Surface & Coatings Technology 362 (2019) 27–34

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Surface & Coatings Technology

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Microstructure, adhesion and tribological properties of CrN/CrTiAlSiN/ T

WCrTiAlN multilayer coatings deposited on nitrocarburized AISI 4140 steel
⁎ ⁎
Yang Lia, , Qianwen Yea, Yijie Zhua, Lei Zhangb, Yongyong Hec, Shangzhou Zhanga, , JunJie Xiua
a
School of Nuclear Equipment and Nuclear Engineering, Yantai University, Yantai 264005, PR China
b
School of Electromechanical Automobile Engineering, Yantai University, Yantai 264005, PR China
c
State Key Laboratory of Tribology, Tsinghua University, Beijing 100084, PR China

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

Keywords: In this study, the CrN/CrTiAlSiN/WCrAlTiN multilayer coatings have been deposited on polished AISI 4140 steel
Multilayer coatings substrates (named only-coating specimens) and plasma nitrocarburized specimens (named duplex specimens) by
Plasma nitrocarburizing cathodic multi-arc evaporation. The microstructure and composition of the specimens were studied using X-ray
Super-hardness diffraction (XRD), scanning electron microscopy (SEM) with Energy dispersive X-ray analysis (EDX), and
Adhesion
transmission electron microscope (TEM) techniques. The micro-hardness and nano-hardness were measured by
Vickers hardness tester and nanoindentation, respectively. The adhesion and tribological behavior were eval-
uated using the Rockwell-C indentation and micro-tribometer, respectively. The results showed that plasma
nitrocarburizing gives rise to a modified layer due to diffusion of nitrogen/carbon, leading to surface hardness,
H, of 13.0 GPa, compared to H = 6.8 GPa for the untreated steel. Notably, it shows that the super-hardness
(H = 47.9 GPa) multilayer coating consists of a bottom CrN layer, a middle CrTiAlSiN layer, and an outmost
superlattice WCrTiAlN layer. The nitrocarburizing pretreatment considerably improves adhesion strength of the
duplex specimen compared with the only-coating one. The improved mechanical and tribological properties of
the duplex specimen are mainly related to the gradient in the hardness profile of the diffusion nitrocarburized
layer.

1. Introduction wear and corrosion resistance [15–18]. The nitrocarburized layer is

CrN-based coatings have been widely utilized in providing bene-
ficial effects for various mechanical parts due to good corrosion re-
sistance and excellent tribological properties [1–5]. Under extreme
conditions, such as heavy load, the difference in hardness between the
coating and the substrate is significant, resulting in cracking and
peeling of the coating. S. Suresh [6] demonstrated that the gradient
structure could effectively improve the soft substrate's load bearing
capacity and prevent the growth defects due to the presence of a lot of
interfaces.
The duplex process composed of plasma nitriding/nitrocarburizing
and the coating deposition improved the hardness and tribological
properties of tools far beyond the only coating [7–11]. However, ni-
trocarburizing is less studied as pretreatment [12,13]. Zhang et al. [14]
reported that plasma nitrocarburizing was used as a pre-deposition
method for producing an interfacial layer that improves the adhesion of
the AlCrN and AlCrTiSiN coatings. Plasma nitrocarburizing is a ther-
mochemical process widely utilized in improving promote the hardness,
commonly composed of a thin compound layer and a thick diffusion
layer containing gradient nitrogen/carbon concentration in depth. The
introduction of the nitrocarburized layer not only significantly im-
proves the carrying capacity of the substrate surface and the coat-
ing–substrate bonding force, but also improving the surface fatigue
strength, thermal shock, and chemical resistance.
Multilayer coatings present greater hardness and wear resistance
than homogeneous coatings of the same material [19–25]. Different
strategies have been followed to improve the CrN-based coatings per-
formances, especially in the field of nano-structure coatings since it is
the case of nanocomposites and multilayer structures [5,26,27]. Sui
et al. [28] considered that the improvement of the tribological perfor-
mance of CrN/DLC/Cr-DLC multilayer coatings was attributed to the
introduction of lubricant DLC and hard CrN layers, the enhancement of
crack propagation inhibition by multilayer design method. Zhao et al.
[29] considered that nanoscale multilayered structurization with W2N
was adopted to increase hardness and wear performance of TiAgN
coatings. Su et al. [30] investigated the hardness of Cr–W–N coatings

