Ceramics International 44 (2018) 11364–11373

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

Study of the structure, properties, scratch resistance and deformation T

behaviour of graded Cr-CrN-Cr(1-x)AlxN coatings
⁎
Mohammad Sharear Kabira, , Paul Munroea, Zhifeng Zhoub, Zonghan Xiec,d
a
School of Materials Science and Engineering, University of New South Wales, Sydney, NSW 2052, Australia
b
Advanced Coatings Applied Research Laboratory, Department of Mechanical and Biomedical Engineering, City University of Hong Kong, Kowloon, Hong Kong, China
c
School of Mechanical Engineering, University of Adelaide, SA 5005, Australia
d
School of Engineering, Edith Cowan University, WA 6027, Australia

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

Keywords: An in-depth investigation of the structure, properties, scratch adhesion characteristics of graded Cr-CrN-Cr(1-
Graded coatings x)AlxN coatings synthesized onto M42 steel substrates using closed – field unbalanced magnetron sputtering
Unbalanced magnetron sputtering (CFUBMS) was carried out. Advanced microscopy (scanning and transmission electron microscopy), focused ion
Plastic deformation resistance (H3/E2) beam (FIB) imaging, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and micro–scratch tests
Nanoindentation
was used to investigate the microstructure, mechanical properties and scratch performance as a function of Al
Adhesion
content. FIB and TEM investigations revealed that the coatings exhibited a distinct structure; i.e., an adhesive Cr
layer, a CrN transition layer and a graded CrAlN top layer with a face centered cubic (FCC) B1 structure. A
columnar morphology was exhibited by the coatings and the dimensions of the columnar grains decreased with
increasing Al content. Residual stress measurements, obtained from the XRD – sin2ψ method, revealed increasing
compressive stresses with increasing Al content. Furthermore, nanoindentation tests showed an increase in
mechanical properties, fracture toughness index (H/E) and plastic deformation resistance (H3/E2) as the Al
content increased, accompanied by a decrease in the critical load, LC, during scratch testing implying a decrease
in scratch toughness.

1. Introduction
Coatings of transition metal nitrides have been extensively used for
the past several decades to improve efficiency in manufacturing and
component quality during machining operations [1]. In particular,
significant breakthroughs have been achieved in various industrial
applications such as cutting, molding, semi-cold forming, etc., using
chromium nitride and carbide based coatings (CrN, CrAlN, CrTiN,
CrTiAlN, CrAlC, Cr2AlC, etc.) owing to their excellent wear [2–6] and
corrosion [7] resistance. Among them CrAlN coatings have attracted
special attention [8–10], since reports have indicated that increasing
the aluminium content in CrAlN coatings could further improve both
hardness and oxidation resistance [11,12].
On the other hand, multilayer and multicomponent systems based
on CrAlN coatings have been explored for enhanced mechanical prop-
erties [13,14]. Notably, a considerable improvement in mechanical,
scratch toughness and tribological properties can be attained when
coating systems are graded compositionally allowing mechanical cou-
pling due to gradual change in mechanical properties throughout the
graded layers [10,15–17]. This has been reported in quite a few number
of graded Cr-CrN-CrAlN systems. For example, Lin et al. [16] in-
vestigated the mechanical properties and scratch adhesion of both
monolithic and graded Cr-CrN-CrAlN systems synthesized onto 304 SS
substrates by pulsed – CFUBMS. It was reported that the graded system
was better than the monolithic system in terms of mechanical and
scratch adhesion behaviour, the details of which will be discussed later.
Cr-CrN-Cr(1-x)AlxN coatings with high Al contents (up to ~ 30 at%)
deposited on steel substrates by CFUBMS were also studied by Li and
co-workers [15]. The coatings were reported to have a remarkable
improvement in mechanical properties, elastic strain to failure or
fracture toughness (H/E) and plastic deformation resistance (H3/E2).
However, the microstructural evolution, as a function of Al content, and
its link with the mechanical behaviour of the CrAlN coatings are still
unclear [10,11,13,16].
The scratch adhesion test has been employed to investigate the
degree of adherence between coating and substrate for many years due
to its repeatability, qualitative feedback and commercial viability.
However, the complexities of the scratch adhesion test in terms of ap-
plied loads and the stress mechanisms that come into play during
scratch event [18,19] makes it quite challenging to decipher results

