coatings
Article
Evaluation of Adhesion Properties of Hard Coatings by Means
of Indentation and Acoustic Emission
Peter Drobný 1, *, David Mercier 2 , Václav Koula 3 , Sára Ivana Škrobáková 1 , L’ubomír Čaplovič 1
and Martin Sahul 1






Citation: Drobný, P.; Mercier, D.;
Koula, V.; Škrobáková, S.I.; Čaplovič,
L’.; Sahul, M. Evaluation of Adhesion
Properties of Hard Coatings by
Means of Indentation and Acoustic
Emission. Coatings 2021, 11, 919.
https://doi.org/10.3390/
coatings11080919
Academic Editor:
Alexander Tolstoguzov
Received: 18 June 2021
Accepted: 27 July 2021
Published: 31 July 2021
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
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iations.
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Coatings 2021, 11, 919. https://doi.org/10.3390/coatings11080919
1 Faculty of Material Science and Technology, Institute of Material Science, Slovak University of Technology in
Bratislava, Jána Bottu 25, 917 24 Trnava, Slovakia; ivana.skrobakova@stuba.sk (S.I.Š.);
lubomir.caplovic@stuba.sk (L’.Č.); martin.sahul@stuba.sk (M.S.)
2 CRM Group-CRM, 4000 Liège, Belgium; david.mercier@ansys.com
3 ZD Rpety-Dakel, Ohrobecká 408/3, 142 00 Praha, Czech Republic; koula@dakel.cz
* Correspondence: peter.drobny@stuba.sk; Tel.: +421-33-599-1600
Abstract: In general, the mechanical properties of hard thin coatings are investigated using inden-
tation methods. Material characteristics of hard coatings, such as elastic modulus and hardness,
are evaluated by means of nanoindentation and an appropriate evaluation methodology. The most
popular method used to obtain the coating properties required using nanoindentation is the evalua-
tion based on the Oliver and Pharr methodology. Adhesion and wear properties can be calculated
using these data. In this study, we used a novel method to evaluate the wear and adhesion of
coatings. A special measuring device combined with static indentation and acoustic emission signal
detection was developed to evaluate the adhesion of coatings. The device consists of a macrohardness
instrumental indentation device equipped with an acoustic emission measuring gauge. It was used to
investigate crack formation and adhesion of coatings deposited on different substrates using acoustic
emissions data. The results using both the existing and novel methods were compared and evaluated.
Keywords: adhesion; coatings; thin films; testing; mechanical properties; indentation; acoustic emis-
sion
1. Introduction
The quality of coated mechanical components mainly depends on the quality of the
coating–substrate system. If the coating fails, the functions of the mechanical components
can be significantly impaired. This is particularly important for deposited coatings used
to increase the mechanical resistance of machine tools. The most important parameter
influencing the coating lifetime under load is the quality of the bonding or adhesion
between the substrate and coating. Adhesion is defined as a state when two surfaces are
bonded together by an inter-layer [1]. The adhesion of coatings to substrates is one of the
most important parameters used for thin layer quality evaluation.
The connection between the coating and its substrate is improved when the mutual
solubility of the coating and substrate components in the solid state allows the formation
of a thin diffusion layer at the coating–substrate interface. Adhesion is a critical component
of the coating–substrate system. The adhesion of coatings depends on the purity of the
substrate, surface finishing (less roughness leads to better adhesion), and the difference in
ductility of the substrate and the layer. Satisfactory values of adhesion significantly affect
the interfacial strength, since it prevents cracking, spalling, and delamination of the layer.
Therefore, knowledge of the type of damage and cracking of the thin film is an important
consideration when evaluating the mechanical properties of the coating–substrate system [2].
However, one of the most popular methods for analyzing the coating–substrate system
adhesion is indentation. Indentation enables the usage of an easy loading configuration
and the possibility to directly observe crack formation and film delamination. During the
https://www.mdpi.com/journal/coatings
Coatings 2021, 11, 919 2 of 17

However, one of the most popular methods for analyzing the coating–substrate sys-
Coatings 2021, 11, 919 2 of 17
tem adhesion is indentation. Indentation enables the usage of an easy loading configura-
tion and the possibility to directly observe crack formation and film delamination. During
the loading stage, both the coating and substrate accomplish the deformation imposed by
the indenter.
loading stage,However, during unloading,
both the coating and substrate theaccomplish
coating is usually harder, and
the deformation thus the
imposed byelas-
the
tic recovery is higher, which means adhesion forces between the substrate
indenter. However, during unloading, the coating is usually harder, and thus the elastic and coating are
not strong enough to avoid delamination [3].
recovery is higher, which means adhesion forces between the substrate and coating are not
The
strong adhesion
enough of hard
to avoid coatings depends
delamination [3]. on mechanical properties such as elastic mod-
ulus,The
E; hardness,
adhesionH;ofand fracture
hard toughness,
coatings depends 𝐾 on [4].mechanical
These mechanical parameters
properties such as are cal-
elastic
culated
modulus, from data obtained
E; hardness, by fracture
H; and nanoindentation
toughness tests.
, K Ic [4]. These mechanical parameters
are calculated
The formationfrom data obtained
of fractures by their
and nanoindentation
propagationtests. in hard coatings is commonly in-
The formation
vestigated of fractures
using indentation and Cracking
tests. their propagation
patterns in arehard coatings
formed as a is commonly
function inves-
of the R/t
tigated
ratio usingRindentation
(where is the radiustests. Cracking
of the tip andpatterns are formed
t is the coating as a function
thickness) of the
[5]. Three R/ttypes
main ratio
of crackRcan
(where is the radius of the
be identified tip and
during t is the coating
indentation of hardthickness) [5]. Threeon
coatings deposited main types
ductile of
sub-
crack can
strates be identified
(Figure 1): during indentation of hard coatings deposited on ductile substrates
•(Figure 1):
Circumferential cracks appear at the periphery of plastic zone;
•• Circumferential
Channel cracks
cracks are appear
initiated at the
under periphery
heavy stress of plastic
caused byzone;
direct contact between the
• Channel cracks are initiated under heavy stress caused by direct contact between the
indenter and coating;
indenter and coating;
•• And radial cracks
And radial cracksoriginate
originatefrom
fromthe
themiddle
middle ofof
thethe indentation
indentation imprint
imprint andand propa-
propagate
gate outwards in the form of beams
outwards in the form of beams [6,7]. [6,7].

(a) (b)

Figure 1. Coating cracks after indentation: (a) Circumferential cracks; (b) channel cracks and radial cracks.
cracks.

If the loading force of the indenter is high enough and the substrate is plastically
deformed, coatings
coatingsbegin
begintotolose
loseadhesion
adhesionand
anddelamination
delamination oror
spalling
spallingcan occur.
can Cracking
occur. Crack-
andand
ing spalling
spallingof hard coatings
of hard coatingsrelease dissipated
release energy
dissipated [8] which
energy propagates
[8] which through
propagates the
through
material
the in the
material form
in the of elastic
form waves.
of elastic waves.Their
Theirformation
formationcan canbebedetected
detected byby an
an acoustic
acoustic
emission (AE)
emission (AE) measuring
measuring device.
device.
The AE event caused by
The AE event caused by indentation
indentation is
is often
often explained
explainedbybyone
oneofofthe
thefollowing
followingmecha-
mech-
nisms as a function of the analysed specimen (ceramic, metal, semiconductor,
anisms as a function of the analysed specimen (ceramic, metal, semiconductor, monolayer, monolayer,
multilayer sample,
multilayer sample, etc.)
etc.) and
and experimental
experimental conditions
conditions (time,
(time, temperature,
temperature, geometry
geometry ofof the
the
indenter, etc.):
indenter, etc.):
•• Dislocations nucleation
Dislocations nucleation (sudden
(sudden yielding
yielding ofof aa material
material under
under load);
load)
• Rupture of a hard-brittle film on an elastic-plastic substrate [9];
• Rupture of a hard-brittle film on an elastic-plastic substrate [9];
• Strain transfer across grain boundaries in metals [10,11];
•• Strain transfer across grain boundaries in metals [10,11];
Crack formation;
•• Phase transformation;
Crack formation;
• Amorphization and densification [12].
 • Phase transformation;
Coatings 2021, 11, 919 • Amorphization and densification [12]. 3 of 17