⁎
Corresponding authors.
E-mail addresses: metalytu@163.com (Y. Li), szzhangyt@163.com (S. Zhang).

https://doi.org/10.1016/j.surfcoat.2019.01.091
Received 26 August 2018; Received in revised form 21 January 2019; Accepted 25 January 2019
Available online 27 January 2019
0257-8972/ © 2019 Elsevier B.V. All rights reserved.
Y. Li et al.
Fig. 1. Schematic representation of interface engineering steps of the multi-
layer coatings deposited on the PNC surface.
Fig. 2. X-ray diffraction patterns of the different specimens.
increased substantially with an increase in the content of W addition,
due to the formation of a WN phase embedded uniformly in the CrN
coatings. Some studies have suggested that the mechanical properties of
coherent CrN-based/W2N multilayers can be improved by periodic
microstructural control [31–33].
Multilayer structure with alternating deposition of two or more
metal nitrides combining the advantages of constituent layers is one of
the most used ways in industrial applications [34]. In this study, CrN/
CrTiAlSiN/WCrTiAlN multilayer coating with the multicomponent and
gradient types was designed to reduce the residual stresses in the
coating. Our previous research showed that pre-nitriding treatment is
more effective in improving the adhesion than the only-coating sample
[11]. Moreover, nitrocarburizing can reduce the brittleness of the single
nitridied compound layer. In this work, AISI 4140 steels were plasma
nitrocarburized and subsequently CrN/CrTiAlSiN/WCrTiAlN multilayer
coatings were deposited. The structural and composition of the
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Surface & Coatings Technology 362 (2019) 27–34
Fig. 3. Cross-sectional OM micrographs of the only-coating (a) and duplex
specimens(b); SEM micrographs of the only-coating(c) and duplex specimens
(d).
multilayer coating is analyzed by XRD, SEM, EDS, and TEM. The ad-
hesion strength and mechanical properties of the multilayer coating on
the different surfaces are discussed.
2. Experiments
The test specimens cut from the commercial AISI 4140 steel (com-
position: 0.040 wt% C, ≤0.05 wt% Si, 0.129 wt% Mn, 0.0156 wt% P,
0.007 wt% S) bar (ϕ = 20 mm) with 6 mm thickness were adopted in
the experiments. The specimens were ground with SiC paper and po-
lished to mirror surfaces with diamond polishing fluid (named un-
treated specimens). Plasma nitrocarburizing experiments were carried
out using an LDMC-20 pulsed plasma device [35]. The AISI 4140 steel
specimens were plasma nitrocarburizing at 525 °C for 6 h (named PNC
specimens). Treatments were performed at a pressure of 4 mbar in a gas
mixture of 94 vol% NH3 and 6 vol% CO2. The voltage and discharge
current between the specimen tables (cathodic) and furnace well
(anodic) were 750–800 V and 5–6 A, respectively.
Depositions were conducted in an industrial cathodic arc evapora-
tion system (HCCE-280, Aomet Nano Technology Ltd., China) [11]. 3
tungsten, 3 chromium, 1 AleTi, and 1 Al-Ti-Si targets were used. Each
target had a power source supply with electric currents, depending on
the desired deposition rate. The CrN/CrTiAlSiN/WCrTiAlN coatings
were deposited onto the polished AISI 4140 steel substrates (named
only-coating specimen) and PNC specimens (named duplex specimens).
These PNC specimens were ground and then mirror polished with
diamond suspension before deposition. Fig. 1 describes the schematic
representation of interface engineering steps of the multilayer coatings
deposited on the PNC surface. First, a very thin Cr interlayer was de-
posited onto the polished surface. Then, the CrN layer was deposited as
Y. Li et al. Surface & Coatings Technology 362 (2019) 27–34

Fig. 4. EDS line and maps of the cross-section of the only-coating specimen.