⁎
Corresponding author.
E-mail addresses: sharearkabir07@gmail.com, m.kabir@student.unsw.edu.au (M.S. Kabir).

https://doi.org/10.1016/j.ceramint.2018.03.187
Received 12 February 2018; Received in revised form 20 March 2018; Accepted 20 March 2018
Available online 22 March 2018
0272-8842/ © 2018 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
M.S. Kabir et al.
both quantitatively [20] and qualitatively. However, there is a strong
correlation between the mechanical properties of coating and substrate
and coating – substrate deformation mechanisms. Hence, the scratch
test can be regarded as a semi-quantitative test. Moreover, further
evidence suggests that a combination of coating and substrate proper-
ties influence deformation behaviour during scratch testing apart from
adhesion strength alone [18,21–23]. CrAlN coatings have been proved
to have better scratch adhesion behaviour as reported by Wang et al.
[24] where monolithic CrAlN coatings (H = 17.7 GPa) had the highest
adhesive energy. Moreover, graded CrAlN coatings studied by Lin et al.
[16] proved to be more scratch resistant than monolithic counterpart.
However, a detailed analysis of the stresses involved during scratch
event is scarce in literature. The CrAlN graded coatings in this study
have been subjected to scratching at high loads (more than industrial
threshold value) to observe scratch adhesion behaviour and to describe
in detail the scratch performance of these graded coatings along with
the stress mechanisms that come into play during scratch event. The
correlation between structure, composition and mechanical properties
and their effect on the scratch adhesion behaviour has also been ex-
plored in this study.
2. Experimental
2.1. Deposition parameters
A UDP650 magnetron sputtering system (Teer Coatings Ltd., UK)
was used to synthesize the Cr-CrN-Cr(1-x)AlxN graded coatings onto M42
steel substrates. The targets consisted of two 99.5% pure Cr targets
(oppositely faced) distanced 650 mm apart, an Al target (99.99%
purity) and a dummy Si target. All of the targets had dimensions of
380 mm × 175 mm × 8 mm. Primary substrate decontamination was
implemented by degreasing and ultrasonic cleaning in ethanol followed
by N2 blow drying. Final decontamination was carried out by sputter
etching the substrate in Ar+ plasma at −500 V for thirty minutes. The
vacuum chamber was brought down to below 2 µTorr. Deposition
process was carried out with a combined Ar + N2 pressure at 2 mTorr
at a constant Ar gas flow rate of 50 sccm with pulsed DC at a frequency
of 250 kHz. Nitrogen gas flow was monitored by OEM (optical emission
monitor or OEM is used to measure the partial pressures of reactive
gases such as N2 in the vacuum chamber) with a setting at 75% to
regulate the reactive gas flow. The Al target current (sputtering power
0.6–2.8 kW) was varied (2 A, 4 A and 8 A). The Cr target was main-
tained at a constant power and current of 1.45 kW and 4 A respectively.
Deposition began with sputtering of Cr on substrate (bias voltage =
−70 V) surface forming the adhesive layer (~ 240 nm). The CrN buffer
layer was then deposited to a desired thickness of ~ 300 nm.
Subsequently the CrAlN graded transition layer was formed on top of
the CrN buffer layer by varying the Al target current (2 A, 4 A and 8 A)
and thus achieving three different coatings, i.e. S1, S2 and S3 with
different Al content. In this study, three coatings with different Al
concentrations were prepared and denoted to be S1, S2 and S3.
2.2. Coating characterization
The cross-sectional structure and morphology of the coatings were
studied using TEM (Philips CM 200 operated at 200 kV) and focused ion
beam microscope (FEI xP200, USA). TEM sample preparation was done
using FEI xT Nova Nanolab 200 followed by an ex-situ lift-out of the
prepared samples. A detailed description of TEM sample preparation
can be found elsewhere [25]. A thin film X-ray diffractometer (PANa-
lytical Empyrean) was used to investigate the composition and crystal
structure of the coatings. The diffraction patterns were obtained over
