Surface & Coatings Technology 429 (2022) 127949

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Surface & Coatings Technology

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

Hard coatings for cutting applications: Physical vs. chemical vapor

deposition and future challenges for the coatings community
Nina Schalk a, b, *, Michael Tkadletz a, Christian Mitterer a
a
Department of Materials Science, Montanuniversität Leoben, Franz-Josef-Straße 18, 8700 Leoben, Austria
b
Christian Doppler Laboratory of Advanced Coated Cutting Tools, Department of Materials Science, Montanuniversität Leoben, Franz-Josef-Straße 18, 8700 Leoben,
Austria

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

Keywords: Since decades, protective hard coatings with thicknesses of a few micrometers are grown by physical or chemical
Hard coatings vapor deposition (PVD, CVD) on cutting tools to improve their application performance. For the huge variety of
PVD cutting applications, different coating materials are used, which typically belong to the material classes of ni­
CVD
trides, carbides, carbonitrides, borides, boronitrides or oxides, frequently in bi- or multilayer stacks. The present
Microstructure
Mechanical properties
work surveys typical hard coatings belonging to the respective material classes, deposited by PVD as well as CVD.
Pioneering studies in this field as well as recent findings contributing to the establishment of comprehensive
“synthesis – structure – property – application performance” relationships of the respective coatings are discussed
and the current state-of-research is reviewed. Condensed summaries and comparisons between PVD and CVD
coatings are given at the end of each subsection. In addition, current and future challenges for the hard coatings
community are surveyed.

1. Introduction There are, of course, older reviews on hard coatings available in

Cutting tools have to withstand severe conditions during application,
such as high temperatures of up to 1000 ◦ C, pronounced friction and
wear, corrosion and oxidation as well as mechanical and thermal fatigue
[1–5]. Thus, hard and wear protective coatings are commonly deposited
on the tools to improve their application performance and lifetime. The
continuing trend of the machining industry towards higher productivity
and cost efficiency results in further increasing cutting velocities and
feed rates and a simultaneous demand for longer tool lifetimes. In
addition, environmental considerations require the reduction of the use
of harmful lubricants and coolants. To meet these demands, continuous
further developments of hard coatings are imperative. Hard coatings for
cutting applications are commonly synthesized by both, physical and
chemical vapor deposition (PVD, CVD). Depending on the particular
application different coating materials are used, which are frequently
also combined to sophisticated coating architectures to further improve
the cutting performance [2,6–8]. Hard materials can be generally clas­
sified according to their chemical bonding character, where the majority
of the hard coatings discussed within this work (e.g. Ti1-xAlxN, TiCxN1-x
or TiB2) are mainly characterized by their metallic bonding, while e.g.
Al2O3 is characterized by its ionic bonding, as shown in Fig. 1. [9,10]
literature [3,4,11–15] as well as reviews focusing on application and
wear characterization [16,17], however, apart from the further devel­
opment of the hard coatings themselves, the implementation and further
development of advanced modern characterization techniques [18]
allow new insights and also enable the in-depth comparison of PVD and
CVD coatings. Here, Ti1-xAlxN is a suitable example. The synthesis of Ti1-
xAlxN coatings by CVD has gained increasing interest in recent years and
the thorough characterization of its nanolamellar microstructure is only
possible due to the availability and complementary application of
transmission electron microscopy and atom probe tomography. Also the
thermal and oxidation stability of hard coatings and thus, the underlying
mechanisms can nowadays be monitored in-situ applying simultaneous
differential scanning calorimetry and synchrotron X-ray diffraction
measurements. Recent developments in the determination of the
thermo-physical properties of coatings [18] have shifted the possibility
of thermal management in the focus of the hard coatings community. All
these recent developments are illumined within the present work on the
examples of representative hard coatings belonging to the material
classes of nitrides, carbides, carbonitrides, borides boronitrides and
oxides, where PVD and CVD coatings are compared. In addition, an
outlook is provided on necessary future changes and developments,

* Corresponding author at: Department of Materials Science, Montanuniversität Leoben, Franz-Josef-Straße 18, 8700 Leoben, Austria.
E-mail address: nina.schalk@unileoben.ac.at (N. Schalk).

https://doi.org/10.1016/j.surfcoat.2021.127949
Received 27 August 2021; Received in revised form 19 November 2021; Accepted 21 November 2021
Available online 4 December 2021
0257-8972/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
N. Schalk et al.
Fig. 1. Chemical bonding triangle of hard materials and associated properties.
Redrawn and supplemented after [9,10].
which need to be addressed by the hard coatings community in
academia and industry, to make their processes and coatings environ­
mentally more friendly and compatible with resource conservation
requirements.
2. Metal cutting and requirements on the coating
Benefiting from synergies between industry, performing cutting
tests, and university, providing the necessary characterization methods,
damage and wear mechanisms and consequently, requirements on the
hard coatings can be assessed. During metal cutting, high forces act in
the contact region between tool and work piece material. The chip
Fig. 2. a) Temperature distribution in the Ti6Al4V work piece/chip and Ti1-xAlxN coated cemented carbide tool after 5 ms in the first cut of a dry milling operation.
b) Temperature profiles along the two paths A-B indicated in a) as a function of the milling time during the first cut. c) Distribution of the plastic strain rate in the chip
after 5 ms in the first cut. d) Temperature distribution after 5 ms in the last cut and corresponding e) temperature profiles along A-B and f) distribution of the plastic
strain rate [21].
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Surface & Coatings Technology 429 (2022) 127949
formation process involves plastic deformation at the shear zones,
generating heat and contact stress in the tool [1,14,19,20] and the tool is
subjected to abrasive and adhesive wear. Exemplarily, the simulated
temperature distribution in a Ti1-xAlxN coated cemented carbide tool
and the Ti6Al4V work piece material/chip as well as the simulated
distribution of the plastic strain rate in the work piece for a dry milling
operation are shown in Fig. 2 [21]. The task of hard coatings is in general
to provide wear and thermal protection of the tool substrate. However,
the specific requirements on the coatings depend on the cutting process
and the work piece material. Basically, continuous or interrupted cutting
processes have to be distinguished. In continuous cutting, e.g. in turning,
high temperatures are reached in the contact region. Commonly, thick
(~ 5–20 μm) coatings with low thermal conductivity are accepted as
favorable for turning applications, since they provide a thermal barrier
to the underlying substrate and the generated heat is deflected into the
chip. Thus, the thermal load of the substrate is reduced, preventing or
retarding plastic deformation [19]. However, for work piece materials
with low thermal conductivity and thus, poor heat deflection into the
chip, high peak temperatures and steep thermal gradients can be ob­
tained, which requires coatings with sufficient thermal conductivity to
dissipate the heat from the contact region [14]. If the cut is interrupted,
like e.g. in milling, heat is not continuously generated and thus, the
temperatures are lower than in continuous cutting, but the cyclic me­
chanical and thermal loading result in fatigue of the cutting edge [14].
Consequently, thinner (~ 3–5 μm) coatings, exhibiting compressive re­
sidual stress and thus, typically PVD coatings, are favorable for such
applications.
The main wear mechanisms are schematically visualized in Fig. 3a
[15]. In Fig. 3b a light optical micrograph of a worn cutting insert after
steel turning is shown, exhibiting crater wear at the rake face, which is a
result of the contact with the flowing chip, and flank wear at the flank
face, which is a result of the contact between work piece and insert. In
N. Schalk et al. Surface & Coatings Technology 429 (2022) 127949

Fig. 3. a) Schematic of main wear types on a cutting insert [15]. b) Light optical micrographs of worn cutting inserts showing crater wear and flank wear, indicating
also the two wear markers VBH(max) on the clearance flank and VBR(max) on the nose [22]. c) Light optical micrographs of cross-sections of worn cutting inserts at the
end of life time after turning of three different steels. In addition to crater and flank wear also plastic deformation of the nose is visible. d) Scanning electron
micrograph of the cross-section of an unused cutting insert superimposed with the worn cutting edges from c), clearly showing the different plastic deformation after
milling of the different steels [22]. e) Scanning electron micrograph of the rake face of a worn milling insert showing comb cracks, marked by white arrows. The black
arrows mark the region for the focused ion beam prepared cross-section shown in f) where a comb crack can be seen, which is filled with work piece material [23].

addition, the two wear markers VBH(max) on the clearance flank and VBR
(max) on the nose are indicated [22]. Fig. 3c shows light optical micro­
graphs of cross-sections of worn cutting inserts after turning of different
steels. In addition to crater and flank wear, also plastic deformation of
the nose, as a result of high contact temperatures, can be observed. The
plastic deformation becomes even better visible in Fig. 3d, where a
scanning electron micrograph (SEM) of a cross-section of an unused
cutting insert is superimposed with the contours of the three worn in­
serts from Fig. 3c, also highlighting the different effects of different work
piece materials [22]. The scanning electron micrograph of a worn
milling insert in Fig. 3e shows the presence of comb cracks, which
typically arise in interrupted cutting and are a result of thermal fatigue
[23]. In Fig. 3a also chipping is included as a main wear mechanism and
it can also be seen in the light optical micrograph of the worn insert after
turning of 100Cr6 work piece material in Fig. 3c. While the coating is
responsible for providing wear resistance and heat protection of the
substrate, the substrate controls the fracture resistance and thus, also the
resistance against chipping of the cutting edge [14]. In order to increase
the toughness and prevent edge chipping, commonly cemented carbide
substrates with Co-enriched near-surface zones are applied [5,24].
However, the choice of the cemented carbide with respect to its
microstructure and composition strongly depends on the application
[25]. Good adhesion between substrate and coating is a prerequisite for
successful coating design [14]. Typically, CVD coatings exhibit better
adhesion as a result of more pronounced atomic diffusion [14], but this
more pronounced diffusion can also be unfavorable, if detrimental
compounds are formed, like W6Co6C (η-phase) or CoWB phases, neces­
sitating the application of diffusion barrier layers, where primarily TiN
is used [26]. To provide sufficient adhesion, substrates are typically
subjected to mechanical, chemical or physical pre-treatments, such as
grinding, blasting, chemical or ultrasonic cleaning prior to PVD [27].
Commonly, the substrates are further cleaned in the deposition chamber
by heating and/or ion etching, to remove contaminations as well as
surface oxides by sputtering [27–30]. Following the coating deposition,
which is discussed in more detail in Section 3, especially CVD coatings
are often subjected to a post-treatment to smoothen the surface and to
introduce compressive residual stress into the surface near zone
[31–36].
3. Coating deposition
Synthesis of hard coatings is commonly realized by condensation
from the vapor phase, applying either PVD or CVD techniques. These
techniques have found their respective application areas, e.g. coating
deposition on cemented carbide substrates for CVD and on steels for PVD
[1,27]. Since within the present manuscript, coatings synthesized by
PVD and CVD are compared, the fundamentals of PVD and CVD pro­
cesses as well as the main film forming mechanisms will be discussed in