Fig. 5. Cross-sectional TEM micrographs and SAED patterns of the only-coating specimen.

29
Y. Li et al.
Fig. 6. (a) Load-displacement curves of the different specimens under nanoindentation; (b) Nano-hardness and elastic-modulus of the different specimens.
Fig. 7. Micro-hardness depth profiles of the different specimens.
Fig. 8. Surface roughness of the different specimens.
the second interlayer. Afterward, the selection of the sputtering targets
(Cr, AleTi, and Al-Ti-Si) depended on the category of the CrTiAlSiN
layers. Finally, the individual layer thickness of W-Cr-Al-Ti-N and Cr-W-
Al-Ti-N layer was controlled by alternately switching the time for
shutters with the aid of a programmable logic control to form the
outermost WCrAlTiN multilayers.
The XRD spectra of the different specimens were obtained using an
X-ray diffractometer (Bruker D8 ADVANCE) with Cu-Kα radiation
(λ = 1.5406 Å). The morphology and composition of the multilayer
coatings were observed by scanning electron-microscope (SEM) with
the Energy dispersive X-ray analysis (EDX). Morphologies and micro-
structures of the coatings were investigated by transmission electron
microscopy (TEM) and selected area diffraction (SAED). Surface
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Surface & Coatings Technology 362 (2019) 27–34
microhardness measurements were performed on the different speci-
mens using a Vickers' indenter. Nanoindentation tests were performed
with an NHT-2 nanoindentation Tester (CSM, Switzerland) to de-
termine the indentation hardness and Young's modulus of the different
specimens. The surface roughness of the specimen was measured using
a Form Talysurf PGI 1230 roughmeter. The adhesion characteristics of
the coatings were investigated using a standard Rockwell-C indentation
tester using a load of 150 kgf and a dwell time of 10 s. The indentation
impresses were observed by OM. The adhesion of the coating was
classified as HF1 (excellent adhesion) to HF6 (total delamination
around the imprint) according to the amount of cracking or coating
delamination around the edges of the indent [36,37].
Ball-on-disc sliding tests were conducted using a universal micro-
tribometer (UMT-3, CETR, USA) with a GCr15 bearing steel ball
(d = 4.0 mm, Hardness 62 HRC) as a counter ball. The hydraulic oil in
the friction tests is 15# aviation hydraulic oil (Great Wall Lube Oil,
China). The lubricant is supplied at the center of the disc in an oil
dispenser that distributes the lubricant across the disc surface. The
sliding tests were carried out at room temperature (25 °C) and in la-
boratory air (50% relative humidity), a normal load of 10 N and a ro-
tation speed of 300 rpm. The topography of the wear tracks was mea-
sured by SEM.
3. Results and discussion
Fig. 2 shows the XRD patterns of untreated and nitrided specimens.
XRD analysis results show that the phase composition of the untreated
specimen is primarily α-Fe phase, while the PNC specimen mainly
consist of ɛ-Fe2–3(C, N) and γ'-Fe4(C, N) phases. A. Celik et al. [38]
found that the compound layer formed during plasma nitrocarburizing
consists of polyphase iron nitrides or iron carbonitrides such as ɛ-Fe2–3N
or Fe2–3(C, N) and γ'-Fe4N or Fe4(C, N) in 75%N2 + 23%H2 + 2%CO2
mixture gas. M.H. Sohi et al. [39] investigated plasma nitrocarburizing
in an 80% N2 with 20% H2 atmosphere, containing 7 vol% CO2 mostly
produced ɛ-Fe2–3(C, N) phase with limited amount of γ'-Fe4(C, N) phase.
According to the Fe–N–C ternary phase diagram, increase of carbon
content enhances formation of ɛ-Fe2–3(C, N) phase in the compound
layer. However, it is difficult to determine whether the phases on the
compound layer of the PNC specimen are the nitrides or carbonitrides,
as the lattice spacing in the iron nitrides or carbonitrides are nearly the
same [40].
The diffraction peaks of α-Fe phases occur in the XRD data of the
only-coating specimen due to the thickness of this coating is too thin.
The coating exhibited a face centered cubic (fcc) structure with strong