It is known that a failure mechanism has an influence on the detectability of AE. AE

events start to occur when the stress caused by indentation exceeds certain limits, beyond
It isthe
which known thatisa released.
energy failure mechanism has an influence on the detectability of AE. AE
eventsThe
startISO
to occur when the stress[13]
14577-1 standard caused by indentation
defines the terms exceeds certain limits,
nanoindentation, beyond
microindentation
which the energy is released.
and macroindentation according to the depth of the imprint and applied loads as follows
The ISO 14577-1 standard [13] defines the terms nanoindentation, microindentation,
• macroindentation
and Nanoindentation: h ≤ 0.2 to
according µm;
the depth of the imprint and applied loads as follows:
•• Microindentation:
Nanoindentation: h ≤F0.2
< 2µm;
N, h > 0.2 µm;
•• Microindentation: F h
Macroindentation: 2 N ≤ F> ≤0.230µm;
< 2 N, kN.
• Macroindentation: 2 N ≤ F ≤ 30 kN.
ISO 14577-4 [14] was especially addressed for coatings and thin films, since ISO
ISO 14577-4 [14] was especially addressed for coatings and thin films, since ISO
14577-1 was not developed with its focus on coatings and thin films. However, the behav
14577-1 was not developed with its focus on coatings and thin films. However, the be-
ior of of
havior viscoelastic
viscoelasticmaterials testedbyby
materials tested indentation
indentation waswas not covered
not covered yet by yet
any by any of thes
of these
documents
documents [15]. [15].
However,it itisispossible
However, possibletotoinvestigate
investigate crack
crack formation
formation andand delamination
delamination of hard coat
of hard
ings after
coatings thethe
after indentation
indentationtest
testby
bycomparing theimprints
comparing the imprintsobserved
observed using
using scanning elec
scanning
electron microscopywith
tron microscopy withthe
thefailure
failure chart
chartaccording
according totoVDI
VDI3198 standard
3198 [16] [16]
standard (Figure 2). 2).
(Figure

Figure2.2.VDI
Figure VDI 3198
3198 indentation
indentation test.test.

AAvisual
visualcomparison
comparisoncancanprovide
provideinformation
informationabout final
about failure
final of the
failure coating–
of the coating–sub
substrate system. However, no further information about the failure can be obtained
strate system. However, no further information about the failure can be obtained durin
during the indentation. The acoustic emission measurement system is able to continuously
the indentation. The acoustic emission measurement system is able to continuously mon
monitor and record acoustic data, which can be used for analysis after the test.
itor In
and record
this study,acoustic data, which
we performed caninvestigation
a detailed be used for analysis after
of material the test. of two
parameters
In this
different typesstudy, we deposited
of coating performed onatwo
detailed investigation
different of material
substrates. Material parameters
parameters mea- of tw
different types of coating deposited on two different substrates. Material
sured and calculated using nanoindentation tests were compared with acoustic emission parameter
measured
data measuredandduring
calculated using nanoindentation
macroindentation tests. tests were compared with acoustic emis
sion data measured during macroindentation tests.
2. Materials and Methods
2.1. Materials Selection
2. Materials and Methods
Two types of coating were investigated in the experiment. Both types were deposited
2.1. Materials
onto Selection
the discs 12.5 mm in diameter and synthesized in company LISS (Rožnov pod Rad-
Two
hoštěm, types
Czech of coating
Republic) were investigated
All samples in the
were deposited by experiment.
LARC (Lateral Both types
rotating were deposited
cathodes)
in
onto the discs 12.5 mm in diameter and synthesized in company LISSfollow-
a PLATIT π80 + DLC (PLATIT AG, Selzach, Switzerland) deposition unit on the (Rožnov pod
ing two different
Radhoštěm, Czechsubstrates: High-speed
Republic) steelwere
All samples HSS deposited
6-5-2-5 (1.3243) (HSS),(Lateral
by LARC and WC-6Co
rotating cath
sintered carbide (SC).
odes) in a PLATIT π80 + DLC (PLATIT AG, Selzach, Switzerland) deposition unit on th
2.1.1. nACo3two
following different
Coating substrates: High-speed steel HSS 6-5-2-5 (1.3243) (HSS), and WC
Characterization
6Co sintered carbide (SC). 3
Two samples with nanocomposite nACo coating were used; the first was deposited on
the HSS substrate and the second on the SC substrate. nACo3 coating can be characterized
by the following architecture: TiN-AlTiN-AlTiN/SiN [17]. The color of the coating is
 2.1.1. nACo3 Coating Characterization
Two samples with nanocomposite nACo3 coating were used; the first was deposited
on the HSS substrate and the second on the SC substrate. nACo3 coating can be character
ized by the following architecture: TiN-AlTiN-AlTiN/SiN [17]. The color of the coating is
Coatings 2021, 11, 919 4 of 17
violet-blue and hardness ranged from 25 to 28 GPa. The entire thickness of the coating
was around 3 µm.
nACo3 coating has a nanocomposite structure. The Si content is influenced by the
violet-blue
depositionand hardness
rate. ranged
Generally, in from 25 toof28aGPa.
the case The entire
Ti-Si-Al-N thickness
coating, the of
Sithe
andcoating
Al ionswassubstitute
around 3 µm.
Ti in the crystal lattice of c-TiN, reducing the coating’s lattice parameters. Nucleation and
nACo3 coating has a nanocomposite structure. The Si content is influenced by the
segregation of the amorphous
deposition rate. Generally, Si3Nof4 phase
in the case present
a Ti-Si-Al-N in thethe
coating, coating
Si and at
Alaions
particular
substituteSi conten
causes
Ti in thesuppression
crystal latticeofofthe nc-(Ti,
c-TiN, Al)N grain
reducing growth.
the coating’s Thisparameters.
lattice effect is accomplished
Nucleation by em
bedding nanocrystalline AlTiN grains into an amorphous Si N matrix
and segregation of the amorphous Si3 N4 phase present in the coating at a particular [18,19].Si
content causes suppression of the nc-(Ti, Al)N grain growth. This effect is accomplished by
2.1.2. TiXCo
embedding 3 Coating Characterization
nanocrystalline AlTiN grains into an amorphous Si3 N4 matrix [18,19].
The second coating, TiXCo3, was deposited only on a high-speed steel (HS6-5-2-5
2.1.2. TiXCo3 Coating Characterization
1.3243) substrate. TiXCo is a3 nanocomposite coating with high silicon content and the
3
The second coating, TiXCo , was deposited only on a high-speed steel (HS6-5-2-5,
following architecture of individual layers: TiN-nACo3-TiN/SiN. The addition of Si leads
1.3243) substrate. TiXCo3 is a nanocomposite coating with high silicon content and the
to phase segregation of an amorphous SiNx matrix that surrounds (nano)crystalline grains
following architecture of individual layers: TiN-nACo3 -TiN/SiN. The addition of Si leads
of phase
to the TiAlN phaseof[20].
segregation These crystalline
an amorphous SiNx matrix grains
that are embedded
surrounds in an amorphous
(nano)crystalline grains matrix
and
of theform
TiAlNaphase
nanocomposite structure,
[20]. These crystalline generally
grains designated
are embedded as nc-MeAlN/a-SiNx.
in an amorphous matrix and Com
pared to the previously mentioned coating, TiXCo is characterized
form a nanocomposite structure, generally designated as nc-MeAlN/a-SiNx. Compared by higher hardness (38
to the previously
GPa), mentionediscoating,
while its thickness TiXCo
3 µm. The is characterized
incorporation of by higher
Si and Alhardness (38 GPa),
atoms leads to a concur
while its thickness
rent decrease is 3 µm.parameters
in lattice The incorporation of Si and
and internal Al atoms
stresses. leadssolution
Solid to a concurrent
strengthening
decrease
which isinassociated
lattice parameters
with anand internalin
increase stresses.
hardness,Solidtoughness,
solution strengthening, which is
elastic modulus, and wea
associated with an increase in hardness, toughness, elastic modulus, and wear resistance
resistance can occur. The formation of a protective SiO2 layer improves the oxidation re
can occur. The formation of a protective SiO2 layer improves the oxidation resistance. The
sistance. The addition of Si leads to the formation of nc-TiAlN and ornc-CrAlN grains in
addition of Si leads to the formation of nc-TiAlN and ornc-CrAlN grains in an amorphous
an amorphous
SiNx matrix [17,21].SiNx matrix [17,21].
Both coatings wewe
Both coatings used
used here
here cancan be characterized
be characterized by highbyhardness,
high hardness, excellent
excellent abrasiveabrasive
wearresistance,
wear resistance, high
high reliability
reliability in dry
in dry machining,
machining, and lowandthermal
low thermal conductivity.
conductivity.
Thetriple
The triplestructure
structure of the
of the coatings
coatings enables
enables thicker
thicker coatingscoatings to be deposited,
to be deposited, which iswhich is
extremely 3
extremely useful for cutting tools [22]. Figure 3 illustrates the cross-sectionnACo
useful for cutting tools [22]. Figure 3 illustrates the cross-section of the of the nACo
coating
coatingdeposited
deposited ononsintered
sinteredcarbide.
carbide.