3
N. Schalk et al.
the following subsections to outline the intrinsic differences.
3.1. Physical vapor deposition
PVD covers a range of non-equilibrium processes, where the
compositional variety of the grown films is not limited by thermody­
namics, enabling the deposition of metastable solid solutions [37].
Depending on the physical method applied to transfer the solid pre­
cursor material (the so-called target) into the vapor phase, PVD pro­
cesses can be classified into sputtering and evaporation [27]. PVD
processes are line-of-sight processes, which means that only the area of
the substrate that is directly exposed to the target is coated. A major
advantage of PVD is that low substrate temperatures close to room
temperature are possible, allowing also the use of temperature sensitive
substrates [27]. Frequently, reactive deposition processes are applied,
where in addition to the working gas (commonly Ar) a reactive gas (e.g.
N2 or O2) is introduced into the deposition chamber [37]. The substrate
holder can be either grounded, or a negative substrate bias voltage can
be applied resulting in bombardment of the growing film with energetic
ions, which promotes the activation of film growth due to atomic scale
heating. As a result of the additional kinetic activation of film growth,
films synthesized by PVD are typically characterized by high defect
densities, small grain sizes and compressive stresses [38]. For the
deposition of hard coatings, magnetron sputtering and cathodic arc
evaporation (CAE) are the prevailing methods, which will be discussed
in more detail in the following.
3.1.1. Cathodic arc evaporation
Using CAE, transfer of the solid target material into the vapor phase
is achieved by an arc between two electrodes in a vacuum chamber,
where the target forms the cathode and the chamber wall the anode
[39]. An arc is a high current, low voltage electrical discharge concen­
trated on a small spot (10− 8 to 10− 4 m), where the arc meets the cathode,
thus resulting in high current densities (106 to 1012 A/m2) and conse­
quently in explosive evaporation of the material. The main benefit of
CAE is the high ionization rate, leading to dense films with increased
wear resistance [39–41]. A major disadvantage of CAE is the emission of
droplets from the cathode spot, which are incorporated into the growing
film, as shown in Fig. 4. These droplets typically exhibit a metallic core,
which is overgrown by coating material (Fig. 4b) and acts as re-
nucleation site causing voids and microstructural coarsening. The
resulting structures provide high diffusivity pathways, represent me­
chanically weak spots and cause high surface roughness [41–43]. While
incorporation of droplets can be avoided by separating them from the
flux of ions by magnetic filtering [41], this approach is barely used for
the deposition of hard coatings on tools.
3.1.2. Magnetron sputtering
Using sputter deposition, the solid target material is transferred into
the vapor phase by bombardment with energetic ions. As a result of
energy and momentum transfer of the incident ions, surface atoms of the
target are ejected. The ejected particles are mainly neutrals. To provide
the ion bombardment, an inert working gas (commonly Ar) is intro­
duced into the vacuum chamber to a pressure in the range of 10− 3 to
10− 2 mbar. Subsequently, a voltage is applied between the target,
forming the cathode, and the anode (the chamber wall), igniting a glow
discharge, which results in ionization of the working gas constituting the
plasma [27]. In magnetron sputtering, permanent magnets are mounted
behind the targets. The thus created magnetic field superimposes the
electric field of the glow discharge, enabling confinement of the elec­
trons close to the targets. As a consequence, the ionization rate is
increased close to the target surface, resulting in enhanced ion
bombardment and thus, increased sputter rates. Depending on the
configuration, balanced and unbalanced magnetron sputtering can be
distinguished. In a balanced magnetron all magnetic field lines loop
between the inner and outer magnets, while in an unbalanced
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Surface & Coatings Technology 429 (2022) 127949
magnetron one magnet is stronger than the other leading to partially
open magnetic field lines towards the substrate holder (Fig. 5), allowing
the plasma to expand in that direction. The benefit of an unbalanced
magnetron is that the ionization rate is also increased near the substrate,
resulting in bombardment of the growing film with low energy ions,
which promotes film growth [37,44]. Compared to CAE, the main
advantage of sputter deposition is the avoidance of droplets allowing the
deposition of smooth films. In addition, the vapor is generated by energy
and momentum transfer and not thermally, which facilitates also the
deposition of materials with high melting points [45].
3.2. Chemical vapor deposition
CVD comprises all methods where gaseous precursors are introduced
into a reaction chamber to synthesize a coating [46]. The activation of
dissociation and chemical surface reactions of the precursors is mainly
achieved thermally, which can for instance be realized using a hot-wall
reactor, where the substrates are heated indirectly. Hot-wall reactors are
frequently applied in the hard coating industry. The substrates can also
be inductively or resistively heated in a cold wall reactor or utilizing
laser assistance. Another possibility is plasma assisted CVD, relying on
kinetic activation [46,47]. In addition to the substrate temperature,
which is in thermally activated CVD in the range between 800 and
1150 ◦ C, the deposition pressure is another decisive process parameter
[6,48,49]. As the internal gas stream velocities, determining the resi­
dence time and the boundary layer thickness and thus the reactant
diffusion to the substrate surface, depend on the pressure, the deposition
pressure affects the homogeneity of the deposition process within the
reactor [47]. A heterogeneous reaction on the surface is the desired
reaction to form a coating. Although compared to PVD, CVD is much
more governed by thermodynamics, it is not an equilibrium process but
also underlies kinetic limitations, which determine the deposition rate
and also strongly affect the coating microstructure. Two rate limitations
can be distinguished: i) surface reaction limitation (Fig. 6a) and ii) mass
transport limitation (Fig. 6b). At low temperatures or pressures the re­
action occurs slowly, the boundary layer is thin, the diffusion fast, the
reactants easily reach the surface. When the process is limited by the
mass transport, the determining parameter is the diffusion rate of the
reactants through the boundary layer. Mass transport limitation usually
occurs at high temperatures and pressures, resulting in low gas velocity
and thicker boundary layers. Commonly, deposition within the surface
reaction kinetics controlled regime is favored, since it yields a more
uniform deposition within the reactor [46,47]. Homogeneous gas phase
reactions typically occur at temperatures above the decomposition
temperatures of the species inside the reactor and result in the formation
of powder, which is undesired in a deposition process [47]. A major
advantage of CVD is the high throwing power, and thus the capability to
also coat complex geometries. Further benefits are the large possible
batch sizes and high attainable coating thicknesses [46]. Apart from the
high deposition temperatures, which limit the choice of substrate ma­
terials, another drawback of CVD coatings is that they commonly exhibit
tensile residual stress and a high surface roughness, which is unfavor­
able in application and thus necessitates a post-treatment [35,36,50].
3.3. Thin film growth
The vaporized species impinge on the substrate surface and are either
immediately reflected or condense on the surface and become loosely
bonded adatoms. These adatoms can be either desorbed after some
residence time or find other adatoms and build stable nuclei or condense
at already existing nuclei, which preferentially form at low energy sites,
like lattice defects, atomic steps or grain boundaries [27]. Following
nucleation, film formation occurs according to the three basic growth
modes: (i) Island (Volmer-Weber) growth ensues when the binding en­
ergy between the film atoms is stronger than between the film atoms and
the substrate, resulting in three dimensional growth of stable nuclei to
N. Schalk et al.
Fig. 4. Scanning electron micrographs of a) a fracture cross-section of a TiAlN coating including a droplet, showing voids beneath the droplet and b) a focused ion
beam prepared cross-section of a TiAlTaN coating, adapted after [42].
Fig. 5. a) Schematic of an unbalanced magnetron sputtering system [4]. b) Photograph of plasma extending from the targets towards the substrate holder (above)
inside an unbalanced magnetron sputtering system.
Fig. 6. Rate limitations in CVD: a) surface reaction limitation and b) mass
transport limitation [46].
form islands. (ii) Layer-by-layer (Frank-van der Merwe) growth occurs
in the opposite case; when the binding energy between the film atoms
and the substrate is stronger than between the film atoms. (iii) In mixed
layer-island (Stranski-Krastanov) growth, which is a combination of the
other two growth modes, first one or more monolayers are formed until
island growth becomes energetically more favorable [37]. Hard coatings
typically exhibit island growth [51].
The film microstructure and consequently also the properties are
determined by the nucleation and growth kinetics, which strongly
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Surface & Coatings Technology 429 (2022) 127949
depend on the deposition parameters. In order to relate the deposition
parameters to the evolving microstructures, structure zone models
(SZM) have been developed. The first SZM was proposed by Movchan
and Demchishin [52] for thick (up to 2 mm) films deposited by thermal
evaporation. Relating the observed structures to the homologous tem­
perature (i.e. the substrate temperature Ts divided by the melting tem­
perature of the film material Tm), they distinguished three different
zones. In zone 1, the surface mobility of the condensed atoms is small or
even zero, leading to porous columnar structures, highly affected by
shadowing effects. Zone 2 is governed by surface diffusion, resulting in
dense columnar grains expanding from bottom to top of the film. In zone
3, bulk diffusion becomes decisive and a recrystallized structure with
equiaxed grains as well as further densification of the film is observed
[52]. Several authors adapted the SZM proposed by Movchan and
Demchishin by considering further deposition parameters. Thornton
[53] additionally considered the inert sputtering gas pressure and
introduced a fourth zone, the transition zone (zone T), between zone 1
and 2. In this zone T, surface diffusion is more pronounced than in zone
1 and competitive growth occurs, resulting in a denser fibrous structure.
Messier et al. [54] added the substrate bias potential to Movchan and
Demchishin's SZM. The most recent adaption of the SZM was published
by Anders [55] in 2010 and is shown in Fig. 7. There, still the originally
proposed three structure zones complemented by zone T are considered,
but in addition to the homologous temperature also the thermal shift
caused by the potential energy of particles bombarding the film surface
is included in the generalized temperature T*. Further, the displacement
and heating effects due to the kinetic energy of impinging particles (i.e.
atomic scale heating [38]) are accounted for in the normalized energy
flux E*. The third parameter considered in the SZM is the net film
thickness t*, which indicates thickness reduction due to densification or
re-sputtering [55].
N. Schalk et al.
Fig. 7. Structure zone model for thin film growth published by Anders [55].
4. Ti1-xAlxN based coatings
Coatings of transition metal nitrides (TMN) have been used since five
decades for various applications, due to their optical appearance, high
melting point, high hardness and reasonable oxidation and corrosion
stability [10]. The most popular representative is TiN, which is not only
used for cutting applications, but also as diffusion barrier in micro­
electronics and due to its golden colour also for decorative purposes
[10,56–62]. In the cutting industry, TiN has been widely replaced by Ti1-
xAlxN as dominating coating layer, but TiN is still indispensable as
barrier layer to avoid inter-diffusion of elements of substrate and coating
[35,42,63–70]. Further, it is a valuable constituent in multilayer ar­
chitectures [71], which will be discussed later, and it is frequently
applied as top-layer, where it primarily serves as wear marker. Other
important representatives for binary TMN coatings are CrN [72–76] and
ZrN [11,77–80], while TaN and HfN only play a subordinate role for
cutting applications [81,82]. Similarly to TiN, CrN and ZrN are
frequently alloyed with Al to further improve the coating properties
[83–90]. Since these ternary Al-containing TMN have continuously
replaced the binary TMN for severe cutting processes, Ti1-xAlxN as the
most prominent and widely used representative is discussed in more
detail in the following, taking into account the well-established micro­
structure – property relations for PVD processes but also those for the
recently introduced synthesis of high Al-containing Ti1-xAlxN coatings
by thermal CVD.
4.1. PVD Ti1-xAlxN based coatings
Ti1-xAlxN is one of the most widely used coating materials for cutting
tools, where it is commonly applied for milling and turning of steels.
Until recently, Ti1-xAlxN has been exclusively synthesized by PVD pro­
cesses, since these are non-equilibrium processes and thus, the compo­
sitional range is essentially not limited by thermodynamics, allowing the
deposition of metastable solid solutions [37,91]. The formation of
metastable face centered cubic (fcc) Ti1-xAlxN is based on the substitu­
tion of Ti atoms by Al atoms in the fcc-TiN lattice and is limited to Al
metal fractions up to x ~ 0.67, where the exact limit depends on the
deposition parameters and the resulting microstructure [68,92–94]. At
higher Al contents a dual-phase structure is formed, consisting of the fcc
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Surface & Coatings Technology 429 (2022) 127949
and the mostly undesired wurtzitic (w) phase,1 followed by a single-
phase w structure, where Ti atoms substitute for Al atoms in the w-
AlN lattice. An increasing Al content results in improved mechanical
properties, as long as the structure remains fcc [43,95–98]. The chem­
ical composition and microstructure and consequently, the properties
and application behavior of Ti1-xAlxN coatings are significantly influ­
enced by the deposition parameters [68,92,93]. In a recent publication,
Liu et al. [94] demonstrated using experimental and theoretical methods
that the solubility limit of Al in fcc-Ti1-xAlxN is significantly affected by
the residual stress, which can be tailored by adjusting the deposition
parameters. They showed that with increasing compressive residual
stress the solubility limit increases [94]. Grossmann et al. [68] studied
the effect of the deposition parameters on cathodic arc evaporated Ti1-
xAlxN coatings grown from targets with four different compositions at
two different bias voltages. Fig. 8a shows that a higher bias voltage re­
sults in higher Al metal fractions in the coating, compared to coatings
deposited at lower bias voltages from the same target. In Fig. 8b, a
single-phase fcc structure can be observed up to an Al metal fraction of
~ 0.50 for both bias voltages. At higher Al fractions, all coatings already
show a dual-phase structure, however, for the coatings grown at the
higher bias voltage the w phase fractions are less pronounced, which
was also observed by Wüstefeld et al. [92] and is in good agreement with
the study of Liu et al. [94], since a higher bias voltage typically results in
higher compressive stress [92,98,99]. The Ti1-xAlxN coatings grown at
the higher bias voltage exhibit broader peaks in the X-ray diffracto­
grams, indicating a smaller grain size and higher defect density as a
result of the more intense ion bombardment [38,68]. The higher
compressive stress and defect density and the smaller grain size is re­
flected in a higher hardness for the coatings grown at the higher bias
voltage, as visible in Fig. 8c. For Al metal fractions >0.50, the hardness
considerably decreases, which is related to the presence of the w phase
fraction. Nevertheless, the milling lifetime, shown in Fig. 8d, increases
up to an Al metal fraction of ~ 0.60, despite the presence of the w phase.
At higher Al fractions, the milling lifetime only slightly decreases for the
coating grown at the higher bias voltage, while it significantly drops for
the coating grown at the lower bias voltage [68]. This evidences that the
presence of small w phase fractions does not necessarily negatively
affect the application behavior, although the hardness immediately
drops. The reasons for this behavior are not clear up to now, but the
higher Al content and thus, the increased oxidation resistance as well as
a possible crack-retarding effect at the interfaces within the dual-phase
structure might overcompensate the loss in hardness
[63,65,95,100,101].
At temperatures above 800 ◦ C, the metastable Ti1-xAlxN spinodally
decomposes into fcc-TiN rich and fcc-AlN rich domains, resulting in age
hardening (Fig. 9a) due to coherency strains between the matrix and the
formed coherent domains, as schematically shown in Fig. 9b. Further
increasing of the temperature entails a transformation of the metastable
fcc-AlN into the stable w phase (Fig. 9b). This phase transformation is
accompanied by a hardness loss, which is clearly evident from Fig. 9a
[43,67,93,102,103]. The hardness decrease observed for TiN at tem­
peratures above 400 ◦ C is related to recovery and recrystallization [67].
Norrby et al. [104] investigated the spinodal decomposition of an arc
evaporated Ti0.6Al0.4N coating occurring during continuous turning.
Transmission electron microscopy (TEM) investigations revealed an
ongoing spinodal decomposition during turning, where the progress of
the decomposition varies along the rake face (Fig. 9c-f), due to the
observed temperature and stress distribution [104].
1
The crystal structure of AlN is commonly referred to as wurtzite or wurtzitic
structure, which corresponds to the hexagonal crystal system, dihexagonal
pyramidal crystal class and the space group is P63mc. Wurtzite is actually a
polymorph of ZnS (β-ZnS). In literature sometimes also hexagonal AlN can be
found, but since wurtzitic AlN is much more common it is also used within this
work.
N. Schalk et al. Surface & Coatings Technology 429 (2022) 127949

