same
cutting length. When the cutting length reached ~400 m and 500 m,
respectively, the flank wear of the coated tools with AlCrN and AlTiSiN
coatings are 0.337 mm and 0.325 mm, which shows these two kinds of
the coated tools reach their cutting lives. After increasing further to 800
m, the tool wear values for the coated tools with AlCrN/AlTiSiN coating
only reach 0.312 mm. Noticeably, the coated tools with AlCrN/AlTiSiN
exhibit much higher tool life compared to those of the AlCrN and
AlTiSiN coatings, indicating good cutting performance of the coated
tools with AlCrN/AlTiSiN coating.
To further research the wear mechanism of the coated tools during
the machining SKD11 cool steel, SEM morphologies and element maps
of the worn tools are investigated. Fig. 15(a) shows the SEM morphol­
ogies and element map for the AlCrN turning tool. It is very clear that the
large wear area obviously occurs on the flank surface and appears the
block coating peeling and crack, which mainly contribute to the thermal
stress. The higher magnification SEM morphologies shows that there are
deep plough grooves and many microchips on the surface of the AlCrN
tool. The hardness of the AlCrN tool is lower, which is easy scratched by
hard particles of the workpiece material in the cutting process and
generate the plough grooves. In addition, high temperature during the
cutting process makes part of the chips to form hard phase oxides, which
will also scratch the surface of the coated tool, and forms plough
grooves, indicating the abrasive wear is occurred. According to EDS
analysis, high concentrations of W and Co elements with low contents Al
and Cr elements are detected, indicating that the coating was nearly
worn out, as shown in Fig. 15(c). There is high concentration of Fe
element on the surface of the coated tool, indicating the adhesion wear is
occurred. The hardness of the AlCrN tool is low, which leads to poor
wear resistance. So it causes to the severe flank wear of the AlCrN tool
B. Xiao et al. Surface & Coatings Technology 433 (2022) 128094

Fig. 16. SEM morphologies of wear morphology and elemental map for the coated tool with AlTiSiN coating (the cutting length for 400 m).

Fig. 17. SEM morphologies of wear morphology and elemental map for the coated tool with AlCrN/AlTiSiN multilayer coating (the cutting length for 400 m).

during machining SKD11 hardened steel. When the AlCrN tool is worn, Fig. 16(a) shows the SEM morphologies and element map for AlTiSiN
the chips are easily adhered to the surface of the AlCrN tool owing to the tool. There also occurs serious wear on the flank face of the tool. The
strong affinity between Co and Fe. magnification SEM micro-graph in Fig. 16(c) shows that there are

10
B. Xiao et al.
obviously deep plough grooves on the flank of the AlTiSiN tool, indi­
cating that there occur abrasive wear owing to the forming of hard phase
oxides by high temperature during the machining. According to EDS
element analysis, the high concentration of O element is found in test
zone, indicating that oxidation wear occurs. The content of W element is
detected, indicating that AlTiSiN coating is worn. Fig. 16(b) shows that
there is also marked the block materials adhesion, which occurs adhe­
sion wear.
Fig. 17 exhibits the SEM morphologies and element map for AlCrN/
AlTiSiN tool. It can be found that the wear area of AlCrN/AlTiSiN tool is
smaller, less worn than that of AlCrN and AlTiSiN tools under the same
machining 400 m. EDS analysis shows that high concentration of Al, Ti,
Cr and N elements without W element, indicating that the AlCrN/AlTi­
SiN coating is not worn, and the integrity of the coating is good. Clearly,
the coating plays a good role as a protective tool substrate. Overall, The
AlCrN/AlTiSiN tool shows the lest damage compared with the other two
coatings, demonstrating that the AlCrN/AlTiSiN multilayer coating
possesses better wear resistance [63]. From above results, AlCrN/AlTi­
SiN coating with nano-multilayered structure markedly prolongs the
tool life of the coated tool compared with AlCrN and AlTiSiN coatings.
4. Conclusions
In this study, AlCrN/AlTiSiN nano-multilayer coatings were devel­
oped based on alternative AlCrN and AlTiSiN sublayers. Microstructure,
mechanical properties, oxidation behavior, as well as the cutting per­
formance was comparatively investigated for AlCrN, AlTiSiN and
AlCrN/AlTiSiN coatings. The following conclusions could be drawn:
1) AlCrN/AlTiSiN multilayer coating exhibited two phase and dense
microstructure, which showed good hardness and adhesion strength.
2) The AlCrN/AlTiSiN multilayer coating showed excellent oxidation
resistance up to 1000 ◦ C. The oxidation scale of AlCrN/AlTiSiN
coating was composed of a dense Al-rich oxide, which acted as an
effective barrier layer blocking both inward diffusions of oxygen and
outward diffusion of metallic ions. Meanwhile, the multilayer
structure of the coating also acted as a more effective barrier to block
elemental diffusion to retard the oxidation process.
3) The cutting test showed that the AlCrN/AlTiSiN coated tool had a
significantly longer tool life of ~800 m, which could be ascribed to
its higher hardness, adhesion strength and oxidation resistance, as
compared with the monolithic AlCrN and AlTiSiN coatings.
CRediT authorship contribution statement
Xiao Baijun: Conceptualization, Methodology. Zhang Teng Fei: Data
curation. Zhu Guo:Writing-Original draft preparation. Zhou Li: Re­
sources. Fan Bin: Data Curation. Chen Ganxin: Writing - Review &
Editing. Xiong Zhihong: Software, Validation. Wang Qimin: Supervision.
Declaration of competing interest
The all authors have no known competing financial interests or
personal relationships that could have appeared to influence the work
reported in this paper.
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