Figure3.3.Cross-section
Figure Cross-sectionof of nACo
nACo 3 surface.
3 surface.

2.2. Measuring Methods

2.2. Measuring Methods
Coating properties were investigated using two indentation methods. The mechanical
Coating properties were investigated using two indentation methods. The mechani
properties of the coatings were first determined by the nanoindentation method and then by
cal Daimler–Mercedes
the properties of the macroindentation
coatings were first determined
method combinedbywith
the the
nanoindentation method and
detection of acoustic
emission signals.
Coatings 2021, 11, 919 5 of 17

Surface spalling and cracking of coatings after the indentation test were examined
by the JEOL JSM 7600 F high resolution scanning electron microscope (HRSEM, JEOL,
Tokio, Japan).

2.2.1. Nanoindentation
Nanoindentation tests were performed using a Nanoindenter Agilent G200 (Santa Clara,
CA, USA) equipped with an indenter XP head Berkovich tip with a maximum indentation
depth of 2 µm. A grid of 6 × 6 measurements were made at room temperature at an
acquisition frequency of 10 Hz, with a strain rate of 0.05 s–1 for each specimen. We adopted
the methodology and calculations from Oliver and Pharr [23,24], while the experimental
method used was continuous stiffness measurement (CSM) mode at a frequency of 75 Hz
and an amplitude of 0:5 nm. Load, displacement, and elastic contact stiffness were continu-
ously recorded during indentation. The area function of the contact depth was carefully
calibrated from measurements performed on a fused silica sample. The Young’s modulus of
each sample was determined using equations from the procedure given by Oliver and Pharr,
by taking a Poisson’s ratio of 0.3 for each sample and removing the elastic contribution
of the indenter, which was made of diamond. The nanoindentation test parameters are
summarized in Table 1.

Table 1. Nanoindentation test parameters.

Maximum Indentation
Strain Rate (N/s) Matrix
Depth (µm)
0.05 6 × 6 indents spaced by 50 µm 2

The plasticity index (H/E) provides more information about wear properties and
overall tribological behaviors of coatings [25,26]. A high H/E∗ value refers to a reduced
contact pressure, since the applied load is distributed over a larger area [27]. According
to Musil, hard coatings with H/E∗ > 0.1 are particularly desirable for many tribological
applications [28]. Another interesting index used in the elastic-plastic approach is the
plastic deformation resistance (H 3 /E2 ). This parameter is proportional to the resistance of
the coating to plastic deformation [25]. This means that the higher the resistance to plastic
deformation, the higher the H 3 /E2 ratio. In general, a low E is desirable, as it allows the
given load to be distributed over a wider area [28,29]. The following mechanical properties
were calculated:
• Elastic modulus (E) and hardness (H). Mean values of E and H were obtained at
indentation depths 100 and 200 nm;
• Plasticity index (H/E) and plastic deformation resistance (H3 /E2 ).

2.2.2. Macroindentation and AE Measuring

The popular Daimler–Mercedes indentation test, which is described in the VDI 3198
standard [30], serves as a basic destructive quality test for the evaluation of coated com-
pound adhesion [16,31]. The loading force applied to the indenter generates an elastic and
then a plastic deformation of the sample surface. When a coating breaks, crack initiation
and propagation as well as spalling release energy, which propagates through the material
in form of waves and they can be captured by AE sensor [32]. The AE signal is generated by
fracture phenomena and can be measured and quantified with an acoustic emission gauge
(ZD Rpety-DAKEL, Prague, Czech Republic). The analysis of these acoustic emission
signals provides information about the adhesion and ductility of the coatings.
The advantages of this indentation method are the fast execution of tests using it,
minimal demands on the measurement device, and the ability to monitor coating behavior
with an acoustic emission device that can be attached directly to the tested specimens
without damaging the sample.
Coatings 2021, 11, 919 6 of 1

Coatings 2021, 11, 919 with an acoustic emission device that can be attached directly to the tested specimen
6 of 17

without damaging the sample.

A special measuring device for the acoustic emission signal detection and evaluatio
of coatings
A special adhesion
measuring has been
device developed.
for the This consists
acoustic emission of a UMZ-3K
signal detection (Micro-Epsilon
and evaluation
ofBechyne,
coatingsCzech
adhesionRepublic)
has been device for the This
developed. measurement
consists ofof a materials’ properties. The devic
UMZ-3K (Micro-Epsilon,
Bechyne,
is equipped Czechwith
Republic) device for
a Rockwell the measurement
C indenter with a oftopmaterials’
angle ofproperties.
120°. TheThe device
movement of th
isindenter
equipped with a Rockwell C indenter with a top angle of 120 ◦ . The movement of the
is stopped automatically when the adjusted force is reached.
indenter is stopped
Acoustic automatically
emission signalswhen the adjusted
generated force
during theis test
reached.
were measured by a DAKEL
Acoustic emission signals generated during the test were measured by a DAKEL-ZEDO
ZEDO device (ZD Rpety-DAKEL, Prague, Czech Republic), which is an advanced an
device (ZD Rpety-DAKEL, Prague, Czech Republic), which is an advanced and powerful
powerful
modular modular
system system for
for detecting anddetecting
evaluatingand evaluating
acoustic emissionacoustic
signals.emission signals.
In this case, a In thi
case, a sophisticated, yet very simple AE sensor type Holder was used,
sophisticated, yet very simple AE sensor type Holder was used, which enables the testing of which enables th
testing without
samples of samples without
a special a special
fixing fixing
mechanism. mechanism.
This This the
sensor facilitates sensor facilitates
detection the detectio
of coating
of coating
cracks, cracks,
spalling, spalling, andThe
and delamination. delamination.
coated sampleThe coated
mounted onsample mounted
the AE sensor on the
is shown in AE sen
Figure 4.
sor is shown in Figure 4.

Figure4.4.Specimen
Figure Specimen indentation
indentation withwith special
special AE sensor
AE sensor DAKELDAKEL type Holder.
type Holder.

Two
Two tests were
tests wereperformed
performedusing maximum
using forcesforces
maximum of 50 and 1500
of 50 andN.1500
WearN.
and tribo-
Wear and tribo
logical properties of the substrate–coating system were evaluated.
logical properties of the substrate–coating system were evaluated.
The first test included a loading with constantly increasing force of 50 N. The second
The first test included a loading with constantly increasing force of 50 N. The secon
test used the maximum force of 1500 N. The indentation parameters of this test are sum-
test used the maximum force of 1500 N. The indentation parameters of this test are sum
marized in Table 2. When the loading force reached 500 N, a 10 s dwell time was applied.
marized
The in Table
force was 2. When the
then increased loading
to the forceload
maximum reached
of 1500500NN, a 10 s dwell
(so-called time was applied
“instrumented
The force was
indentation”). then
First, theincreased to the
applied loads maximum
generated loadand
an elastic of 1500 N (so-called
then plastic “instrumente
deformation.
indentation”). First, the applied loads generated an elastic and then plastic deformation
Table 2. Parameters of the indentation test (Fmax = 1500 N).
Table 2. Parameters of the indentation test (F = 1500 N).
Speed of Indenter
Maximum Force (N) Holding Force (N) Dwell Time (s)
Maximum Force (N) Holding Force (N) Dwell Time (s) Speed(mm/min)
of Indenter (mm/min)
1500
1500 500500 10
10 0.2 0.2