Fig. 8. a) Comparison of the Al/(Al + Ti) metal ratio of the respective targets and of arc evaporated Ti1-xAlxN coatings deposited at two different bias voltages (VB).
b) X-ray diffractograms of the Ti1-xAlxN coatings deposited at two different bias voltages, from bottom to top with increasing Al fraction in the target. c) Hardness and
d) milling lifetime of the same Ti1-xAlxN coatings as a function of the Al metal fraction [68].

Fig. 9. a) Comparison of hardness of TiN and Ti0.34Al0.66N after annealing [67]. b) Illustration of spinodal decomposition of Ti1-xAlxN into fcc-TiN and fcc-AlN rich
domains (left) and dual-phase structure (right) after transformation of fcc-AlN into w-AlN at higher annealing temperatures [102]. c-f) Scanning transmission
electron micrographs of a Ti0.6Al0.4N coating after turning application taken at different distances from the cutting edge, where from c) to f) the distance increases
and the progress of spinodal decomposition decreases [104].

7
 N. Schalk et al.
The oxidation resistance is reported to increase significantly from ~
600 ◦ C for TiN to ~ 800 ◦ C for Ti1-xAlxN, as a result of the formation of a
stable Al2O3 scale on top [63,65,95]. Greczynski et al. [100] recently
showed that the oxide scale formation in Ti1-xAlxN is governed by the Al
concentration and the oxidation temperature, as summarized in Fig. 10.
They observed two basic oxidation types; Type 1, the commonly re­
ported passivating TiO2/Al2O3 double layer, which actually only
occurred at rather low Al contents and high oxidation temperatures in
their study, and type 2, a mixed non-conformal TiO2-Al2O3 layer,
forming at higher Al contents and lower oxidation temperatures, which
does not provide sufficient protection from further oxidation and results
in thicker oxide layers [100].
Further improvement of PVD Ti1-xAlxN can be achieved by alloying
with different elements, like Ta, W, V, B or Si [105–116], where Ta and
Si are the most commonly used alloying elements. The addition of Ta has
beneficial effects on the mechanical and tribological properties as well
as on the thermal and oxidation stability [105,106,117–119]. Recently,
Ta has been shown to also be a highly promising constituent for other
nitride based hard coatings, such as Cr1-xTaxN [120]. Earlier works
suggest that the addition of Ta to Ti1-xAlxN fosters the formation of the
fcc phase and consequently results in a shift of the w phase formation to
higher Al contents [117,121]. However, Grossmann et al. [118]
observed a considerably decreasing Al content with increasing Ta con­
tent for arc evaporated Ti1-x-yAlxTayN coatings, deposited from six
different target compositions with Ti/Al ratios of 50/50 and Ta contents
from 0 up to 15 at.%. In Fig. 11a-c, the metal fractions of Al, Ti and Ta of
the coatings are compared to the target compositions. While the Al
content in the coating significantly decreases with increasing Ta content
in the target, the Ta content in the coatings is substantially higher than
in the respective targets. In contrast, the deviation of the Ti metal
fraction between coating and target decreases with increasing Ta con­
tent. Grossmann et al. [118] explained this compositional evolution by
the huge mass difference between Al, Ti and Ta atoms and consequently
increased scattering of the light Al atoms in the gas phase. In addition,
preferred re-sputtering of Al might also contribute to the differences
between the coating and the target composition [113,118]. Considering
the compositional evolution with increasing Ta content observed in
Fig. 11, the decreasing Al content can be assumed to significantly
contribute to the stabilization of the fcc phase at higher Ta contents, in
addition to the decreasing energy of formation for fcc-Ti1-x-yAlxTayN
with increasing Ta content reported by Rachbauer et al. [117]. Rach­
bauer et al. also reported a slightly decreasing Al metal fraction with
increasing Ta content for sputtered Ti1-x-yAlxTayN coatings [117].
At elevated temperatures, the metastable fcc-Ti1-x-yAlxTayN spino­
dally decomposes analogously to fcc-Ti1-xAlxN, into fcc-Ti1-zTazN and
Fig. 10. Different oxidation types for Ti1-xAlxN, depending on the Al concen­
tration and oxidation temperature [100].
8
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Surface & Coatings Technology 429 (2022) 127949
fcc-AlN enriched domains, followed by the fcc to w transformation of
AlN. However, with increasing Ta content the onset of spinodal
decomposition and w phase formation are shifted to higher tempera­
tures [117,118]. Grossmann et al. [118] observed age hardening for arc
evaporated coatings with rather low Ta contents (Fig. 12a), where the
hardness maxima are shifted to higher temperatures with increasing Ta
content, which is in good agreement with the detected shift of the onset
of spinodal decomposition. For higher Ta contents, no hardness increase
at elevated temperatures was determined (Fig. 12b), but the high initial
hardness is retained up to ~1000 ◦ C. The suppression of age hardening
might be related to the presence of the hexagonal Ta2N phase, which
was detected in these coatings [118]. In contrast, Koller et al. observed
pronounced age hardening for an arc evaporated Ti0.45Al0.36Ta0.19N
coating, which did not exhibit the hexagonal Ta2N phase [122].
The improved oxidation stability of Ti1-x-yAlxTayN compared to Ti1-
xAlxN is based on the formation of a layered oxide scale, consisting of an
Al-rich top-layer and a Ti-Ta-rich sublayer (Fig. 13a) [117,123]. Reddy
et al. [123] suggested that the presence of Ta5+ ions might result in less
O vacancies and consequently, in a reduced mass transport of O in TiO2,
slowing down the oxidation kinetics. Grossmann et al. [119] proposed
that the addition of Ta results in the formation of sub-stoichiometric
mixed (Ti,Ta)nO2n-1 Magnéli phases. In addition to less O vacancies,
due to oxygen deficiency by the higher valence of the substituting Ta5+
favoring the formation of Ti3+ instead of Ti4+, these phases exhibit su­
perior friction and wear properties compared to the stoichiometric
phase [106,123]. Grossmann et al. [119] investigated the relation be­
tween tribological properties and oxide scale formation for Ti1-x-yAlx
TayN coatings with different Ta contents at 900 ◦ C and found that the
oxide scale formation is strongly influenced by the Ta content, as sum­
marized schematically in Fig. 13b. At low Ta contents, anatase TiO2 is
formed in addition to rutile TiO2. Transformation of the metastable
anatase to the stable rutile phase is accompanied by a volume shrinkage,
leading to pores which provide additional diffusion pathways [124].
With increasing Ta content, less anatase is formed until its formation is
completely suppressed, resulting in a decreasing number of pores. For
Ti1-xAlxN, two oxide layers are observed; an Al2O3-rich top-layer and the
porous TiO2-rich layer below. Already at low Ta contents, a separation of
the TiO2-rich layer into two sections is noticeable (marked by the dashed
green line in Fig. 13b); a dense layer exhibiting dark spots, indicating
Al2O3-rich globules within the TiO2 layer beneath the Al2O3-rich top-
layer and a porous TiO2-rich layer below, at the interface to the
remaining Ti1-x-yAlxTayN. With increasing Ta content, the thickness of
the Al2O3-rich top-layer decreases. The separation of the TiO2-rich layer
into two sections is still observed, but as the anatase fraction and thus,
the pore density decreases, the lower TiO2-rich layer becomes dense and
considerably increases in thickness [119].
In addition to their hardness, wear resistance, thermal and oxidation
stability, also the thermal conductivity of hard coatings plays a crucial
role in cutting applications where severe heat is generated [1,125].
Samani et al. [126] observed a thermal conductivity of ~ 11.9 W/(mK)
for TiN. With the addition of Al, the thermal conductivity can be
decreased to values as low as ~ 4.6 W/(mK). As shown in Fig. 14a, a
higher Al content results in a lower thermal conductivity within the
single phase fcc regime. When a dual phase structure is formed the
conductivity increases, as AlN exhibits with ~ 30 W/(mK) a consider­
ably higher thermal conductivity than TiN [127–129]. The addition of
Ta to the Ti1-xAlxN system results in a further decrease of the thermal
conductivity (Fig. 14b), due a combination of phonon scattering pro­
cesses. On the one hand, the phonons are scattered at grain boundaries,
which increase in number as the grain size slightly decreases with
increasing Ta content. On the other hand, the incorporation of an
alloying element results in lattice distortion and local strain fields,
which reduce the local mean free path of the phonons [130]. Since Ta is
a heavy element, small contents already lead to pronounced phonon
scattering [131].
However, for coatings exhibiting low thermal conductivity high peak
N. Schalk et al. Surface & Coatings Technology 429 (2022) 127949

Fig. 11. a) Al/(Ti + Al + Ta), b) Ti/(Ti + Al + Ta) and c) Ta/(Ti + Al + Ta) metal fractions determined for arc evaporated Ti1-x-yAlxTayN coatings as a function of the
respective target compositions, drawn after [118].

Fig. 12. Hardness of Ti1-x-yAlxTayN coatings with a) low and b) high Ta content after vacuum annealing [118].

Fig. 13. a) Scanning electron micrograph or the surface near region of an arc evaporated Ti0.46Al0.37Ta0.17N coating after oxidation at 900 ◦ C for 1 h and corre­
sponding elemental distribution, adapted after [119]. b) Schematic of oxide scale formation as a function of the Ta content. The green dashed line separates the TiO2-
rich layer into two sections; the lower one is characterized by pores (drawn in white) at lower Ta contents, while the upper section exhibits dark spots, representing
Al2O3 globules [119]. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

temperatures can be reached in the contact region between coating and
work piece material during application, resulting in distinct thermal
gradients. Consequently, tailoring of an anisotropic thermal conductiv­
ity, with low thermal conductivity in out-of-plane, meaning along the
coating thickness, direction and high thermal conductivity in in-plane
(in the coating plane) direction could be the key to further improve of
the cutting performance [21,126,132,133]. An approach to realize this
anisotropic thermal conductivity is the deposition of multilayered
coatings with alternating layers with high and low thermal conductivity
[133], where Ti1-x-yAlxTayN could be a suitable candidate for the layer
exhibiting low thermal conductivity.
Adding Si to the Ti1-xAlxN system also results in enhanced mechan­
ical properties and improved thermal as well as oxidation stability
[109,134]. Si has been reported to be either incorporated in a Ti1-x-
yAlxSiyN solid solution or within an amorphous SiNx tissue phase sur­
rounding nanocrystalline Ti1-xAlxN grains in a nanocomposite structure