(111), (200) and (311) peaks. The (111), (200) and (311) peaks of the
fcc W2N phase (JCPDS card #25–1257) are located at 2θ of 37.2°, 43.0°
and 74.3°, respectively. The peak positions of W2N phase shifted to
lower angles may be due to the excess nitrogen in over-stoichiometric
coatings and the compressive stress, which is in good agreement with
Y. Li et al.
Fig. 9. Rockwell indentations of the only-coating and duplex specimens (150 kgf).
Fig. 10. The variation of friction coefficient versus time of the different spe-
cimens.
the results obtained previously by other authors [29,31]. It is also ob-
served that the AlN phase forms at peaks of about 44.0° and 75.0°. The
diffraction peaks located at 2θ of 36.8°, 43.2° and 74.4° are identified as
(111), (200) and (311) of fcc CrN/TiN structure (JCPDS card #11–0065
and 38–1420). The peaks are slightly shifted to lower diffraction angle
as compared to the databases, indicating a decrease in the lattice
parameters as the Cr atoms were replaced by the smaller Al atom [41].
Tu et al. [32] also revealed that W might be the incorporation as solid
solution agent to the CrN crystalline structure in the deposition process.
For the duplex specimen, its diffraction peaks show that the W2N, CrN,
AlN and TiN phases are predominant and some peaks of γ'-Fe4(C, N) and
ɛ-Fe2–3(C, N) can also be detected. It found that duplex specimen pre-
sented the ɛ-Fe2–3(C, N) phase are lower intensity than those of the PNC
specimen at 38.2° and 43.6°. This is due to the ɛ-Fe2–3(C, N) phase ri-
cher outer layer was removed by grinding.
Fig. 3 shows the cross-section OM and SEM images of the different
specimens. For the only-coating specimen, a uniform and compact light-
grey layer was firmly developed on the surface of the polish matrix, and
no crack was observed between the light-grey layer and substrate
(Fig. 3a). Fig. 3b shows a cross-sectional SEM image of the multilayer
coating with a thickness of 2.3 μm. To confirm a distributed composi-
tion of the elements of the only-coating specimen, SEM-EDS line and
map examinations were carried out as shown in Fig. 4. The EDS line
profiles showed that the element composition of W, Cr, Al, Ti and N in
the multilayer coating. It found that the W was mainly distributed in the
outermost layer. It further indicates that Cr, Al, Ti and Si atoms are
uniformly distributed in the inner layer of the coating. Presence of N in
all the coating was also observed. As seen in Fig. 3b and d, the modified
layer of the duplex specimen consists of a multilayer coating and an
8–10 μm nitrocarburized compound layer.
Cross-section TEM micrographs of the multilayer coating are
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Surface & Coatings Technology 362 (2019) 27–34
presented in Fig. 5. It discovers that a 2.3 μm multilayer coating layer
consisted of a 0.7 μm top W-Cr-Ti-Al-N layer, a 1.3 μm middle
CrTiAlSiN layer, and a 0.3 μm bottom CrN layer. It found that the CrN
and CrTiAlSiN layer is characterized by pronounced columnar grains, in
which the columnar boundaries are clearly visible. The SAED patterns
corresponding to the fcc CrN (111), (200), (220) and (311) reflections
were clearly shown (see inserts area C). In contrast, the middle
CrTiAlSiN layer exhibits a dense morphology and columnar grains,
elongated in the growth direction (see inserts area B). The SAED pattern
presents a continuous ring pattern, which can be indexed to fcc (111),
(200), (220) and (311) reflections. As shown in inserts area A, a lami-
nate structure was revealed in the top of the coating. The W-Cr-Al-Ti-N
and Cr-W-Al-Ti-N layers alternating in growth direction were shown as
dark and bright layers in the micrograph, respectively. Our previous
research showed that a higher content of W in the bright layer and the
lower content in the dark layer [11]. Compared with the CrN layer, the
SAED pattern of the WCrAlTiN layer exhibited more continuous rings
which confirms a smaller grain size in the superlattice coatings [23,42].
The diffraction pattern revealed the diffraction planes of the NaCl-type