Themost
The most commonly
commonly used
used AE parameters
AE parameters for thefor the evaluation
evaluation of coating
of coating adhesionadhesion
are ar
asfollows
as follows [32]:
[32]:
•• Hit:
hit:aasignal
signalthat exceeds
that exceedsthe the
threshold and causes
threshold a system
and causes channelchannel
a system to accumulate
to accumulat
data. It is frequently used to show the AE activity with counted number for
data. It is frequently used to show the AE activity with counted number for a perioa period
or accumulated numbers. In general, one waveform corresponds to one “hit”. It
or accumulated numbers. In general, one waveform corresponds to one “hit”. It rep
represents the number of cracks and other structural instabilities that arose and grew
resents the number of cracks and other structural instabilities that arose and grew i
in a specimen.
• a specimen.
Hits energy is an integral of squared (or absolute) amplitude over time of signal
• Hits energy
duration. is an
There are integral
differentof squared (or absolute)
approximations amplitude
for AE signal energyover
(withtime
unitsofofsignal du
2 ·s), most frequently it is expressed in energy units (eu). According to previous
Vration. There are different approximations for AE signal energy (with units of V2·s
studies there is relationship
most frequently betweeninfracture
it is expressed energyenergy
units and
(eu).AE signal energy,
According it gives studie
to previous
information about the energy released into the material because of crack initiation
there is relationship between fracture energy and AE signal energy, it gives infor
mation about the energy released into the material because of crack initiation an
propagation [30]. More intense crack initiation causes more energy to be released
 Usually, more energy is released when spalling or delamination in hard coatings o
curs.
It is possible to set more thresholds and record more AE signals of different amp
Coatings 2021, 11, 919 tudes within the AE system. 7 of 17
Coatings 2021, 11, 919 7 of 17

3. Results
and propagation [30]. More intense crack initiation causes more energy to be released.
3.1. Nanoindentation
Usually,
Usually, more
moreenergy
energyisisreleased
releasedwhen
whenspalling or or
spalling delamination in hard
delamination coatings
in hard oc-
coatings
The nanoindentation
curs.
occurs. tests were performed to determine the main material param
ters, hardness
ItIt is H, and
is possible
possible to Young’s
to setmore
set modulus.
morethresholds
thresholds Both
and
and hardness
record
record more
more AEAEand elastic
signals
signals modulus
of different
of different were calc
ampli-
amplitudes
lated tudes
withinwithin
using the the
Oliver
the AE AEand
system.system.
Pharr method, which considers the projected area of the Berk
vich indenter and the indentation contact depth.
3.3.Results
Results
Figure
3.1.
5 shows the load-displacement curve of specimens deposited with nACo3 an
Nanoindentation
3.1. Nanoindentation
TiXCo3 coatings, indicating the difference in behavior of the coatings.
The nanoindentation tests were performed to determine the main material parameters,
The nanoindentation tests were performed to determine the main material parame-
hardness
ters, H, and
hardness Young’s
H, and modulus.
Young’s BothBoth
modulus. hardness and and
hardness elastic modulus
elastic werewere
modulus calculated
calcu-
using the Oliver and Pharr method, which considers the projected area of
lated using the Oliver and Pharr method, which considers the projected area of the the Berkovich
Berko-
indenter
vich and and
indenter the indentation contact
the indentation depth.
contact depth.
Figure55shows
Figure showsthetheload-displacement
load-displacement curve
curve of
of specimens
specimens deposited
deposited with nACo33 and
with nACo and
TiXCo 3 coatings, indicating the difference in behavior of the coatings.
TiXCo coatings, indicating the difference in behavior of the coatings.
3

Figure 5. Load-displacement curves of all samples.

Load-displacement
Figure5.5.6a
Figure
Figure curvesof
shows the difference
Load-displacement curves ofall
allin coating hardness. A higher hardness 𝐻 of TiXC
samples.
samples.
coating was documented atdifference
small depths. This effect was caused by the higher
TiXCo33Si conte
Figure
Figure 6ashows
6a showsthethedifference in incoating
coating hardness.
hardness. AAhigher
higher hardness
hardness 𝐻H of
of TiXCo
in thecoating
top layer
coating was of the coating.
wasdocumented
documented at By depths.
atsmall
small contrast,
depths.This slightly
This higher
effectwas
effect was caused
caused hardness
by the
by at higher
the higher
higher depths w
Si content
Si content
inthe
confirmed
in thetop
topthe
in layer ofthe
nACo
layer of the coating.
3 coating.
coatingByBy contrast,slightly
deposited
contrast, slightly higherhardness
on sintered
higher hardness
carbide.atathigher
higher depths
depths was
was
confirmed in the nACo33 coating deposited on sintered carbide.
confirmed in the nACo coating deposited on sintered carbide.

(a) (b)
Figure 6. Calculated(a)
mechanical properties of experimental samples: (a) hardness (b)
H; (b) elastic modulus E.
Figure 6. Calculated
Figure 6. Calculated mechanical
mechanical properties
properties of of experimental samples:
experimental (a) hardness H; (b)H; modulus E.
elasticelastic
The elastic module curves showsamples:
different (a) hardness
behavior (Figure(b)6b). There modulus E.
is a difference
in the Young’s modulus for the same coating, nACo3, which is caused by the use of differ-
The elastic module
ent substrates. curves
A decrease show
in elastic different
modulus behavior
means (Figure
that the coating 6b). There
exhibits is a differen
better elastic
in the Young’s modulus for the same coating, nACo3, which is caused by the use of diffe
ent substrates. A decrease in elastic modulus means that the coating exhibits better elast
 8 of 17
Coatings 2021, 11, 919 8 of 17

properties and higher resistance to cracking.

The elastic module The different
curves show TiXCo3 behavior
coating(Figure
deposited on the
6b). There high- in
is a difference
speed steel (HSS) substrate
the Young’shad approximately
modulus for the samethe samenACo
coating, values
3 of elastic
, which modulus
is caused by the useasofthe
different
nACo coating at higher indentation depths. The elastic modulus value was higher at lowelastic
3 substrates. A decrease in elastic modulus means that the coating exhibits better
properties and higher resistance to cracking. The TiXCo3 coating deposited on the high-
indentation depths and then began to decrease with the indentation depth. This could be
speed steel (HSS) substrate had approximately the same values of elastic modulus as the
caused by the increase
nACo3 Si
in content,
coating which
at higher usuallydepths.
indentation leads The
to aelastic
decrease in the
modulus mean
value valueat low
was higher
of the elastic modulus.
indentation depths and then began to decrease with the indentation depth. This could be
Figure 7a,b shows
causedthe
by curves of the
the increase in Si plasticity index,
content, which represented
usually by thein 𝐻/𝐸
leads to a decrease ratio,
the mean value of
the elastic modulus.
while plastic deformation resistance is represented by the H /E ratio; the latter expresses
3 2
Figure 7a,b shows the curves of the plasticity index, represented by the H/E ratio,
the resistance of a material to plastic deformation and the probability of plastic defor-
while plastic deformation resistance is represented by the H3 /E2 ratio; the latter expresses
mation of hard coatings. Materials
the resistance defined
of a material by high
to plastic hardness
deformation and theandprobability
low elastic modulus
of plastic deformation
have a high plastic deformation resistance.
of hard coatings. Materials defined by high hardness and low elastic modulus have a high
plastic deformation resistance.

(a) (b)
Figure
Figure 7. 7. Calculated
Calculated mechanical
mechanical properties
properties of experimental
of experimental samples:
samples: (a) Plasticity(a) Plasticity
index H/E, (b)index
plasticH/E, (b)
deformation
resistance 3
H /E .2
plastic deformation resistance 𝐻 /𝐸 .
3.2. Macroindentation and AE Measuring
3.2. Macroindentation andThe
AEmacroindentation
Measuring test was performed to determine the resistance of the coatings
to cracking,
The macroindentation testspalling, and delamination.
was performed However,
to determine thetoresistance
investigate the adhesion
of the and wear
coatings
parameters of the coatings, a high loading force is needed. Following this test, data from all
to cracking, spalling, and delamination. However, to investigate the adhesion and wear
substrate–coating systems must be compared. We assumed that the coatings’ tribological
parameters of the coatings, a high loading
behavior depends force isproperties,
on the substrate’s needed. as Following this
the substrate test, datadeformed
is plastically from by
all substrate–coating systems must be compared. We assumed that the coatings’ tribolog-
high loads, which significantly influences the results of coatings’ wear behavior.
ical behavior depends on the substrate’s properties, as the substrate is plastically de-
3.2.1. Number of Hits
formed by high loads, which significantly influences the results of coatings’ wear behav-
The thresholds were adjusted to detect all of the AE events that occurred during the
ior. test. Thresholds were adjusted to slightly above ambient noise and then the measuring
gauge was able to detect small energy dissipations into the measured material. Acoustic
3.2.1. Number of Hits
events represented by hits could be caused by different mechanisms mentioned in Section 1.
However, they are mostly caused by the formation of cracks. The adjusted threshold level
The thresholdsand
were adjusted to detect all of the AE events that occurred during the
chosen amplification are given in Table 3.
test. Thresholds were adjusted to slightly above ambient noise and then the measuring
gauge was able to detect
Table 3.small energy
AE detection dissipations into the measured material. Acoustic
thresholds.
events represented by hits could be caused by different
Maximum Force (N)
mechanisms mentioned
Threshold (dB)
in Section
Amplification (dB)
1. However, they are mostly caused50
by the formation of 20
cracks. The adjusted threshold
96
level and chosen amplification1500are given in Table 3. 20 66

Table 3. AE detection thresholds.