9
N. Schalk et al.
Fig. 14. Thermal conductivity of a) Ti1-xAlxN coatings as a function of the Al/Ti metal ratio [129] and b) Ti1-x-yAlxTayN coatings as a function of the Ta/(Ti + Al +
Ta) metal ratio [131].
[135–140]. The detection of the amorphous tissue phase is challenging,
since in X-ray photoelectron spectroscopy, being frequently used to
study the presence of amorphous phases, the binding energies of crys­
talline and amorphous Si3N4 differ only slightly [136]. Thus, sophisti­
cated characterization techniques, such as high-resolution TEM, are
required to verify its presence. Exceptionally high hardness values of
above 40 GPa can be achieved for TiAlSiN coatings, due to the formation
of the nanocomposite structure, which inhibits grain boundary sliding
[134,135,137–139,141]. However, if the Si content exceeds a limit of
7–10 at.%, depending on the deposition process and the chosen pa­
rameters as well as the Al content, the hardness decreases as a result of a
thick tissue phase and thus an increased amorphous phase fraction
[108,135,142,143]. In order to obtain superhard coatings, the thickness
of the amorphous tissue phase should not exceed one or two atomic
layers [139,144]. The addition of Si fosters the formation of the w phase
in as deposited state, where depending on the process parameters and
the Al content already small amounts of Si can be sufficient
[108,137,145–147]. Nevertheless, if a nanocomposite structure is
formed its beneficial effects can overcompensate the unfavorable effect
of the w phase on the hardness [137].
Recently, the investigation of the fracture behavior of hard coatings
has attracted increasing interest, since it also significantly affects the
application behavior. Moritz et al. [148] examined the fracture tough­
ness and fracture stress of arc evaporated TiAlSiN coatings with two
different Al contents and compared them to TiSiN and TiN coatings, as
Fig. 15. a) Fracture stress and fracture toughness of arc evaporated Ti(Al,Si)N coatings. Scanning electron micrographs showing cross-sections of the b) TiN, c)
Ti84Si16N, d) Ti81Al3Si16N and e) Ti70Al14Si16N coatings displayed in a) [148].
10
Surface & Coatings Technology 429 (2022) 127949
summarized in Fig. 15a. The fracture stress was evaluated in micro-
bending experiments using un-notched cantilevers, while for the eval­
uation of the fracture toughness notched cantilevers were used. The
determined fracture stress of 2.7 ± 0.1 GPa and fracture toughness of
2.4 ± 0.3 MPa × m1/2 for TiN are in good agreement with literature
[149–151]. Adding Si to TiN resulted in an increase of both, the fracture
stress and toughness to 3.1 ± 0.5 GPa and 2.7 ± 0.4 MPa × m1/2,
respectively. Bartosik et al. [149] reported a comparable fracture
toughness for sputter deposited TiSiN coatings. The addition of Si to TiN
results in a significant grain refinement (compare Fig. 15b and c).
Further addition of a low amount of Al to the TiSiN (Ti/Al/Si metal ratio
of 81/3/16) did not distinctly alter the fine grained microstructure, as
visible in Fig. 15c and d, and also the fracture stress remained largely
unaffected (3.1 ± 0.2 GPa). However, an increased fracture toughness
can be observed. Further increasing the Al content (Ti/Al/Si metal ratio
of 70/14/16, see Fig. 15e) yielded a fracture stress of 5.3 ± 0.5 GPa and
a fracture toughness of 3.3 ± 0.2 MPa × m1/2 and thus, significantly
improved fracture properties. The authors suggested that local structural
transformation from fcc-AlN to w-AlN beyond the elastic-response
regime, dissipating stress and preventing brittle failure, might be
responsible for the improved fracture properties [148,152,153].
Although the addition of Si to the Ti1-xAlxN system favors the for­
mation of the w phase in as deposited state, it positively affects the
thermal stability as the formed tissue phase retards the decomposition
and (further) formation of the w phase during annealing, even if the as
N. Schalk et al.
deposited structure is dual-phase fcc + w [108,116,137,145]. Several
authors reported that the oxidation stability of Ti1-xAlxN can be
considerably improved by the addition of small amounts of Si
[109,137,145]. Pfeiler et al. [109] observed a lower thickness of the
oxide scale for a Ti30.4Al68.4Si1.2N coating compared to Ti30Al70N, which
consisted of an Al-rich top-layer and a Ti-rich sub-layer, where the Si
was homogenously distributed in both layers. In contrast to Ti1-xAlxN, a
significantly higher content of anatase TiO2 was detected in the Si-
containing coating, which was attributed to hindered grain growth of
the anatase phase and consequently a retarded anatase to rutile trans­
formation [109]. The anatase phase is known to be stabilized at grain
sizes below ~ 11 nm [154,155]. Pilloud et al. [154] investigated the
oxidation of TiSiN coatings and proposed that grain coarsening during
oxidation is significantly reduced by the presence of an amorphous tis­
sue phase, which was corroborated in a recent work by Moritz et al.
[156], where they studied the oxidation behavior of TiSiN coatings by
in-situ synchrotron X-ray diffraction and complementary high-
resolution TEM investigations. Pfeiler et al. [109] suggested that the
retarded anatase to rutile transformation in TiAlSiN results in a reduced
time for coarsening of the rutile phase and thus, smaller rutile grains
and/or a reduced thickness of the oxide scale, resulting in lower
compressive stress which could provoke cracks in the protective top-
layer.
4.2. CVD Ti1-xAlxN coatings
In recent years, the deposition of Ti1-xAlxN coatings by CVD has
gained increasing interest. The development of a suitable deposition
process is challenging, since the process parameters and there especially
11
Surface & Coatings Technology 429 (2022) 127949
the high deposition temperatures in conventional thermal CVD might
lead to decomposition of the metastable Ti1-xAlxN coating already dur­
ing deposition. Nevertheless, nowadays CVD processes for the deposi­
tion of Ti1-xAlxN are available, in general based on low pressures (~ 100
mbar) and moderate temperatures (800–900 ◦ C) [157–159]. Using such
processes, the deposition of purely fcc-Ti1-xAlxN coatings with Al metal
fractions of up to x ~ 0.8 and fcc and w mixtures up to even x ~ 0.9 is
possible, showing remarkable performance in cutting tests
[157,158,160–167]. CVD Ti1-xAlxN coatings exhibit a particular char­
acteristic; they form a self-organized nanolamellar structure of alter­
nating Al- and Ti-rich Ti1-xAlxN lamellae. There, the Ti-rich lamellae
always show the fcc structure, while the Al-rich lamellae can be either
fcc or w structured. The nanolamellae exhibit a periodicity of several nm
within individual grains, as visible in the transmission electron micro­
graphs shown in Fig. 16a and b and the 3D atom probe tomography
including the corresponding metal ratio profile in Fig. 16c
[161–163,166,168]. The origin of this nanolamellar structure is
controversially discussed. It is suggested to be either decomposition or
diffusion driven or a result of oscillatory reactions occurring already in
the gas phase [161,166].
Similarly to PVD fcc-Ti1-xAlxN, the CVD coatings also undergo spi­
nodal decomposition during annealing, where the nanolamellar struc­
ture influences the decomposition and subsequent transformation
behavior [162,164,168]. Tkadletz et al. [168] studied the phase evo­
lution with increasing temperature of a powdered nanolamellar CVD
fcc-Ti1-xAlxN coating with a global Al metal fraction of x ~ 0.8
(Fig. 16b), in an in-situ high temperature synchrotron X-ray powder
diffraction experiment. They applied sequential Rietveld refinement to
evaluate the obtained diffractograms and the determined phase
Fig. 16. Scanning transmission electron micro­
graphs a) recorded using a high angle annular dark
field detector, showing randomly oriented nano­
lamellar grains in a CVD fcc-Ti1-xAlxN coating
[163] and b) recorded using a dark field detector
of a 220 oriented grain within a CVD fcc-Ti1-xAlxN
coating, exhibiting chevron-like oriented lamellae,
including an insert of the corresponding selected
area electron diffraction pattern [168]. c) 3D atom
probe tomography of a 110 oriented crystallite
with the corresponding metal ratio profile below
[168].
N. Schalk et al.
Fig. 17. a) Phase evolution with increasing annealing temperature of a nanolamellar CVD fcc-Ti0.2Al0.8N coating. Corresponding evolution of b) phase fractions and
c) lattice parameters determined from in-situ high temperature synchrotron X-ray powder diffraction. d) Differential scanning calorimetry signal and deconvolution
into four individual peaks related to (1) recovery, (2) spinodal decomposition, (3) fcc → w transformation and (4) domain growth [168].