structure, which was consistent with the result of XRD (Fig. 3). In
summary, the multilayer coating is consisted of a bottom CrN layer and
a middle CrTiAlSiN with columnar structure growth, and an outmost
superlattice WCrTiAlN layer.
Indentation loading curves corresponding to the different specimens
were shown in Fig. 6a. These curves correspond to the tests with a
maximum penetration depth of around 232 nm for the untreated ma-
trix, then of about 182 nm for PNC specimen, and finally those with the
depth of approximately 129 nm for the duplex specimen. As shown by
the load-displacement curves, the maximum contact depths for the
only-coating specimen is approximately 0.13 μm, which is much
smaller than 10% of the coating thickness 2.3 μm (Fig. 4), indicating
that the contribution to the deformation behavior from the underlying
substrate is negligible [43]. Fig. 6b shows the nano-hardness and elastic
modulus values of the different specimens. The H and E of the untreated
matrix are 6.8 GPa and 227 GPa, respectively. Compared to the un-
treated matrix, the PNC specimen has both a higher hardness (H,
13.0 GPa) and elastic modulus (E, 220 GPa). This improvement is due to
the interstitial diffusion of nitrogen/carbon in α-Fe [44,45]. The mul-
tilayer coating has a maximum nano-hardness (47.9 GPa) and highest
elastic modulus (424.8 GPa), which is related to the W2N phase [31,32]
and super-lattice structure [46–48]. The introduction of W into CrN-
based coatings increased the hardness, which was attributed to the
Hall–Petch effect from crystal size refinement and the formation of
highly covalent bonded WeN secondary phase in CrN coatings [33,49].
This finding means that the CrN/CrTiAlSiN/WCrTiAlN multilayer
coating is likely to exhibit higher hardness for the initiation of plastic
deformation than these of the CrN-based coatings.
Micro-hardness depth profiles of the different specimens are shown
in Fig. 7. The surface hardness of the PNC specimen was > 950 HV0.05,
which is about 2.7 times higher than that of the untreated substrate
(350 HV0.05). The micro-hardness values measured from the only-
Y. Li et al.
Fig. 11. Details of the worn surfaces of the different specimens.
coating surface was observed to be 720 HV0.05. It found that the hard-
ness value of only-coating from vickers hardness tester was very low
compared with that measured from nanoindentor. When the load is
larger, the micro-hardness of the coating is affected by the softer ma-
trix, which is much lower than its intrinsic hardness. The highest
hardness values (2300 HV0.05) observed in the duplex specimen can be
related to the presence of the hard coating and nitrocarburized layer.
The PNC specimen show high hardness values, which remain approxi-
mately constant through the diffusion layer and then gently decrease to
matrix values. The thickness of the diffusion layer is about 180 μm for
the PNC specimen, which the minimum hardness of diffusion layer was
50 HV0.05 higher than the that of the matrix. The hardness of the du-
plex-treated specimen decreases gradually to the value of the core of the
substrate through the diffusion layer, while for only-coatings deposited
on the untreated matrix, it rapidly drops to the substrate hardness.
The surface roughness of the different specimen is given in Fig. 8. It
can be seen that the surface roughness Ra of the polished surface is
increased from 0.020 to 0.386, 0.058, 0.162 for the PNC, Only-coating,
duplex specimens, respectively. It found that the PNC specimen showed
the highest surface roughness value in the all specimens. The surface
relief caused by volumetric expansion associated with the formation of
carbonitrides is also believed to result in surface roughening [50]. It
found that the surface roughness of the only-coating specimen was
lower than that of the PNC one. It is also noticed that the duplex spe-
cimen shows a much smoother surface due to the ground and polishing
before depositing.
Fig. 9 demonstrates the OM images of Rockwell-C indentation of the