Maximum Force (N) Threshold (dB) Amplification (dB)

50 20 96
1500 20 66
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Coatings 2021, 11, 919 9 of 17

Figure 8 documents the results from the macroindentation test with the data recorded
using AE.

(a)

(b)
Figure
Figure8.8.Number
Numberof hits (originally
of hits exported
(originally from from
exported Daemon system):
Daemon (a) Fmax =(a)
system): 50FN;
max(b)
= F50 = 1500
maxN; (b) Fmax =
N.
1500 N.

Figure
Figure8a8ashows
shows thethehits curves
hits curvesrecorded during
recorded the macroindentation
during the macroindentation tests of all of all
tests
coating–substrate
coating–substrate systems
systems at aatmaximum
a maximum loadload
of 50ofN.
50The hit parameter
N. The was adjusted
hit parameter to
was adjusted to
count every event which arose in the material during the indentation
count every event which arose in the material during the indentation test. The thresholdtest. The threshold
was
wassetsetaccording
accordingtoto Table
Table 3. 3.
Figure
Figure8b 8b
illustrates the the
illustrates same hits hits
same curves. However,
curves. they they
However,
were captured at a maximum load of 1500 N. We obtained different results
were captured at a maximum load of 1500 N. We obtained different results from acoustic from acoustic
data
datarecorded
recordedatatdifferent
different loads.
loads.A smaller
A smaller number
numberof hits was was
of hits found in theinnACo
found
3 coating
the nACo 3 coating
deposited on sintered carbide in both tests. This is related to the material properties of the
deposited on sintered carbide in both tests. This is related to the material properties of the
substrate. As previously confirmed by nanoindentation, this coating had better resistance
substrate. As previously confirmed by nanoindentation, this coating had better resistance
to plastic deformation than the other coating we tested (Figure 7). The nACo3 coating 3de-
to plastic deformation than the other coating we tested (Figure 7). The nACo coating
posited on HSS substrate had most hits.
deposited on HSS substrate had most hits.
A higher loading force also influences the number of AE events. We suggest that this
A higher loading force also influences the number of AE events. We suggest that
is caused by the substrate type, because sintered carbide is more resistant to plastic defor-
mation. caused
this is The areaby the substrate
around type, because
the indentation imprint sintered carbide
is not widely is more
influenced byresistant to plastic
the indenta-
tion. The coating undergoes elastic deformation up to the brittle failure as a result of con-by the
deformation. The area around the indentation imprint is not widely influenced
indentation.
tact The coating
pressure caused by theundergoes
indentation. elastic deformation
Compared to HSS,upthe to sintered
the brittle failureisasde-
carbide a result
of contact pressure caused by the
formed plastically at relatively high loads. indentation. Compared to HSS, the sintered carbide is
deformed plastically at relatively high loads.
Coatings 2021, 11, 919 10 of 17

Coatings 2021, 11, 919 10 of 17

3.2.2. Hits Energy

3.2.2. Hits
TheEnergy
hits energy parameter is usually involved when the amount of energy dissipated
Thethe
into hitsmaterial
energy parameter
is under is usually involved
investigation. Aswhen the amount
mentioned of energy
before, whendissipated
more energy is
into the material is under investigation. As mentioned before,
dissipated into the material it leads to higher amplitudes and longer when more energy is dissi- of the
durations
pated into the material it leads to higher amplitudes and longer durations
events that are detected. This means that if larger cracks appear, or spalling of of the events
the coating
that are detected. This means that if larger cracks appear, or spalling of the
occurs, more energy is dissipated. The creation of cracks and occurrence of spalling can coating occurs,
more energy isatdissipated.
commence The creation
different loading forces.of When
cracks the
andloading
occurrence
force ofexceeds
spallingthe cancritical
com- value
mence
then cracks and spalling start and can be detected by a hits energy curve. A then
at different loading forces. When the loading force exceeds the critical value hits energy
cracks and spalling start and can be detected by a hits energy curve. A hits energy curve
curve can therefore be used to detect the loading force at which cracking and spalling
can therefore be used to detect the loading force at which cracking and spalling occur.
occur. These material defects depend on the coating material behavior and properties of
These material defects depend on the coating material behavior and properties of the coat-
the coating–substrate system [33].
ing–substrate system [33].
However, by using the hits energy parameter, it is possible to analyze every step
However, by using the hits energy parameter, it is possible to analyze every step of
of loading and estimate the volume of coating–substrate system damage from energy
loading and estimate the volume of coating–substrate system damage from energy dissi-
dissipation
pation causedindentation.
caused during during indentation. The hits
The hits energy energy
curves curves
of all samplesof all
aresamples
given inareFig-given in
3
ureFigure 9. Further
9. Further observation
observation revealed
revealed that
that the the3nACo
nACo coatingcoating
depositeddeposited
on HSSon HSS started
started to to
increase dissipated energy at relatively low loads compared to the
increase dissipated energy at relatively low loads compared to the other specimens. This other specimens. This
coating
coating alsoalso reached
reached the the highest
highest totaltotal
energyenergy
of allof
AEallevents.
AE events.
FigureFigure
9b shows 9b shows
the hitsthe hits
energy curves of all coatings captured at the maximal
energy curves of all coatings captured at the maximal force of 1500 N. force of 1500 N.

Start of Cracks creation

(a)

(b)

Figure 9. Hits Energy curves for TiXCo3/HSS, nACo3/HSS, and nACo3/SC captured at the maximal
force of (a) 50 N and (b) 1500 N.
Coatings 2021, 11, 919 11 of 17

Coatings 2021, 11, 919 11 of 17

Figure 9. Hits Energy curves TiXCo3/HSS, nACo3/HSS, and nACo3/SC captured at the maximal
force of (a) 50 N and (b) 1500 N.

The
The values
valuesofofthe
thehits
hitsenergy
energycurve
curveforfor
thethe
nACo 3 coating
nACo deposited
3 coating on sintered
deposited car-
on sintered
bide (Figure 9b) were the lowest. The hits energy curve of the nACo 3 coating
3 deposited
carbide (Figure 9b) were the lowest. The hits energy curve of the nACo coating deposited on
HSS exhibited almost intermediate values. The TiXCo 3 coating
3 had the maximum
on HSS exhibited almost intermediate values. The TiXCo coating had the maximum value value
of
of hits
hits energy
energy of
of cracks
cracks identified
identified byby acoustic
acoustic emission
emission and
and most
most of
of this
this acoustic
acoustic event
event
caused
caused bybyindentation
indentationwaswasrelated
relatedto
tothe
thecreation
creationof
ofcracks
crackswhich
whichdissipated
dissipatedmore
moreenergy.
energy.
This
This is
isbecause
becausewhen
whenlarger
largercracks
cracksare
arecreated,
created,more
moreenergy
energyisisdissipated
dissipatedinto
intothe
thematerial.
material.