evolution with increasing temperature is shown in Fig. 17a. A w phase
fraction of below ~ 4 mol% was determined in the as deposited state,
which was primarily observed at grain boundaries of large columnar fcc
grains. Up to ~ 900 ◦ C, the sample mainly undergoes recovery processes
and the fcc phases are stable (Fig. 17a). Above 900 ◦ C, the fcc → w
transformation starts, as evidenced by the slight increase of the w phase
fraction and simultaneous decrease of the fcc-(Al,Ti)N phase fraction
(corresponding to the Al-rich lamellae) in Fig. 17b. Above 1000 ◦ C, the
changes of these two phases are more pronounced, until they reach a
steady-state at ~ 1175 ◦ C, which means a fully decomposed and trans­
formed state. The sum of fcc-TiN and fcc-(Ti,Al)N (corresponding to the
Ti-rich lamellae) fractions stays basically constant, which is related to a
compensation of the decreasing amount of fcc-(Ti,Al)N during decom­
position by an increasing amount of newly formed fcc-Ti(Al)N, which is
also confirmed by the distinct increase of the lattice parameter of fcc-(Ti,
Al)N in Fig. 17c. In contrast, the lattice parameter of fcc-(Al,Ti)N stays
almost constant with increasing temperature, suggesting that the Al-rich
fractions do not undergo pronounced decomposition, but rather trans­
form directly into the stable w structure. The corresponding differential
scanning calorimetry signal, shown in Fig. 17d, can be de-convoluted
into four Gaussian peaks, which, considering what is known on spino­
dal decomposition of PVD fcc-Ti1-xAlxN and the microstructural evolu­
tion observed in Fig. 17a-c, can be related to (1) recovery processes, (2)
decomposition of fcc-Ti1-xAlxN into fcc-TiN and fcc-AlN, followed by (3)
transformation of fcc-AlN into the stable w phase and (4) recrystalliza­
tion and crystallite growth. Scanning and transmission electron micro­
scopy (SEM, TEM) and electron backscatter diffraction of annealed
coatings on substrates showed that during decomposition and trans­
formation intact nanolamellar regions co-exist with fully decomposed
and transformed areas. In the final state, globular fcc-TiN precipitates
are embedded within a w-AlN matrix [168].
Todt et al. [163] reported on an outstanding oxidation resistance up
12
Surface & Coatings Technology 429 (2022) 127949
to 1050 ◦ C of CVD Ti0.05Al0.95N coatings, exhibiting the characteristic
nanolamellar microstructure. However, in contrast to the powdered
coating studied with respect to the spinodal decomposition by Tkadletz
et al. [168], which showed a predominant fcc structure, their coating
contained alternating fcc and w lamellae. In Fig. 18a, light optical mi­
crographs of the oxidized surfaces of commercially available PVD Ti1-
xAlxN and Cr1-xAlxN coated cutting inserts are compared to CVD
Ti0.05Al0.95N coated inserts, highlighting the superior oxidation resis­
tance of the CVD Ti0.05Al0.95N coating. The CVD Ti0.05Al0.95N coating
maintained its hardness of ~ 29 GPa until oxidation started. The re­
sidual stress depth gradient of the CVD Ti0.05Al0.95N coating in as
deposited state is presented in Fig. 18b on the left hand side and reveals
high compressive residual stress in the surface near region, which de­
creases towards the interface to the TiC0.5N0.5 base layer, which shows
low tensile stress. The authors do not comment on the origin of this
stress gradient, however, such gradients are typically observed after post
deposition blasting treatments of the coating [36,169]. After oxidation
at 1050 ◦ C (Fig. 18b, right hand side), the stress gradient vanishes and
the coating exhibits moderate compressive residual stress. Only minor
microstructural changes were observed in the CVD Ti0.05Al0.95N coating
beneath the oxide scale after oxidation at 1050 ◦ C, evidencing only
starting spinodal decomposition, where the nanocomposite structure
was still largely preserved. In order to illuminate the influence of the
nanolamellar microstructure on the oxidation sequence in detail, Sar­
inger et al. [170] investigated a powdered nanolamellar CVD fcc-Ti1-
xAlxN coating using synchrotron X-ray diffraction (XRD) coupled with
differential scanning calorimetry (DSC). In Fig. 19a, the phase evolution
as a function of the oxidation temperature is shown. The phase plot can
essentially be divided into four zones. In zone 1, up to ~ 600 ◦ C, only fcc-
TiN (stemming from a ~ 200 nm thin TiN base layer) and fcc-Ti1-xAlxN
can be detected. In zone 2, between ~ 600 ◦ C and ~ 900 ◦ C, rutile TiO2
is formed. At ~ 900 ◦ C, in zone 3, α-Al2O3 starts to form and above ~
N. Schalk et al.
Fig. 18. a) Light optical micrographs of as deposited and oxidized PVD Ti1-xAlxN, PVD Cr1-xAlxN and CVD Ti0.05Al0.95N coatings. b) Residual stress depth gradient of
the as deposited CVD Ti0.05Al0.95N coating (left) and after oxidation at 1050 ◦ C (right) [163].
1250 ◦ C, in zone 4, Al2TiO5 is observed. The quantitative phase analyses
obtained by sequential Rietveld refinement of the diffraction data is
summarized in Fig. 19b. At temperatures below 500 ◦ C, no distinct
changes in the phase composition are visible. At ~ 500 ◦ C the amount of
TiN starts to decrease, while simultaneously rutile TiO2 is formed,
coinciding with the appearance of a small exothermic peak in the DSC
signal. This initial oxidation of the TiN base layer observed here for the
powdered sample is not assumed to take place in a compact sample,
where the base layer is buried beneath the Ti1-xAlxN coating. The next
distinct changes in Fig. 19b are visible at ~ 680 ◦ C, where the Ti(Al)N
fraction starts to decrease, associated with a minor exothermic DSC
peak. Simultaneously, the Al(Ti)N fraction increases, indicating spino­
dal decomposition, which is further corroborated by the evolution of the
lattice parameter in Fig. 19c. There, above ~ 680 ◦ C, the lattice
parameter of Ti(Al)N increases, as a result of the loss of Al, towards the
value of TiN. The constant increase of the lattice parameters of TiN and
Al(Ti)N with increasing temperature is related to the thermal expansion
of the lattice. At ~ 880 ◦ C, the spinodal decomposition is completed and
a slight increase of the w-AlN phase fraction can be detected, associated
with a small exothermic DSC peak. Three different oxidation reactions
contribute to the main peak in the DSC signal: oxidation of i) Ti(Al)N, ii)
Al(Ti)N and iii) w-AlN. The respective peak intensities in the DSC signal
are in good agreement with the determined phase compositions. Above
1000 ◦ C, the entire coating is oxidized to rutile TiO2 and α-Al2O3, which
transform into Al2TiO5 above ~ 1250 ◦ C. In Fig. 19d, the oxidation of
the powdered CVD Ti1-xAlxN coating is summarized and all peaks
occurring in the DSC signal are assigned to the respective event taking
place [170].
13
Surface & Coatings Technology 429 (2022) 127949
4.3. Summary and comparison PVD and CVD Ti1-xAlxN coatings
First of all, the microstructure of PVD and CVD Ti1-xAlxN coatings is
fundamentally different. While the PVD coatings are commonly char­
acterized by a fine grained columnar structure [66,95,131,171], the
CVD coatings typically exhibit a particular self-organized nanolamellar
structure of alternating Al- and Ti-rich Ti1-xAlxN lamellae
[161–163,166,168]. This nanolamellar structure facilitates the deposi­
tion of purely fcc-Ti1-xAlxN coatings with Al metal fractions of up to x ~
0.8 [157,158,160–167], whereas for PVD coatings the solubility limit of
Al in the fcc regime is x ~ 0.67 [68,92–94]. While the PVD Ti1-xAlxN
coatings typically exhibit compressive residual stress [92,95,117,172],
for CVD Ti1-xAlxN coatings both, tensile [161,173–175] and compressive
[157–160,163,167] residual stresses have been determined. For purely
fcc CVD Ti0.2Al0.8N coatings hardness values between ~ 31 and ~ 36
GPa have been reported [161,162,164,167,173], which is comparable
to values reported for PVD fcc-Ti1-xAlxN coatings synthesized at high
bias voltages [68,92]. However, for both, PVD and CVD Ti1-xAlxN
coatings, the hardness immediately drops when the w structure is
formed [68,92,164]. Both, PVD and CVD fcc-Ti1-xAlxN coatings spino­
dally decompose at elevated temperatures. While the onset of spinodal
decomposition is typically observed at temperatures of ~ 800 ◦ C for PVD
coatings [67,118], a higher onset temperature of ~ 900–1000 ◦ C has
been reported for CVD coatings [164,168]. The following trans­
formation of fcc-AlN into the stable w phase occurs at ~ 1000 ◦ C for
both, PVD and CVD Ti1-xAlxN coatings [67,162,168]. For PVD Ti1-xAlxN
coatings typically an oxidation stability of up to ~ 950 ◦ C can be found
in literature [95], while for CVD Ti1-xAlxN coatings, due to the higher Al
N. Schalk et al. Surface & Coatings Technology 429 (2022) 127949