range of 30–85° at a grazing incidence angle of 4.14°. Moreover, XRD –
sin2ψ method [26–28] was applied to measure the residual stresses in
the graded coatings following Rietveld refinement of the diffraction
peaks. XPS (ESCALAB250Xi, Thermo Scientific, UK) investigation was
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carried out by using Al Kα radiation as an excitation source after ion
beam cleaning (etching) using Ar+ ions at 3 keV for 200 s to remove
surface contamination. High-resolution scans of Cr, Al and N were ob-
tained at a pass energy of 20 eV. Calibration of the XPS instrument was
carried prior to analysis. Data quantification obtained post-scan was
carried out after performing a C 1s calibration. The mechanical prop-
erties were obtained after performing nanoindentation tests with a
Hysitron Triboindenter (TI900, Minneapolis, USA) by applying a max-
imum load of 8mN in a time duration of 10 s. A 3 × 3 matrix of indents
was made at different sites on the sample surface and the hardness and
Oliver-Pharr method [29,30] was employed to calculate the hardness
and modulus of the coatings.
Scratch testing was performed to determine the nature of failure in
the coatings, i.e. adhesive and/or cohesive. Scratch testing was carried
out by progressive loading at scratch speed of 4 mm/min from 1–150 N
using a CSM REVETEST (CSM Instruments, Switzerland) scratch tester
equipped with a diamond stylus (tip radius = 200 µm). The scratch
took place at a loading rate of 100 N/min over a 6 mm track. Repetitive
scratches (four scratches on each sample) were performed on each
sample. Cross-sections of the scratch tracks were investigated in detail
by back scattered scanning electron microscopy (BSE-SEM, Hitachi S-
3400N) and focused ion beam microscopy.
3. Results
3.1. Chemical composition and bonding states
The chemical composition of graded Cr-CrN-CrAlN coatings char-
acterized by x-ray photoelectron spectroscopy is summarized in
Table 1. The ratio of Al and N content to metallic (Al + Cr) content
defined as x and y respectively as seen in Table 1. It can be seen that Al
content increases slightly for coatings S1 and S2, but increases by ~
36% in coating S3. The ratio of N content to metallic content is non-
stoichiometric (non-integral coefficients or varying ratios of atoms). A
very small (~ 1%) amount of oxygen was observed in each of these
coatings.
Fig. 1(a)–(c) illustrates the high resolution spectra of Cr 2p, Al 2p
and N 1s respectively. The deconvoluted Cr 2p spectrum [Fig. 1(a)]
indicated the presence of Cr-Cr (Cr metal), Cr-N and Cr (III) oxide. The
deconvoluted Al 2p spectrum indicates that most of the Al is bonded to
N in all the coatings and the peak intensity increases as Al content is
increased due to increasing IAl. Deconvolution of N 1s spectrum of all
the coatings indicates that majority of the nitrogen is bonded to chro-
mium and only a small amount bonded to aluminium. However, the
XPS analysis only suggests the bonding states between elements, it
cannot unambiguously confirm the presence of any compound such as
the presence of AlN phase.
The data in Table 2 provides information on the bond fraction
percentage of the elements present in the coatings after deconvolution
of Cr 2p, Al 2p and N 1s spectrum, which was ascertained by calculating
the area under the peaks. Moreover, the Cr–Cr bond fraction decreases
(Table 2) as the Al content is increased and from the deconvolution of N
1s and Al 2p spectrum, it is clear that the N–Al bond fraction increases
by ~ 27%. Furthermore, the presence of O–Cr=O after Cr2p decon-
volution suggests that the coatings reacted with residual oxygen in the
Table 1
Surface chemical composition of coatings.
Coating Surface composition (at%) Al/ N/ Coating
sample (Al (Al composition
Cr Al N O + + Cr(1-x)AlxNy
Cr) Cr)
S1 35.0 13.2 51.0 0.8 0.28 1.05 Cr0.70Al0.28N1.05
S2 32.2 14.2 52.4 1.2 0.31 1.11 Cr0.69Al0.31N1.11
S3 27.3 19.6 52.5 0.6 0.42 1.12 Cr0.58Al0.42N1.12
M.S. Kabir et al. Ceramics International 44 (2018) 11364–11373