3.2.3.
3.2.3. High-Resolution
High-ResolutionAnalysis
Analysis of
of Indentation
Indentation Imprints
Imprints
Figures
Figures10 10and
and1111depict
depictmicrographs
micrographs of the indentation
of the imprints
indentation takentaken
imprints with with
an elec-
an
electron
tron microscope
microscope (HRSEM).
(HRSEM). FigureFigure 10 shows
10 shows micrographs
micrographs of imprints
of imprints after after the at
the test test
a
at a loading
loading force force
of 50 of
N. 50
TheN.imprint
The imprint
on theon the surface
surface nACo3 coating
of the3 coating
of the nACo deposited deposited
on HSS
on HSS substrate
substrate is shownis inshown
Figure in Figure
10a. 10a.areas
Spalling Spalling
can beareas
seencan be seen
at the edgesatofthe
theedges of the
imprint. In
imprint. Inthe
theTiXCo
case of coating
the TiXCo 3 coating
the case of 3 (Figure 11a),(Figure
a higher11a), a higher
number number of circumferential
of circumferential cracks are
cracks are obvious. 3 coating
obvious. Less cracksLess cracks
can be can bearound
observed observed thearound
imprintthe
of imprint
the nACo of3 the nACo
coating deposited
deposited on HSSbut
substrate, 3
on HSS substrate, spallingbut
wasspalling was documented.
documented. The nACo
The nACo3 coating coatingondeposited
deposited sintered
on sintered carbide substrate is characterized by less cracks and insignificant
carbide substrate is characterized by less cracks and insignificant spalling near the circum- spalling near
the circumferential
ferential crack. crack.

(a) (b)

(c)
Figure10.
Figure 10.Indentation
Indentationimprints
imprintsatatF Fmax== 50
50 N:
N:(a)
(a)TiXCo
TiXCo33/HSS,
/HSS, (b)
(b) nACo
nACo3/HSS,
3
/HSS,and
and(c)
(c)nACo
nACo/SC.
3
3 /SC.
max
Coatings 2021, 11, 919 12 of 17
Coatings 2021, 11, 919 12 of 17

(a) (b)

(c)
Figure11.
Figure 11.Indentation
Indentationimprints
imprintsatatFmax
Fmax==1500
1500N:
N:(a) TiXCo33/HSS,
(a)TiXCo /HSS, (b) nACo33/HSS,
/HSS,and
and(c)
(c)nACo 3 /SC.
nACo3/SC.

The results
The results from
from the microscopic
microscopic examination
examination accord
accord with
with the data captured using
AE (Figure
(Figure9a,b).
9a,b).The
TheTiXCo
TiXCo 3 coating is characterized by the highest values of hits en-
AE 3 coating is characterized by the highest values of hits energy,
ergy, which
which were caused
were caused by plastic
by plastic deformation
deformation of the substrate
of the substrate at the periphery
at the periphery of the
of the inden-
indentation imprint. The TiXCo 3 coating, according to the material parameters calculated
tation imprint. The TiXCo coating, according to the material parameters calculated from
3

from nanoindentation
nanoindentation data (Figure
data (Figure 6), had 6), the
hadhighest
the highest plasticity
plasticity indexindex
andand deformation
deformation re-
resistance. Therefore, it must also have the best tribological behavior
sistance. Therefore, it must also have the best tribological behavior out of all out of allthe
the speci-
speci-
mens. This
mens. This statement
statement was
was confirmed
confirmedmainly mainlyafter
afterusing
usingsmall
smallloads
loadswhere
where thetheinfluence
influenceof
substrates is negligible. However, this coating was not the best solution
of substrates is negligible. However, this coating was not the best solution in the case of in the case of high
loadsloads
high where plastic
where deformation
plastic deformation of theof substrate occurs.occurs.
the substrate This behavior is explained
This behavior by the
is explained
high hardness and small elastic modulus of the coating. This conclusion
by the high hardness and small elastic modulus of the coating. This conclusion can be can be confirmed
based on results 3
confirmed based with the nACo
on results with coating
the nACo deposited
3 coatingon the sameon
deposited substrate.
the sameAs can be seen
substrate.
3 coating deposited on different substrates reached
As
in Figure 9, the specimen with an
can be seen in Figure 9, the specimen with nACo an nACo 3 coating deposited on different sub-
different valuesdifferent
of hits energy. 3 coating deposited on the SC reached a slightly
strates reached valuesThe nACo
of hits energy. The nACo3 coating deposited on the SC
reached a slightly lower value, which may have hard
lower value, which may have been caused by the been substrate
caused by resistant
the hardto deformation.
substrate re-
sistant to deformation.
4. Discussion
The mechanical and tribological behavior of two coatings were investigated by two
4. Discussion
different indentation methods. The nanoindentation method was used to determine the
The properties
material mechanicalofand tribological
coatings. Then, behavior of two
supplemental coatings were
parameters from investigated by data
the indentation two
different indentation methods. The nanoindentation
were calculated and their wear was estimated. method was used to determine the
material
Theproperties of coatings.
second method Then, supplemental
was indentation of the sameparameters from thebut
coatings systems, indentation data
with acoustic
were calculated and their wear was estimated.
emission signals recorded, which enabled an investigation of crack formation and spalling
of coatings at higher loading forces.
Coatings 2021, 11, 919 13 of 17

A comparison of results using both methods results was performed and evaluated.

4.1. Nanoindentation
According to the material parameters obtained from the nanoindentation tests, we
obtained the following findings:
• The TiXCo3 coating deposited on HSS has the highest hardness of all measured
specimens at low indentation depths. However, as depths increase the hardness
reduces. The elastic modulus curve followed a similar pattern.
• The nACo3 coating deposited on both substrates had the same hardness at low depths.
The hardness of both nACo3 coatings also increased with an increase of indentation
depths. The opposite phenomenon was observed for the elastic modulus. The nACo3
coating deposited on SC had higher values over the whole range of depths.
• All hardness changes of coatings due to an increase of indentation depths were
probably caused by differences in the substrates.
• The plasticity index and plastic deformation resistance reached the highest values for
the TiXCo3 coating deposited on HSS.
• The nACo3 coating showed different values of plasticity index and plastic deforma-
tion resistance parameters. nACo3 deposited on SC had the lowest values of both
calculated parameters.
According to the measured and calculated parameters, we can assume that the most
durable coating is TiXCo3 . This coating is very hard and resistant to high loadings.
We also confirmed our findings that there is a difference in measured material param-
eters between both nACo3 coatings deposited on different substrates. nACo3 deposited on
SC reached higher values of elastic modulus but also had the lowest values of plasticity
index and plastic deformation resistance.

4.2. Macroindentation and AE Measuring

The acoustic emission signals captured during macroindentation tests at maximum
loading forces of 50 and 1500 N were evaluated and confirmed by microscopic examination
of indentation imprints. We made the following findings:
Low load tests Fmax = 50 N
• The coating-substrate systems with the lowest number of cracks was nACo3 deposited
on sintered carbide and TiXCo3 on HSS.
• Hits energy parameters showed that the nACo3 coating deposited on high-speed steel
is susceptible to spalling at low indentation loading force.
High load tests Fmax = 1500 N
• From the number of hits parameter, we found that the most susceptible coatings to
cracking are both the TiXCo3 and nACo3 coatings deposited on high speed steel.
• Based on the hits energy parameter, we were able to determine that the TiXCo3 coating
on HSS was more susceptible to a loss of adhesion and spalling of the coating at high
loads, while nACo3 deposited on high-speed steel was less susceptible at high loads,
but the least susceptible was nACo3 deposited on sintered carbide.
All of our findings were confirmed by micrographs of indentation imprints according
to the VD3198 standard [30]. All coatings were acceptable but the TiXCo3 coating was
characterized by the most serious failures. The best results during the high load indentation
test were obtained with the nACo3 coating deposited on sintered carbide. This was
confirmed with the curves shown in Figure 12. The number of hits of all measured
specimens, captured during the tests at maximum loading force of 1500 N, exceeded all
three thresholds adjusted accordingly based on Table 3. Less hits were captured during the
test with the nACo3 coating deposited on sintered carbide and their occurrence started at
higher loading forces compared to the other specimens. The wear resistance of the nACo3
coating was higher when deposited on sintered carbide substrate than HSS. This difference
 confirmed with the curves shown in Figure 12. The number of hits of all measured speci-
mens, captured during the tests at maximum loading force of 1500 N, exceeded all three
Coatings 2021, 11, 919 thresholds adjusted accordingly based on Table 3. Less hits were captured during 14 theoftest
17
with the nACo3 coating deposited on sintered carbide and their occurrence started at
higher loading forces compared to the other specimens. The wear resistance of the nACo3
coating was higher when deposited on sintered carbide substrate than HSS. This differ-
may
encehave
maybeen caused
have been by differences
caused in the elasto-plastic
by differences properties between
in the elasto-plastic thebetween
properties substrates.
the
However, the TiXCo3 coating deposited
3 coating deposited on HSS was similarly susceptibleas
on HSS was similarly susceptible to cracking
substrates. However, the TiXCo to
nACo3 deposited on the same substrate.
cracking as nACo3 deposited on the same substrate.