Fig. 19. a) Phase evolution of CVD Ti1-xAlxN with increasing annealing temperature obtained from an in-situ synchrotron experiment. b) Evolution of the phase
composition with increasing annealing temperature determined by applying sequential Rietveld analysis on the data from a) in combination with the DSC signal as
function of the temperature. c) Lattice parameter of the observed fcc phases from a) obtained by Rietveld analysis. d) DSC signal from b), where all peaks are assigned
to an event [170].

contents, a higher oxidation stability of up to ~ 1050 ◦ C has been
observed [163].
5. TiCxN1-x coatings
The deposition of carbides and carbonitrides using PVD is chal­
lenging. C can either be introduced as reactive gas, where typically
hydrocarbons are used, resulting in H incorporation in the coating, or as
component of the target material, where the variation of the C content is
restricted [4,176–180]. Thus, carbides and carbonitrides are commonly
rather synthesized by CVD than PVD. TiC synthesized by CVD was
widely used in the 1970s, due its higher hardness compared to TiN
[8,56,181]. Nowadays it has been largely replaced by CVD TiCxN1-x,
which is frequently used as base layer below Al2O3 [8]. There, the co­
efficient of thermal expansion (CTE) plays a crucial role. Due to the high
deposition temperatures of up to 1000 ◦ C in thermal CVD and the
different CTEs of coatings and cemented carbide substrates, typically
tensile residual stresses arise, commonly resulting in thermal cracks in
the coatings [182–184].
expansion of magnetron sputtered TiCxN1-x coatings. There, the depo­
sition was realized in non-reactive mode, applying co-sputtering from
TiC and TiN targets. Coating compositions ranging from pure TiC to pure
TiN were obtained by varying the discharge currents for the two mag­
netrons. All coatings exhibited a fcc structure and the lattice parameters
followed essentially a Vegard's like behavior. The TiN coating was
roughly stoichiometric, while for the TiCxN1-x coatings, especially at
high C contents, a significant amount of excess C was detected,
accommodated in an additional amorphous C phase (a-C). The presence
of such an additional a-C phase is commonly observed and another
drawback of carbide and carbonitride coatings synthesized by PVD, in
particular by sputter deposition [186,187]. In order to determine the
CTE, powdered coatings were measured between 25 and 1000 ◦ C using
high temperature XRD and the obtained data was analyzed by Rietveld
refinement. As shown in Fig. 20a, the CTE decreases with increasing C
content and increases with temperature, demonstrating the shift from a
pronounced metallic bonding of TiN to a more covalent bonding for TiC
(Fig. 1). In Fig. 20b, the average TECs between RT and 1000 ◦ C as a
function of the C/(C + N) ratio are shown [185].

5.1. PVD TiCxN1-x coatings 5.2. CVD TiCxN1-x and ZrCxN1-x coatings

In a recent work, Saringer et al. [185] investigated the thermal According to Gassner et al. [183] and Stylianou et al. [184], the

14
N. Schalk et al. Surface & Coatings Technology 429 (2022) 127949

Fig. 20. a) Linear thermal expansion coefficient for sputtered Ti(C,N) coatings with C/(C + N) ratios varying from 0 to 1 [185]. b) Corresponding average thermal
expansion coefficient between RT and 1000 ◦ C, drawn after [185].

Fig. 21. a) Scanning electron micrograph of the surface of a CVD TiCxN1-x coating deposited on a WC-Co substrate with 7.5 wt.% Co, exhibiting thermal cracks [184].
b) Evolution of the mean distance of thermal cracks on the surface of TiCxN1-x coatings with increasing substrate Co content, drawn after [184]. c) Mean thermal
expansion coefficients of WC-Co substrates with different Co contents in comparison to the TiCxN1-x coating in the range between 20 and 800 ◦ C [184].

thermal cracks (Fig. 21a) in CVD TiCxN1-x proceed through the coating
into the substrate. Stylianou et al. reported on a decreasing crack density
in CVD TiCxN1-x coatings with increasing Co content in the cemented
carbide substrate (Fig. 21b), as a result of the decreasing mismatch be­
tween the CTE of coating and substrate (Fig. 21c) [184]. However, for
industrial applications it is not feasible to freely increase the Co content
in the substrate, which is typically adjusted according to the respective
application [25]. The C content of the TiCxN1-x coatings is not given in
the work of Stylianou et al., but the coatings were prepared applying
CH3CN as C precursor and a deposition temperature of 800 ◦ C. This
process is frequently referred to as medium temperature (MT) process,
where the use of CH3CN as C precursor limits the C/(C + N) ratio in the
coatings to ~ 0.66. Another possible C precursor is CH4, which was more
widely utilized before the MT process was successfully established on an
industrial scale. The drawback of CH4 is that deposition temperatures in
the range of 950 ◦ C and above are required. The higher deposition
temperature compared to the MT process constitutes a higher driving
force for thermal crack formation and formation of the undesired brittle
η-phase [8,188,189]. However, considering the in Fig. 20 discussed
decrease of the CTE with increasing C content for the sputtered coatings
[185], an increase of the C content in CVD TiCxN1-x coatings might be
another promising approach to reduce the crack density in the coatings.
An alternative C precursor, combining the advantages of both, the MT
and the HT process and thus, allowing to freely adjust the C content for
TiCxN1-x with x ranging from 0 to 1 at moderate deposition temperatures
was recently suggested by Kainz et al. [190]. They did not observe any
cracks in their coatings, not even in TiN or TiC0.32N0.68 (exhibiting the
lowest C content in this study), which, however, might be owed to the