Fig. 1. Deconvoluted high resolution XPS spectra of (a) Cr 2p, (b) Al 2p and (c) N 1s.

Table 2
Assigned bonds and bond fraction of elements post deconvolution of HR-
spectra.
Coating Cr 2p Al 2p N 1s
sample
Assigned Bond Assigned Bond Assigned Bond
bond fraction bond fraction bond fraction
(%) (%) (%)

S1 Cr–Cr 21.4 Al–N 14.6 N–Cr 42.9

Cr–N 8.7 N–Al 8.4
O–Cr=O 4.2
S2 Cr–Cr 19.3 Al–N 14.7 N–Cr 43.6
Cr–N 9.0 N–Al 9.0
O–Cr =O 4.4
S3 Cr–Cr 17.1 Al–N 19.8 N–Cr 43.4
Cr–N 7.3 N–Al 9.5
O–Cr=O 3.0

vacuum chamber during XPS analysis. However, the O–Cr=O bond Fig. 2. X-ray diffraction patterns of graded Cr-CrN-CrAlN coatings showing
fraction is low compared to Cr–Cr and Cr–N. peak shift towards higher 2θ values as a function of Al sputtering current (IAl).

fine grained structure owing to high nucleation rate during deposition

3.2. Structure and morphology
The grazing incidence x-ray diffraction patterns of the graded
coatings are shown in Fig. 2 with respect to increasing IAl, which show
diffraction peaks consistent with a face centered cubic structure with
(111), (200), (220), (311) and (222) peaks, revealing the polycrystal-
line nature of the coatings. Moreover, any distinct Cr2N phase and/or
AlN phase are not detectable. All of them show a strong preferred or-
ientation towards < 111 > crystallographic direction with increasing
relative peak intensity as the Al content increases, which can also be
seen for (220). In addition, peak shifts towards higher 2θ angles due to
lattice distortion caused by the introduction of Al in the CrN lattice can
be seen in Fig. 2 as IAl increases from 2 A to 8 A.
The FIB and XTEM micrographs of the graded coatings from
Figs. 3(a)–(c) and 4(a)–(c) clearly illustrates the distinct graded layers:
a coarse grained Cr adhesive layer [Fig. 3(d)] on top which exists the
fine grained CrN intermediate layer [Fig. 3(d)] and then a graded CrAlN
transition layer, found in the coatings. The intermediate CrN layer has a
process. The CrAlN graded layer consists of fine columnar grains closer
to the intermediate CrN layer and becomes gradually coarser towards
the top layer of the coating because of increasing Al content gradually
towards the top layer. Furthermore, TEM micrographs also indicate a
15% increase in the thickness of the coatings because of an increase in
IAl from only 2 A to 8 A. Whereas, the Cr adhesive layer (~ 240 nm) and
CrN layer (~ 320 nm) had constant thickness in all the coatings. Cross-
sectional TEM micrographs [Fig. 4(a)–(c)] reveal well defined grain
morphologies and distinct and densely packed columnar structures with
decreasing columnar grain dimensions as follows evident from the
micrographs:
S1(505 ± 62 nm) > S2(495 ± 78 nm) > S3(439 ± 59 nm)
And the width of the columnar grains decreases in the order:
S1(120 ± 41 nm) > S2(107 ± 40 nm) > S3(85 ± 36 nm)
Selected area diffraction (SAD) patterns obtained from TEM