only-coating and duplex specimens. It found that the only-coating
specimen exhibited a delaminated zone, which showed lateral cracks
perpendicular to the scratch direction due to the deformation of the
substrate. The adhesion in this case is evaluated to adhesive strength
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Surface & Coatings Technology 362 (2019) 27–34
(HF5) [36]. The release of the interfacial bonds was correlated with
shear stress components of the stress tensor, which cause micro/macro-
delamination [51]. For the duplex specimen, the indentation impresses
show similar radial cracks. These radial cracks indicated a strong ad-
hesive strength (HF1) between the multilayer coating and the ni-
trocarburized layer. It is related to the compressive stress on the ni-
trocarburized layer caused by the diffusion of nitrogen and carbon
atoms during the PNC process. The duplex specimen shows higher ad-
hesion strength than that of the only-coating one. This improvement
could be attributed to the diffusion nitrocarburized layer has stronger
abilities to resist the plastic deformation. The nitrocarburized layer
considerably improves load capacity and adhesion strength of the
coating as a result of the thicker nitrocarburized layer [12].
Fig. 10 shows the friction coefficients vs sliding time curves of the
different specimens. It was clearly observed that the average friction
coefficients value of the untreated specimen is 0.06–0.07. SEM ob-
servations of the wear tracks of each of the different specimens, as
shown in Fig. 11, revealed that the morphologies of the wear tracks are
entirely different. As can be seen from Fig. 11a, high plastic deforma-
tion and ploughing were observed on the worn surface of the untreated
specimen. This is because the substrate has a relatively lower hardness
as compared to the counter-act material (GCr15 ball). The PNC spe-
cimen has a relatively higher friction coefficient (0.14–0.16), which is
associated with its high surface roughness and relatively high hardness.
The wear track of PNC specimen is smaller than that of untreated one
(Fig. 11b). In contrast, the only-coating specimen exhibited the lowest
friction coefficient (~0.02) in all specimens. As shown in the Fig. 11c,
nearly no damage could be observed. It can also be seen that the highest
friction coefficients values of the duplex specimen are 0.18–0.20, This is
attributed to its highest hardness and larger surface roughness, which
causes damage to counter-act GCr15 ball. The track of wear became
Y. Li et al.
abrasion wear accompanied by a few scratches arising from the increase
of surface hardness, and some dark pitches were formed in the duplex
specimen (Fig. 11d). The change of the friction coefficient is correlated
with the surface hardness, phase structure, its proportion, and the
roughness of the surface layer.
4. Conclusions
The CrN/CrTiAlSiN/WCrTiAlN multilayers coating was successfully
prepared using cathodic multi-arc evaporation. It can see that the
2.3 μm total thickness multilayer coating was consisted of a top
WCrTiAlN multilayer, a periodic CrTiAlSiN interlayer, and a bottom
CrN layer. It has super-hardness (47.9 GPa), elastic modulus
(424.8 GPa) and lowest friction coefficient of 0.02.
For the duplex system, it can be discovered that a modified layer
consists of two distinct layers as a result of the nitrocarburizing and
deposition processes described previously: a 180 μm nitrocarburized
layer followed by a multilayers coating. Improvement of adhesion
strength of the duplex specimen was attributed to the formation of the
nitrocarburized layer with a graduated hardness.
Acknowledgments
The project was supported by the National Key Basic Research
Program of China (973) (2014CB046404), the Shandong Provincial
Natural Science Foundation, China (ZR2018MEE016), the Shandong
Provincial Key Research and Development Plan, China
(2017GGX20140), and the National Natural Science Foundation of
China (51301149).
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