15
N. Schalk et al.
rather high Co content of 12 wt.% of the used cemented carbide
substrates.
A different approach to avoid thermal cracks is to not only adjust the
composition of the existing coating material, but to consider alternative
material systems, where ZrCxN1-x is a promising candidate. First of all,
the CTE of ZrCxN1-x (~ 7.7 × 10− 6 K− 1) [191] is already distinctly lower
than that of TiCxN1-x (~ 8.7 × 10− 6 K− 1) [184,191], resulting in a lower
mismatch to the CTE of cemented carbide [192–194], but ZrCxN1-x also
exhibits superior toughness compared to TiCxN1-x [195]. While El Azhari
et al. [194] detected a dense crack network on the surface of TiCxN1-x, as
shown in Fig. 22a, no thermal cracks were visible on the surface of
ZrCxN1-x (Fig. 22b). Both coatings were deposited at ~ 900 ◦ C onto the
same cemented carbide substrates containing 6 wt.% Co and exhibited a
C/N ratio of roughly 50/50 [194,196]. In another work, El Azhari et al.
[195] performed compression tests on focused ion beam milled micro-
pillars of TiC0.5N0.5 and ZrC0.5N0.5 and observed pronounced differ­
ences. The stress-displacement curves of both coatings, shown in
Fig. 22c, start with linear behavior, typically followed by a pop-in event
related to crack initiation, followed by catastrophic failure if the
experiment was not interrupted. However, a higher stiffness was
detected for TiC0.5N0.5 compared to ZrC0.5N0.5 and a different cracking
behavior. While the cracks propagated intergranular in TiC0.5N0.5, they
appeared to propagate in a mixed intra− /intergranular fashion in
ZrC0.5N0.5, suggesting a higher cohesive strength between the grains in
ZrC0.5N0.5. As visible in Fig. 22c, ZrC0.5N0.5 reaches higher displace­
ments compared to TiC0.5N0.5 until the pop-in events occur, indicating a
superior toughness of ZrC0.5N0.5. In addition, some ZrC0.5N0.5 pillars did
not show pop-in events at all during compression testing. The authors
Fig. 22. Scanning electron micrographs of the surface of a) a CVD TiC0.5N0.5 coating showing a thermal crack network and b) a CVD ZrC0.5N0.5 coating where no
cracks are present [194]. c) Stress displacement curves for micro-pillar compression tests on TiC0.5N0.5 and ZrC0.5N0.5, showing that the pop-in events occur at higher
displacements for ZrC0.5N0.5. d) Stress displacement curves for two successive compression tests on ZrC0.5N0.5, where no pop-in occurred in the first test, showing
strain hardening during the second test [195].
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Surface & Coatings Technology 429 (2022) 127949
tested them again until a pop-in event occurred and observed strain
hardening (Fig. 22d), implying that plastic deformation takes place
[195].
5.3. Summary and comparison PVD and CVD TiCxN1-x coatings
While using CVD, the synthesis of purely crystalline TiCxN1-x coat­
ings over a wide compositional range is possible [190], the deposition by
PVD can be realized using hydrocarbons as C source, which typically
results in H incorporation in the coating, or C can be a component of the
target material, which restricts the variation of C [4,176–180]. Further,
especially in sputter deposited TiCxN1-x coatings, commonly an addi­
tional amorphous C phase (a-C) is present [186,187]. For PVD coatings,
growth is predominantly controlled by kinetic process parameters, like
the applied bias voltage, typically resulting in compressive residual
stress. In contrast, for CVD coatings the residual stress state is essentially
governed by the thermal component. Thus, one characteristic of CVD
TiCxN1-x coatings grown on cemented carbide substrates is their tensile
residual stress, which typically results in a crack network in the coating
[182–184]. This tensile stress as well as the commonly larger grain size
of CVD TiCxN1-x coatings explain the typically reported lower hardness
values of up to ~ 30 GPa [190,197], compared to hardness values of up
to ~ 46 GPa reported for PVD TiCxN1-x coatings, which in general
exhibit smaller grain sizes and compressive residual stress [180,198].
However, for both, PVD and CVD TiCxN1-x coatings a dependence of the
hardness on the C/(C + N) ratio is observed; up to x ~ 0.5 the hardness
increases, where it reaches a small plateau, followed by a decline at x >
0.6 [180,190]. TiN and TiC are miscible over the complete
N. Schalk et al. Surface & Coatings Technology 429 (2022) 127949

compositional range [199] with TiCxN1-x exhibiting a negative enthalpy

of formation [200], which is thus thermally stable. Oxidation studies of
TiCxN1-x coatings are rare, which is probably owed to the fact, that they
are nowadays predominantly synthesized by CVD as a base layer below
Al2O3. An oxidation stability of up to ~ 500 ◦ C has been reported
[201,202], where a higher C/(C + N) ratio results in a lower oxidation
stability for both, PVD and CVD coatings [201–203].

6. TiB2 and TiBN coatings

Among the boride coatings, TiB2 is the most commonly used material
system for cutting tools. Due to its high hardness, high wear resistance
and good chemical stability, TiB2 serves as protective coating in
machining of Ti and Al alloys as well as carbon fiber reinforced plastics
[4,69,204–206]. Its outstanding properties are a result of the crystal and
atomic bonding structure. The Ti atoms in TiB2 are arranged in a hex­
agonal structure, with strong covalently bonded B atoms situated in the
interstices, resulting in alternating Ti and B planes along the c-axis
[207]. The deposition of borides and boronitrides by PVD is possible,
applying the respective boride targets, but entails the problem of low
resistance of the ceramic target material against thermo-shock. Since
thermal cracking is even more an issue during cathodic arc evaporation,
boride coatings for commercial use are typically either synthesized by
the less efficient sputter deposition process or by CVD [4,208–212].
Boride and boronitride coatings received considerable attention in the
late 1980s/early 1990s, when several authors reported on sputter
deposited TiB2 and TiB(C)N coatings [208,209,213–223] and experi­
enced a revival in recent years [69,70,210,212,224–229].
6.1. PVD TiB2 and TiBN coatings
In recent years, several works have been published on possibilities to
overcome the low resistance of TiB2 against thermo-shock
[212,228,229]. Zhirkov et al. [212] reported on a stable arc plasma
generated from a TiB2 cathode and complete utilization of the target
material by (i) mounting a Mo cylinder around the TiB2 cathode to
improve arc ignition and keep the arc spot at the cathode surface, (ii) the
addition of 1 wt.% C in the target to further improve the process stability
and (iii) the utilization of a separate anode to increase the plasma
density [212]. Another possibility is the application of high power im­
pulse magnetron sputtering (HiPIMS), since HiPIMS uses extremely high
power densities in short pulses at low duty cycles for sputtering
[228–231].
TiB2 coatings frequently exhibit significantly higher hardness values
than bulk TiB2, which are often explained by the high compressive
stresses in these coatings [207,217]. Mayrhofer et al. [213] observed the
formation of a nanocomposite structure for over-stoichiometric TiB2.4
coatings synthesized by sputter deposition. There, the excess B forms a
tissue phase, which surrounds broader TiB2 columns consisting of bun­
dles of sub-columns also separated by a B-rich tissue phase, as visible in
the transmission electron micrograph in Fig. 23. This complex nano­
composite structure hinders nucleation and gliding of dislocations as
well as grain boundary sliding, leading to the reported high hardness.
Mainly due to the strong covalently bonded B network, TiB2 exists in a
quite narrow single-phase field (between 65.6 and 66.7 at.% B) [232].
Using TiB2 targets, different sputter yields [233] and scattering proba­
bilities of Ti and B atoms during the transport phase from the target to
the substrate typically result in over-stoichiometric TiB2+x coatings
[213,234–237]. Petrov et al. [210] reported that the application of
highly magnetically unbalanced magnetron sputtering enables tailoring
of the B/Ti ratio and thus, also the deposition of stoichiometric TiB2
coatings. There, the sputtered Ti atoms can be selectively ionized and
directed towards the growing film by applying an external magnetic
field [210].
For PVD TiBN coatings with low B contents, the formation of an fcc
structure where B substitutes for N has been reported [218,238,239]. If
Fig. 23. Bright-field plan-view (0001) high resolution transmission electron
micrograph of a sputtered TiB2.4 coating. The insert shows a Z-contrast
image [213].
the B content exceeds a certain limit, a nanocomposite structure is
formed. Mayrhofer et al. [239] observed a limit of ~ 18 at.% B for the
formation of a solid solution. However, the majority of the existing
literature focuses on PVD TiBN coatings exhibiting a nanocomposite
structure consisting of fcc-TiN and hexagonal TiB2 based nanocrystals
and an amorphous BN grain boundary phase, which results in high
hardness values exceeding 50 GPa [218,240–243]. Such nanocomposite
coatings have been synthesized by non-reactive co-sputtering from TiN
and TiB2 targets and by reactive sputtering from TiB2 targets and N2
containing atmospheres [208,209,214–216,218,240,243,244]. Neid­
hard et al. [242] have realized the deposition of nanocomposite TiBN
coatings by reactive arc evaporation, applying Ti/TiB2 targets, where
TiB2 grains are embedded in a Ti matrix to achieve the required thermo-
shock resistance. They varied the N2 partial pressure and observed a
significant effect on the phase composition and consequently on the
mechanical properties (Fig. 24). The coating synthesized at the lowest
N2 partial pressure exhibits a rather low hardness, comparable to that of
the coating grown without N2 (Fig. 24b). The authors attribute that to
the under-stoichiometric composition (Ti0.52B0.17N0.31) and a resulting
weakening of the tissue phase due to the formation of Ti-rich amorphous
compounds. At an N2 fraction of 0.1 in the process gas, the highest
hardness value is observed. There, the availability of N2 is still limited,
favoring the solid solution of B in fcc-TiN, with only small amorphous
phase fractions forming a thin tissue phase surrounding the fcc-TiBN
nanocrystals, fostering the high hardness. At N2 fractions ≥0.25, the
bonding structure changes distinctly, as visible in Fig. 24a, since it be­
comes energetically more favorable for the B atoms to dislodge into an
amorphous BN tissue phase, which occupies a significant volume frac­
tion, resulting in a deteriorating hardness [242].
6.2. CVD TiB2 and TiB(C)N coatings
TiB2 coatings synthesized by CVD typically exhibit very small grain
sizes and high compressive stress (Fig. 25a and b) [69,211], which is
quite unusual for CVD coatings. As discussed already in subsection 5,
typically thermal stress constitutes the main contribution to the residual
stress state in CVD coatings due to the high deposition temperatures.