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Fig. 3. FIB micrographs of coating (a) S1, (b) S2 and (c) S3; (d) XTEM bright field micrograph of coating S2.
micrographs [the bright red spots on the TEM micrographs indicate
acquiring spot] are illustrated and labelled in Fig. 4(d)–(f). Diffraction
reflections of (111), (200), (220), (311) and (222) can be clearly seen in
the SAD patterns and are similar for all three coatings in this study.
Moreover, the patterns are similar to standard SAD patterns of fcc CrN.
However, the SAD patterns do not indicate any reflections from neither
AlN nor Cr2N phase confirming formation of solid solution of CrAlN.
3.3. Residual stress and mechanical properties
The stress along φ = 90° was determined by means of the sin2ψ
method, whereby the diffracted patterns were obtained using Cu-Kα
radiation as shown in Fig. 2. The CrN (111) peak was chosen for these
measurements, as it is the peak with highest intensity. A detailed in-
vestigation of the residual stresses in the coatings has been provided in
an earlier study [31] which reported increasing residual stresses
(compressive in nature) with increasing Al content as follows:
S1(−1.84 ± 0.55 GPa) < S2(−2.23 ± 0.30 GPa) < S3(−4.85 ± 0.78 GPa)
The load – displacement curves along with the maximum penetra-
tion depth (hmax) [Fig. 5(a)], calculated hardness (H) [Fig. 5(b)] and
modulus (E) [Fig. 5(c)] have been plotted as a function of IAl including
their respective error bars. It is evident from Fig. 5 that the mechanical
properties increase as IAl increases as seen in Fig. 5(a) that clearly il-
lustrate decreasing hmax (penetration depth) values. According to Ley-
land and Mathews [32], the H3/E2 ratio calculated from H and E values
indicates the coating resistance to plastic deformation. This ratio in-
creased with increasing Al content [Fig. 5(b)] by about ~ 56% sug-
gesting a remarkable increase in plastic deformation resistance. How-
ever, the abrasive resistance of a material indicated by the ratio 1 / HE 2
[33–35], decreased by ~ 27% in the coatings, which indicates that
further Al addition reduces the damage resistance leading to lower
damage tolerance. Moreover, it should be noted that the hardness (H =
9.7 ± 0.6 GPa) and modulus (E = 241 ± 2.1 GPa) of the substrate
were found to be less than that of the coatings.
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3.4. Analysis of scratch behaviour
Critical loads are loads detectable when material failure occurs.
They are an important aspect in ascertaining the adhesion character-
istics of materials [36] and are determined from friction force curves
such as illustrated in Fig. 6(a) obtained post-scratch test. The curves are
an indication of coating failure evident in Fig. 6(a) where the friction
force rapidly increases when critical load LC2 (upper critical load re-
presents dramatic coating failure leading to substrate exposure) is ex-
ceeded. However, LC1 (lower/initial critical load represents the first
complete confocal cracking event) was difficult to point out from fric-
tion force curves and acoustic emission (A.E) signals alone and hence
required careful observation of SEM micrographs as shown in Fig. 7 to
detect initial failure. Repetitive readings were taken (fifteen readings)
to avoid error which makes a total reading of forty five critical loads for
each coating sample. The average of these readings are shown in
Table 3. Moreover, scratch toughness has also been defined by Zhang
et al. [37], known as scratch crack propagation resistance parameter
(CPRS). Critical loads i.e. both LC1 and LC2 of coating S1 (highest Al
content) are comparatively higher than the coatings S2 and S3
[Figs. 6(a) and 7].
From the SEM micrographs (Fig. 8) of the scratch tracks, events
leading to coating failure can be clearly analyzed. As soon as sliding
starts (stylus is in contact with coating surface), superficial plastic de-
formation dominated by intrinsic coating properties occurs at loads less
than 50 N, i.e. FN < 50 N. The plastic deformation progresses to for-
mation of scratch groove as the normal load increases progressively, i.e.
50 N < FN < LC1. The contact stress increases rapidly due to the
transfer of load to the front half of the indenter which is characteristic
of ductile materials. As loading progresses, material pile-up occurs
ahead and to the sides of the scratch indenter due to compressive stress
leading to bending of the coating along with radial tensile stresses to-
wards the sides of the indenter due to friction between the indenter and
the coating leading to buckling failures [38,39]. The radial tensile
stresses also cause cracks at the outlines of the scratch track parallel to
M.S. Kabir et al.
Fig. 4. Bright field XTEM micrographs of coating (a) S1, (b) S2 and (c) S3 and corresponding SAD patterns of coating (d) S1, (e) S2 and (f) S3.
scratch direction. Partial ring cracks can also be seen to form which can
be seen to push into the scratch track. All these failures result in
through thickness cracking at three sides of the indenter. This type of
failure is characteristic of a ductile failure mode during scratch testing
known as conformal cracking. As soon as upper critical load LC2 is
reached, the stresses due to friction between indenter and coating in-
creases dramatically and the underlying substrate is exposed.
3.5. Cross-sectional investigation of scratch tracks
Coating failure observed in this study post-scratch test is distinctive
to hard coating-soft substrate systems. Cross-sections of coating S3 after
scratch test were milled at various locations parallel and perpendicular
to scratch direction and are shown in Figs. 8 and 9. The sites were
labelled using Roman numerals as seen in Fig. 8. Sites I, II, V and VI
represent milled sections parallel to scratch direction while sites III and
IV represent milled sections perpendicular to scratch direction. Site V
shows plastic deformation of the softer substrate [Fig. 9(e)] at loads
greater than LC1, i.e. FN > LC1 along with deformation of coating which
is still firmly adhered to the substrate. Similar features are shown in site
II [Fig. 9(b)] but with higher degree of substrate deformation since it
occurs at a site very near to LC2 and coating fragments are pinned
within the substrate. Sites I [Fig. 9(a)] and VI [Fig. 9(f)] represent cross-
sections parallel to scratch direction but are also perpendicular to the
cracks caused by the radial tensile stresses as discussed in the previous
section. In these locations, the crack extends outwards from the scratch
track. The milled cross-sections showed complete substrate exposure at
the center of the crack with the coating firmly adhered to the substrate
on either side of the conformal crack. These cracks are about ~ 2–3 µm
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in length and extend below Cr adhesive layer into the substrate. Sites III
and IV shown in Fig. 9(c) and (d) respectively represent milled sections
at the edge of the scratch track and perpendicular to scratch direction.
These sites confirm the presence of deep through thickness cracking
which occurs towards the front and sides of the indenter evident from
Figs. 9(c) and (d) as there is severe cracking and deformation at the
scratch edge. However, in all the sites we can clearly see that no de-
lamination has occurred and the coating firmly adheres to the substrate
indicating excellent adhesion characteristics.
4. Discussions
Surface chemical analysis by XPS showed an increase in Al content
which is apparent from the increase in target current. Moreover, this
also leads to increase in bond fractions of Al–N/ N–Al as a result of
greater affinity of N for Al compared to Cr (ΔHAlN = −317.98 kJmol−1,
ΔHCrN = −117.15 kJmol−1 [40]). However, this also leads to slight
reduction in N–Cr/Cr–N bond fraction. Furthermore, the Al 2p, Cr 2p
and N 1s HR-spectra revealed that a small amount of oxygen has
bonded to Cr and exists as Cr(III) oxide. This can be due to con-
tamination of the surface during XPS analysis or probably during
sample preparation due to oxygen leakage in the deposition chamber as
Cr has a high affinity towards oxygen (ΔHCr2O3 = ~
−1134.70 kJmol−1 [40]). HR-spectra of both Cr and N revealed the
absence of Cr2N phase in the coatings as distinctive B.E levels of
576.10 eV, 574.80 eV in Cr 2p [Fig. 1(a)] [41] and 397.20 and
397.40 eV in N 1s [Fig. 1(c)] [41] were absent. Equilibrium phase
diagram of the Cr-N system [42] further provides evidence that hex-
agonal Cr2N phase can be present only below a threshold value
M.S. Kabir et al. Ceramics International 44 (2018) 11364–11373