Figure12.
Figure 12.Cumulative
Cumulativenumber
numberofofhits.
hits.

Webelieve
We believethethehithit parameter
parameter is related
is related to crack
to crack formation
formation andand other
other material
material insta-
instabili-
bilities caused by high tensile stress in the plastic deformation zone
ties caused by high tensile stress in the plastic deformation zone around the imprint, and around the imprint,
and
by by compression
high high compression stressstress
in thein the imprint
imprint area. area.
Thehits
The hitsenergy
energyparameter
parametercan canbe beused
usedforforquantification
quantificationofofcracks
crackssize
sizeand
andspalling
spalling
areaofofthe
area thecoating
coatinglayer.
layer.
Figure13
Figure 13shows
showsthe thehits
hitsenergy
energyrecorded
recordedduring
duringthe
thetests
testsatatmaximum
maximumloading
loadingforce
force
ofof1500
1500NNforforevery
everytested
testedcoating–substrate
coating–substratecombination.
combination.ItItcan
canbe beseen
seenthat
thatless
lessenergy
energy
was 3 3coating deposited on sintered carbide, confirming
wasreleased
releasedduring
duringthe thetest
testofofnACo
nACo coating deposited on sintered carbide, confirming
Coatings 2021, 11, 919 our
ourprevious
previousfindings.
findings.MostMostenergy
energywas wasreleased
releasedduring
duringindentation
indentationfor forthe
thecombination
combination
15 of 17
ofofthe 3 3coating deposited on HSS.
theTiXCo
TiXCo coating deposited on HSS.
Comparing the results in Figures 12 and 13, it is possible to see how the coatings are
susceptible to cracking and spalling. The nACo3 coating deposited on sintered carbide
released least energy during indentationHits Energy and therefore we can assume that it is the best
solution for high loading applications based on its good elastic properties of the coating.
35
The substrate is also highly resistant to plastic deformation.
30 Contrary to parameters calculated from nanoindentation tests, where only the coat-
ing
25 was investigated, the most durable coating–substrate system at high loads was nACo
3

deposited on sintered carbide (Figure 14).

20
15
10
5
0
TiXCo³/HSS nACo³/HSS nACo³/SC

Hit Energy

Figure13.
Figure 13.Maximum
Maximumhits
hitsenergy
energyreached
reachedatatFFmax = 1500 N.
max = 1500 N.

Radar plot
nACo³/HSS TiXCo³/HSS nACo³/SC

Normalized Max
 35
30
25
Coatings 2021, 11, 919 15 of 17
20
15
10 Comparing the results in Figures 12 and 13, it is possible to see how the coatings are
susceptible
5 to cracking and spalling. The nACo3 coating deposited on sintered carbide
released least energy during indentation and therefore we can assume that it is the best
0
solution for high loading applications based on its good elastic properties of the coating.
TiXCo³/HSS nACo³/HSS nACo³/SC
The substrate is also highly resistant to plastic deformation.
Contrary to parameters calculated from nanoindentation tests, where only the coating
Hit Energy
was investigated, the most durable coating–substrate system at high loads was nACo3
deposited on sintered
Figure 13. Maximum carbide
hits energy(Figure
reached14).
at Fmax = 1500 N.

Radar plot
nACo³/HSS TiXCo³/HSS nACo³/SC

Normalized Max
Usage Temperature
1.0
0.8
0.6
Normalized Hits 0.4 Normalized H/E
Energy 0.2
0.0

Normalized
Cumulated number of Normalized H³/E²
Hits

Figure14.
Figure 14.Graphic
Graphicradar
radarrepresentation
representationof
ofacoustic
acousticemission
emissionparameter
parameterresults
resultsin
incomparison
comparisonwith
with
values from nanoindentation.
values from nanoindentation.

5.5.Conclusions
Conclusions
In
Inthis
thisstudy,
study,samples
sampleswith nACo3 3and
withnACo TiXCo33coatings
andTiXCo coatingsdeposited
depositedon onhigh-speed
high-speedsteel
steel
HS6-5-2-5
HS6-5-2-5(1.3243)
(1.3243)and
andsintered
sinteredcarbide
carbidesubstrates
substrateswere wereinvestigated
investigatedin interms
termsofofcoating
coating
wear
wearandandadhesion
adhesionproperties
propertiesusing
usingtwo
twodifferent
differentmethods.
methods.Nanoindentation
Nanoindentationisisthe themost
most
popular
popular method currently used to characterize a coating’s parameters. In this paper,we
method currently used to characterize a coating’s parameters. In this paper, we
used
used the
the coating
coating hardness
hardness and
andelastic
elasticmodulus
moduluscalculations
calculations developed
developed by byOliver
Oliverand
and
Pharr
Pharr[23,24]
[23,24]and
andused
usedthe
theresults
resultstotocalculate
calculateother
otherparameters
parametersincluding
includingthetheplasticity
plasticity
index, 3 3 22 . These parameters were used to evaluate
index,H/E,
H/E, and
and deformation
deformationresistance,
resistance,HH/E /E . These parameters were used to evaluate
the
thetribological
tribologicalandandwear
wearresistance
resistanceofofcoatings
coatingsby byhigh
highloading
loadingtest
testperformance
performancedata.
data.
The
The second indentation method used to determine wear resistanceatathigh
second indentation method used to determine wear resistance highloads
loadswas
was
the
theinstrumented
instrumentedDaimler–Mercedes
Daimler–Mercedes test, while
test, acoustic
while emission
acoustic was used
emission was to detect
used crack
to detect
formation and spalling
crack formation of coatings.
and spalling A special
of coatings. measuring
A special device
measuring havehave
device beenbeen
developed for
developed
this purpose.
for this purpose.
The
Thecoatings
coatingswere
weredeposited
depositedon ondifferent
differentsubstrates,
substrates,which
which resulted
resulted in
in different
differentme-
me-
chanical properties being obtained for the same coating. The results of nanoindentation
chanical properties being obtained for the same coating. The results of nanoindentation
were compared with the results of recorded AE data analysis captured during macroinden-
tation tests. According to the acoustic emission analysis we conclude the following:
• Comparing the acoustic emission events represented by the number of hits parameter,
we conclude that for high loading applications the substrate has a major influence on
the mechanical properties. We found around the same number of hits for different
coatings deposited on HSS substrate and approximately the half number of hits
for coatings deposited on sintered carbide. If the substrate is resistant to plastic
deformation, then the coating is also more resistant to cracking and spalling.
Coatings 2021, 11, 919 16 of 17

We have demonstrated that the use of acoustic emission measuring technology is

more appropriate when the adhesion and wear properties of coatings must be investigated.
This method is easy to use and is significantly faster, as there is no need to make a large
number of indentations. There is also no need to use precise measuring technology. We
can see crack creations in real time and quickly evaluate a hard coating’s susceptibility to
loss of adhesion when a large strain is applied.
The acoustic emission signal detection and evaluation makes it possible to evaluate:
• The susceptibility of the coating to untimely cracking;
• Spalling of coatings;
• The loading force when spalling starts to occur.
The aim of this paper was to find a more effective and accurate method to determine
overall tribological properties of hard coatings deposited on hard substrates. One of
the most outstanding advantages of the acoustic emission method is its fast and precise
detection of cracking and spalling in a coating. It is also possible to determine the critical
forces when cracking and spalling occurs.