Fig. 5. (a) Load-displacement curves, (b) hardness, (c) modulus and (d) H3/E2 vs 1/ (HE2) of coatings S1, S2 and S3.

(35–40 at% N), else cubic CrN will be dominant. Moreover, Reiter et al.
[43] verified the existence of hcp-AlN phase (wurtzite) only after ex-
ceeding a threshold value of 46 at% Al content in CrAlN coatings. The
presence of dominant cubic CrN can be seen and confirmed from XRD
peaks in Fig. 2. The XRD peaks shift towards higher 2θ angles is due to
lattice distortion caused by the substitution of Cr (atomic radius =
0.139 nm) by Al (atomic radius = 0.121 nm) as Al content increases.
Moreover, strong (111) preferred orientation can be noticed in Fig. 1 as
this plane has the lowest strain energy [44]. The presence of Cr2N phase
and AlN phase are not clearly distinguishable which suggest that Cr2N
phase is probably absent in the coatings and the presence of alloyed
phase, i.e. Cr(1-x)AlxNy solid solution rather than discrete phases.
Residual stresses in coatings arise during growth of sputtered films
and in order to obtain high quality coatings, these stresses must be
controlled. Haghiri‐Gosnet et al. [45] and Windischmann [46] have
reported that process parameters and microstructure immensely influ-
ence residual stresses in coatings. Furthermore, they also showed that
the degree of residual stress have strong co-relation with Thornton's
structure zone model (SZM) [47]. Compressive stresses determined in
the coatings in this study increased by a factor of three as a result of
increase in lattice distortion as discussed before. Similarly, compressive
stresses in graded Cr-CrN-CrAlN coatings in another study [48] were
found to increase by about ~ 52% when Al content increased to 30 at%.
These stresses also arise from insufficient release of strain energy that is
generated by Al incorporation during coating growth. As such, the
presence of residual stresses affect the mechanical properties of coat-
ings in terms of increase in hardness and modulus. The decrease in
columnar grain size dimensions (13% decrease in length and 30% de-
crease in width by only 6 at% increase in Al content) evident from TEM
micrographs (Fig. 4) also increase the mechanical properties of the

Fig. 6. (a) Friction force curves of coatings, (b) acoustic emission (AE) signal corresponding to friction force (Ft) curve of coating S3.

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Fig. 7. Back scattered electron micrographs of scratch tracks of coating (a) S1,
(b) S2 and (c) S3.
Table 3
Critical loads in scratch test with CPRS.
Sample LC1 (N) LC2 (N) CPRS
LC1(LC2 – LC1)
S1 94.6 ± 2.1 143.5 ± 3.2 4625.94
S2 88.4 ± 0.7 126.6 ± 2.8 3376.88
S3 85.8 ± 1.2 115.5 ± 2.9 2548.26
Fig. 8. Ion induced SE micrograph of scratch track of S3 showing milled cross-
sections at various sites.
coatings apart from the increase in residual stresses. This increase also
led to increase in fracture toughness index (H/E ratio) and plastic de-
formation resistance (H3/E2 ratio) as seen in Fig. 5(d) which influence
the scratch adhesion behaviour of these coatings.
Scratch deformation mechanisms strongly co-relates to the me-
chanical properties of both coating and substrate [21–23,49–51] be-
sides adhesion strength of coating alone. Scanning electron (Fig. 7) and
FIB microscopy (Fig. 9) of the scratch tracks reveal coating failure due
to substrate exposure and detailed analysis further associates this
failure, i.e. drastic plastic deformation followed by disintegration and
cracking because of the softer nature of the substrate. The analysis of
coating failure has already been provided in the results section which
confirms conformal cracking of the coating accompanied by buckling to
be responsible for coating failure at loads higher than LC2. This phe-
nomenon of plastic deformation of hard coatings on soft substrate has
been reported in detail by Bull et al. [18] and other researchers [52,53].
A 2D model relating to the initial events during scratch testing was also
explored in detail elsewhere [52], describing the stages involved in
coating impingement into the substrate.
The stresses that come into play during scratch testing as a result of
material loading conditions and contact responses have been divided
into three stages by Holmberg [54]. The ploughing action of the stylus
into the substrate is represented by stage I, where the substrate is de-
formed as a result of elastic and plastic deformation leading to the
formation of a scratch groove behind the stylus as seen in Fig. 10.
Following the ploughing action, the coating is drawn and bent like a
thin sheet as the front surface of the stylus grazes the coating surface
and the force required to pull the coating is equal to the friction force
on the coating against the front surface of the stylus. Moreover, the
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bending leads to both stress generation and release in the coating.
Following bending, the coating is pulled from the contact point on the
surface while still adhered to the substrate. As a result of increasing
normal load, the pulling force increases which leads to increase in de-
formation. Consequently, tensile stresses and cracks are generated at
the point of maximum tensile stress. The stresses generated in the
graded coatings in this study is schematically presented in Fig. 10,
where a stylus deforms the coating both elastically and plastically. In-
itially, the stylus creates a small spherical indent that pushes the ma-
terial around the indent due to plastic material flow in a geometric
torus shape as seen in Fig. 10. Compression and tensile stresses are
generated from the pushing force in front of the stylus tip and from
pulling forces behind the stylus respectively due to friction force be-
tween the stylus tip and coating surface. A deeper groove forms as the
stylus tip moves progresses. The geometrical changes, i.e. spherical
indent, groove and torus shaped (i.e. a surface of revolution generated
by a circle revolving in 3D space about an axis coplanar with the circle)
results in bending of the coating due to elastic and plastic deformations
accompanied by both compression and tensile stresses. Furthermore,
plastic deformation of the substrate due to the spherical indentation
pattern reaches its peak value at a 45° angle from the plane of symmetry
in the coating plane. As the tip progresses, the surface towards the rear
of the stylus tip consists of only the plastic part, whereas both elastic
and plastic part exists under the stylus tip. Moreover, another torus
shape forms in front of the tip as seen in Fig. 10.
The scratch adhesion behaviour of ternary CrTiN and CrAlN
monolithic coatings were compared with monolithic binary CrN coat-
ings by Wang et al. [55]. The coatings were deposited by unbalanced
magnetron sputtering under a chamber pressure of 4 × 10−4 Pa. The
CrN (H = 14.5 GPa; E = 271 GPa), CrTiN (H = 13.9 GPa;
E = 295 GPa) and CrAlN (H = 17.7 GPa; E = 315 GPa) coatings were
subjected to scratch testing at a maximum load of 30 N at a loading rate
of 30 N/min for a scratch distance of 3 mm. The critical loads, de-
termined by optical microscopy revealed that CrAlN monolithic coat-
ings had the best adhesive behaviour (LC1 = 13.4 N and LC2 = 24.9 N)
amongst the other coatings with an adhesive energy of 313 J/m2 that is
more than two times than that of binary CrN and ternary CrTiN coat-
ings. However, grading leads to enhanced mechanical properties and
scratch adhesion characteristics. Lin et al. [56] reported better scratch
adhesion of graded CrAlN coatings synthesized by unbalanced magne-
tron sputtering compared to monolithic homogeneous CrAlN coatings
as the critical loads (LC2) increased by 50% while their hardness and
modulus remained almost similar. Moreover, graded CrAlN coatings in
this study achieved critical loads almost three times than that men-
tioned above with coating S1 achieving the highest critical load of LC2
= 143.5 N.
The present study on scratch adhesion characteristics of coatings
reveal an opposite trend to that expected for conventional studies
where coatings with higher fracture toughness index (H/E ratio) and
plastic deformation resistance (H3/E2 ratio) are typically more crack
and wear resistant [24,57]. An earlier study on the tribological beha-
viour of the coatings in this study also revealed an atypical trend with
decreasing wear resistance even though the fracture toughness index
(H/E) and plastic deformation resistance (H3/E2) [31] improved with
increasing Al content. The critical loads of the coatings decrease by
28 N while the CPRs decrease by 45% as Al content increases. However,
all the coatings show excellent mechanical properties and adhesion
characteristics with coating S1 being the best among them. This is in
accordance with Beake et al. [58], who reported that coatings with H/
E < 0.1 have optimum combination of properties and thus are more
favourable in industrial applications. Moreover, coating S1 has the least
damage tolerance among the three coatings in this study, which is re-
presented by the abrasive resistance ratio 1/HE2. Furthermore, ac-
cording to Vishnyakov et al. [59,60] and Musil [61], films should have
lower modulus implying wider load distribution which in turn increases
plastic deformation resistance. This has been further confirmed from
M.S. Kabir et al. Ceramics International 44 (2018) 11364–11373