Author Contributions: Conceptualization, P.D., M.S. and L’.Č.; methodology, L’.Č.; software, D.M.
and V.K.; validation, L’.Č., D.M. and V.K.; formal analysis, P.D. and V.K.; investigation, P.D.; resources,
P.D. and D.M.; data curation, M.S.; writing—original draft preparation, P.D.; writing—review and
editing, D.M., M.S. and S.I.Š.; visualization, P.D. and D.M.; supervision, L’.Č. and V.K.; project
administration, L.Č.; funding acquisition, L’.Č. and V.K. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was supported by the Slovak Research and Development Agency under
the contract No. APVV-15-0168, and the Slovak Republic Scientific Grant Agency (VEGA) within
Grant No. 1/0540/19. This publication was supported by the Operational Programme Research and
Innovation for the project: “Scientific and Research Centre of Excellence SlovakION for Material and
Interdisciplinary Research” project ITMS2014+: 313011W085, co-financed by the European Regional
Development Fund.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors would also like to thank the Walloon region for financial support in
the frame of the INDMAT project (BEWARE FELLOWSHIPS), co-funded by the European Union
(FP7—Marie Curie Actions).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Baldan, A. Adhesion phenomena in bonded joints. Int. J. Adhes. Adhes. 2012, 38, 95–116. [CrossRef]
2. Popov, V.L.; Pohrt, R.; Li, Q. Strength of adhesive contacts: Influence of contact geometry and material gradients. Friction 2017, 5,
308–325. [CrossRef]
3. Duminica, F.D.; Belchi, R.; Libralesso, L.; Mercier, D. Investigation of Cr(N)/DLC multilayer coatings elaborated by PVD for high
wear resistance and low friction applications. Surf. Coat. Technol. 2018, 337, 396–403. [CrossRef]
4. Sousa, V.F.C.; Silva, F.J.G. Recent advances in turning processes using coated tools—A comprehensive review. Metals 2020, 10,
170. [CrossRef]
5. Mercier, D.; Mandrillon, V.; Parry, G.; Verdier, M.; Estevez, R.; Bréchet, Y.; Maindron, T. Investigation of the fracture of very thin
amorphous alumina film during spherical nanoindentation. Thin. Solid. Films 2017, 638, 34–47. [CrossRef]
6. Krabbe, M. Crack Mechanisms and Crack Interaction in Thin Films; Department of Engineering, Technical report ME-TR-1; Aarhus
University: Aarhus, Denmark, 2012; pp. 18–28, ISSN 2245-4594. Available online: https://tidsskrift.dk/me/article/view/21125/
18625 (accessed on 17 May 2021).
7. Fu, K.; Tang, Y.; Chang, L. Toughness Assessment and Fracture Mechanism of Brittle Thin Films Under Nano-Indentation, Fracture
Mechanics—Properties, Patterns and Behaviours; IntechOpen: Rijeka, Italy, 2016; pp. 121–144. [CrossRef]
8. Malzbender, J.; Den Toonder, J.M.J.; Balkenende, A.R.; De With, G. Measuring mechanical properties of coatings: A methodology
applied to nano-particle-filled sol–gel coatings on glass. Mater. Sci. Eng. R Rep. 2002, 36, 47–103. [CrossRef]
Coatings 2021, 11, 919 17 of 17

9. Azizpour, A.; Hahn, R.; Klimashin, F.F.; Wojcik, T.; Poursaeidi, E.; Mayrhofer, P.H. Deformation and cracking mechanism in
CrN/TiN multilayer coatings. Coatings 2019, 9, 363. [CrossRef]
10. Kramer, D.E.; Yoder, K.B.; Gerberich, W.W. Surface constrained plasticity: Oxide rupture and the yield point process. Philos. Mag.
2001, 81, 2033–2058. [CrossRef]
11. Wang, M.G.; Ngan, A.H.W. Indentation strain burst phenomenon induced by grain boundaries in niobium. J. Mater. Res. 2004, 19,
2478–2486. [CrossRef]
12. Mercier, D. PopIn Toolbox Documentation; GitHub. Available online: https://www.researchgate.net/publication/328530953_
PopIn_Toolbox_documentation (accessed on 30 July 2021).
13. International Organization for Standardization. ISO 14577-1, -2, -3, Metallic Materials–Instrumented Indentation Test for Hardness and
Materials Parameters–Part 1: Test Method, Part 2: Verification and Calibration of Testing Machines, Part 3: Calibration of Reference Blocks;
International Organization for Standardization: Geneve, Switzerland, 2002.
14. International Organization for Standardization. ISO 14577-4, Metallic Materials–Instrumented Indentation Test for Hardness and
Materials Parameters–Part 4: Test Method for Metallic and Non-Metallic Coatings; ISO–International Organization for Standardization:
Geneve, Switzerland, 2007.
15. Silva, F.J.G. Nanoindentation on tribological coatings. In Applied Nanoindentation in Advanced Materials; John Wiley and Sons, Ltd.:
Hoboken, NJ, USA, 2017; pp. 111–133. ISBN 9781119084495.
16. Vidakis, N.; Antoniadis, A.; Bilalis, N. The VDI 3198 indentation test evaluation of a reliable qualitative control for layered
compounds. J. Mater. Process. Technol. 2003, 143, 481–485. [CrossRef]
17. Haršáni, M.; Sahul, M.; Zacková, P.; Čaplovič, L’. Study of cathode current effect on the properties of CrAlSiN hard coatings
deposited by LARC. Vacuum 2017, 139, 1–8. [CrossRef]
18. Polcar, T.; Cavaleiro, A. High-temperature tribological properties of CrAlN, CrAlSiN and AlCrSiN coatings. Surf. Coat. Technol.
2011, 206, 1244–1251. [CrossRef]
19. Ding, X.; Zeng, X.T.; Liu, Y.C. Structure and properties of CrAlSiN Nanocomposite coatings deposited by lateral rotating cathod
arc. Thin. Solid. Films 2011, 519, 1894–1900. [CrossRef]
20. Carvalhoa, S.; Ribeiroa, E.; Reboutaa, L.; Pacaudb, J.; Goudeaub, P.; Renaultb, P.O.; Rivièreb, J.P.; Tavares, C.J. PVD grown
(Ti,Si,Al)N nanocomposite coatings and (Ti,Al)N/(Ti,Si)N multilayers: Structural and mechanical properties. Surf. Coat. Technol.
2003, 172, 109–116. [CrossRef]
21. Mishra, S.K. Toughening of nanocomposite hard coatings. Rev. Adv. Mater. Sci. 2020, 59, 553–585. [CrossRef]
22. Cselle, T.; Coddet, O.; Galamand, C.; Holubar, P.; Jilek, M.; Jilek, J.; Luemkemann, A.; Morstein, M. TripleCoatings3® –New
generation of PVD-coatings for cutting tools. J. Mach. Manuf. 2009, 49, 19–25.
23. Oliver, W.; Pharr, G. An improved technique for determining hardness and elastic modulus using load and displacement sensing
indentation experiments. J. Mater. Res. 1992, 7, 1564–1583. [CrossRef]
24. Oliver, W.; Pharr, G. Measurement of hardness and elastic modulus by instrumented indentation: Advances in understanding
and refinements to methodology. J. Mater. Res. 2004, 19, 3–20. [CrossRef]
25. Musil, J. Tribological and mechanical properties of nanocrystalline-TiC/a-C nanocrystalline-TiC/a-C nanocomposite thin films. J.
Vac. Sci. Technol. 2010, 28, 244. [CrossRef]
26. Musil, J. Hard and superhard nanocomposite coatings. Surf. Coat. Technol. 2000, 125, 322–330. [CrossRef]
27. Musil, J. Hard nanocomposite coatings: Thermal stability, oxidation resistance and toughness. Surf. Coat. Technol. 2012, 207, 50.
[CrossRef]
28. Musil, J.; Kunc, F.; Zeman, H.; Poláková, H. Relations between hardness, youngs modulus and elastic recovery in hard
nanocomposite coatings. Surf. Coat. Technol. 2002, 154, 304–313. [CrossRef]
29. Leyland, A.; Matthews, A. On the significance of the H/E ratio in wear control: A nanocomposite coating approach to optimised
tribological behaviour. Wear 2000, 246, 1–11. [CrossRef]
30. Verein Deutscher Ingenieure Normen, VDI 3198; VDI-Verlag: Dusseldorf, Germany, 1991.
31. Grosse, U.C.H.; Ohtsu, M. Acoustic Emission Testing, 1st ed.; Springer: Berlin/Heidelberg, Germany, 2008; pp. 41–51. ISBN
978-3-540-69895-1.
32. Youyuan, L.; Zongjin, L. Study of the relationship between concrete fracture energy and AE signal energy under uniaxial
compression. J. Mater. Civ. Eng. 2012, 24, 538–547. [CrossRef]
33. Drobný, P. Acoustic emission analysis of hard coatings cracking during indentation test. IOP Conf. Ser. Mater. Sci. Eng. 2020, 726,
012004. [CrossRef]