Fig. 9. FIB micrographs of scratch track cross-sections of (sites I to VI) coating S2 (yellow arrow indicates scratch direction). (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)

other studies [21,58,60] that lower modulus coatings with moderate
hardness had better crack resistance than the much harder and stiffer
coatings. The cohesive nature of the coatings, which is a function of
hardness, does increase with increasing hardness. However, the mod-
ulus mismatch also increases leading to a decrease in scratch toughness.
5. Conclusions
The intensive investigation on the scratch adhesion behaviour of
graded Cr-CrN-Cr(1-x)AlxN coatings synthesized by closed – field un-
balanced magnetron sputtering revealed that composition, micro-
structure and process parameters greatly influence the adhesive beha-
viour of coatings under dynamic loading. The XPS and XRD results
indicate the increase in Al content in the coatings as a result of in-
creasing the target current. TEM investigation revealed that increase in
Al content refined the columnar structure of these coatings considerably
leading to increase in the mechanical properties, fracture toughness
index (H/E ratio) and plastic deformation resistance (H3/E2 ratio) of
these coatings to some extent. However, in contrast to conventional
findings, the scratch resistance/toughness decreased significantly by
two times as seen from reduction in LC2 loads and CPRs values. FIB
cross-sectional analysis strongly indicates conformal cracking accom-
panied by buckling failure at higher loads to be responsible for coating
failure at high loads which is typical of ductile hard coatings on com-
paratively softer substrate. However, the coatings performed well
during scratching tests, where the critical load values in all coatings
significantly exceeded the industrial threshold set for hard coatings. As
such graded coatings have been proved to have better mechanical
properties than their monolithic counterparts to be utilized in heavy
machining operations. However, a detailed comparison of scratch ad-
hesion characteristics between graded and multilayer coatings have yet
to be explored.

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M.S. Kabir et al. Ceramics International 44 (2018) 11364–11373

Fig. 10. Stress fields generated in a graded coating system because of friction force, bulk plasticity concentration, residual stresses and geometrical deformations.

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