17
N. Schalk et al.
Fig. 24. a) XPS spectra of the Ti2p, B1s and N1s orbital for arc evaporated TiBN coatings deposited with increasing N2 fractions. b) Hardness and reduced modulus
for the same TiBN coatings [242].
Fig. 25. a) Bright-field transmission electron micrograph of a commercially grown CVD TiB2 coating, showing a nanocrystalline structure. b) Residual stresses and
domain size determined by synchrotron X-ray nanodiffraction as a function of the coating thickness of the same TiB2 coating deposited on a TiN base layer [69].
This seems not to be the case for CVD TiB2, where also other factors play
a major role, as reported by Schalk et al. [69]. However, the mean CTE
αm = (2αa3+αc ) (where αa and αc are the thermal expansion coefficients
related to the a and c axis of the hexagonal TiB2) of TiB2 is with 7.4 ×
10− 6 K− 1 [245] lower compared to e.g. TiCxN1-x (~ 8.7 × 10− 6 K− 1)
[184] or Al2O3 (αm= 8.7 × 10− 6 K− 1) [246], resulting in a lower
mismatch to the CTE of the cemented carbide substrate. In addition, the
anisotropy of the CTE (αa ~ 6.4 × 10− 6 K− 1, αc ~ 9.2.x10− 6 K− 1) [245]
in combination with the elastic anisotropy of TiB2 [247] and the pres­
ence of a texture can also be assumed to affect the stress state. Never­
theless, the most important source for the observed compressive stress is
the small grain size in the range of a few nm (Fig. 25a and b), which is a
result of the strong covalent B–B bonds. The increasing Laplace pres­
sure on the surface atoms of these small grains can be expected to
considerably contribute to the formation of the high compressive stress
[69]. Further, the coatings investigated by Schalk et al. were slightly
sub-stoichiometric in B, leading to an increased defect density. Addi­
tionally, indications for local epitaxy in the early stage of TiB2 growth on
the TiN base layer were detected, which might also contribute to the
formation of compressive stress [69,247,248]. A drawback of the high
compressive stress and also of the different microstructures and me­
chanical properties of the TiB2 layer and the typically applied TiN base
layer to prevent B diffusion is poor. An approach to combat this issue
with the implementation of a graded TiBN layer between the TiN and the
TiB2 layer was presented by Tkadletz et al. [70]. Czettl et al. [224]
showed that the introduction of such a TiBN transition layer indeed
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Surface & Coatings Technology 429 (2022) 127949
results in better adhesion (Fig. 26a and c) and improved performance in
milling tests, where the coatings with the transition layers exhibited
reduced wear and especially a reduced tendency for edge chipping
(Fig. 26b and d).
Several authors reported on CVD TiBN or TiBCN coatings with
varying compositions [26,211,225,226,249,250]. Kainz et al. [225]
studied the mechanical properties and fracture behavior of the CVD Ti
(C,B)N coatings shown in Fig. 27a. The addition of B to TiN results in a
grain refinement and thus, in a hardness increase due to the Hall-Petch
effect, as visible in Fig. 27b [211,225]. However, at high B contents of ~
45 at.% the hardness is known to drop again, which is attributed to the
transition from a predominantly fcc-TiN based structure to sub-
stoichiometric hexagonal TiB2-xNy [70]. Also the addition of C to TiN
results in a smaller grain size, although the effect of C on the grain size is
not that pronounced as the effect of B and consequently also the hard­
ness increase is slightly less distinct. The microstructure of TiCBN is also
very fine grained and combines features of both, TiBN and TiCN
(Fig. 27a). The TiCBN coating reveals the highest hardness, which is
attributed to the fact that it exhibits the smallest grain size, the highest
defect density and the highest fraction of covalent bonding partners of
the four investigated coatings. The evolution of the fracture toughness
(Fig. 27b) is comparable to that of the hardness and can also be related
to the evolution of the grain size. In Fig. 27c, scanning electron micro­
graphs of the fracture cross-sections are shown, which also evidence the
different grain sizes. Kainz et al. [225] detected a small fraction of the
amorphous TiB phase in the CVD TiBN coating. The presence of this
N. Schalk et al.
Fig. 26. Light optical micrographs of the TiN/TiB2 coating after a) calo wear
adhesion test and after 39 min milling of Ti 555.3 (an Ti alloy containing 5 wt.
% of Al, Mo and V as well as 3 wt.% Cr) and of the TiN/TiBN/TiB2 coating also
after c) calo wear test and d) 39 min milling lifetime [224].
amorphous phase was already reported earlier by Dreiling et al. [249]
for TiBN coatings with B contents <18 at.%. They assumed that it
positively affects the oxidation resistance, since coatings containing this
amorphous TiB phase showed superior oxidation resistance compared to
TiN and TiBN coatings with higher B contents. Kainz et al. [226] re­
ported an excellent thermal stability up to 1000 ◦ C (Fig. 28a) for Ti(B,N)
coatings with compositions varying between TiN and TiB2 and a
decreasing CTE with increasing B content (Fig. 28b). They also observed
a decreasing thermal conductivity with increasing B content, shown in
Fig. 28c, as a result of increased phonon scattering due the lower grain
size and higher defect density.
An approach to realize further improved hard coatings with
Fig. 27. a) Scanning electron micrographs of the surface and of cross-sections prepared by focused ion beam milling of CVD TiN, TiBN, TiCN and TiCBN [225]. b)
Fracture toughness and roughness of the fracture cross-section for the coatings shown in a), after [225]. c) Scanning electron micrographs of the respective fracture
cross-sections [225].
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Surface & Coatings Technology 429 (2022) 127949
outstanding properties is the application of multilayers, which is of
particular importance when utilizing hard and brittle boride-based
coating materials. There, dislocation movement is hindered at the in­
terfaces, resulting in an increased hardness. Further, cracks are deflected
at the interfaces leading simultaneously to an improved toughness [7].
Since the combination of two materials with different hardness to a
multilayer is the most promising strategy to achieve hard yet tough
coatings [251], TiN and TiBN are suitable candidates [71,252,253].
Kainz et al. [71] studied the influence of the bilayer thickness (λ) on the
mechanical properties and fracture behavior of CVD TiN/TiBN multi­
layer coatings. In Fig. 29 it can be seen that with decreasing λ the
hardness slightly increases from 28 ± 3 GPa to 31 ± 2 GPa. Notched and
un-notched micro-cantilevers were tested to determine the fracture
toughness and fracture stress, respectively. Similarly to the hardness, the
fracture toughness increases with decreasing λ and is for the lowest λ
even higher than for the TiBN single layer, which demonstrates the
effective deflection of cracks at interfaces leading to a retarded failure.
The fracture stress (not shown) follows the same trend, although the
highest value determined for the multilayer with the lowest λ is still
lower than the fracture stress of the TiBN single-layer, indicating that
the chemical composition has a stronger influence on the fracture stress
than the multilayer architecture [71].
Alternative TMNs of relevance for the formation of diboride or bor­
onitride coatings are Zr, Hf and Nb, indicating a similar evolution of
phase composition, microstructure and properties as observed for TiB2
and TiBN coatings [254–263].
6.3. Summary and comparison PVD and CVD TiB2 and TiBN coatings
The deposition of stoichiometric TiB2 by PVD is challenging;
commonly over-stoichiometric TiB2+x coatings with a nanocomposite
structure consisting of TiB2 nanocolumns surrounded by a B tissue phase
are formed [213,235–237]. In contrast, using CVD typically stoichio­
metric or slightly sub-stoichiometric TiB2 coatings are obtained, which
exhibit - unusual for CVD coatings - small grain sizes and high
compressive residual stress [69,70]. For PVD TiB2 coatings hardness
values between ~ 42 and ~ 77 GPa have been reported
[207,213,222,227,236,237,264], where especially the higher values are
attributed to a nanocomposite structure. The nanocrystalline single
phase CVD TiB2 coatings show hardness values of ~ 44 GPa [69,70].
N. Schalk et al.
Fig. 28. a) Phase evolution of CVD Ti(B,N) coatings with increasing annealing temperature. b) Estimated TiB2 phase fraction based on the determined B content
(neglecting possible nonstoichiometries) and mean thermal CTE for CVD Ti(B,N) coatings. c) Estimated heat capacity and measured thermal conductivity for CVD Ti
(B,N) coatings [226].
Fig. 29. Scanning electron micrographs of cross-sections of TiN and TiBN
single layers and transmission electron micrographs of TiN/TiBN multilayers
with different bilayer (λ) thickness superimposed with the respective hardness
and fracture toughness (KIC) values, after [71].
TiB2 exhibits a negative enthalpy of formation [265] and is thermally
stable [69,226]. Oxidation onset temperatures between ~ 400 and ~
600 ◦ C have been reported for PVD TiB2 coatings [220,227], compared
to ~ 600 ◦ C for CVD TiB2 [266].
For PVD TiBN coatings with B contents <18 at.%, the formation of an
fcc solid solution has been observed [218,238,239]. However, the
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Surface & Coatings Technology 429 (2022) 127949
majority of publications on PVD TiBN report a nanocomposite structure,
consisting of fcc-TiN and hexagonal TiB2 based nanocrystals embedded
in an amorphous BN tissue phase [218,238–243]. In contrast, the for­
mation of an amorphous BN phase has not been detected for CVD TiBN
coatings. Already at B contents as low as ~ 5 at.%, CVD TiBN coatings
show, in addition to the dominating fcc structure, hexagonal TiB2 frac­
tions which increase with increasing B content, until the structure is
dominated by the hexagonal phase at B contents of ~ 45 at.% [70,226].
In addition, the presence of an amorphous TiB phase has been reported
for B contents ≤ 18 at.% in CVD TiBN coatings [225,249]. Depending on
the deposition conditions and B content, hardness values of up to ~ 55
GPa have been obtained for PVD TiBN coatings [218,240], where the
highest hardness values have been observed for moderate B contents,
when a nanocomposite structure with a boundary phase not exceeding a
few atomic layers is formed [242]. For CVD TiBN the hardness increases
up to ~ 37 GPa with increasing B content as long as the structure is fcc
dominated. At higher B contents, the hardness drops significantly due to
the suggested formation of a disordered hexagonal Ti(B,N)2 structure
[70]. For PVD TiBN solid solutions, precipitation of TiB2 at temperatures
above the deposition temperature has been reported [239], while PVD
TiBN nanocomposites are thermally stable to temperatures exceeding
1000 ◦ C [239,267]. Similarly, CVD TiBN coatings are also stable up to
1000 ◦ C, independent of the phase composition [226]. For PVD TiBN an
N. Schalk et al. Surface & Coatings Technology 429 (2022) 127949

oxidation onset temperature of ~ 750 ◦ C has been reported [267]. For

CVD TiBN coatings with B contents ≤ 18 at.%, exhibiting an additional
TiB phase fraction, an oxidation stability up to temperatures of ~ 700 ◦ C
has been observed, while coatings with higher B contents show a lower
oxidation stability [249].

7. Al2O3 coatings

Al2O3 is undoubtedly the workhorse among the oxide hard coatings,

due its high hot hardness and chemical inertness [8,268,269]. In addi­
tion to the stable α-phase, it exists in several metastable polymorphs (γ,
η, δ, θ, χ and κ) [270]. Al2O3 coatings are predominantly synthesized by
CVD, where the stable α-phase is prevalent. However, the deposition by
PVD is also possible.

7.1. PVD Al2O3 coatings

Using PVD for the synthesis of Al2O3, temperatures between 350 and
650 ◦ C are necessary to obtain crystalline fcc structured γ-Al2O3. Al2O3
coatings grown at lower temperatures are typically amorphous
[271–275]. The phase fractions of amorphous and γ-Al2O3 can also be
influenced by the ion bombardment, where a more intense ion
bombardment results in a higher fraction of the crystalline phase [275].
Although sputter deposited and arc evaporated γ-Al2O3 coatings show
an excellent thermal stability up to 1100 ◦ C [274–276], the stable
α-phase is generally the favored polymorph, since a phase trans­ Fig. 30. a) Transmission electron micrograph showing an overview of an
(Al0.25Cr0.75)2O3/(Al0.85Cr0.15)2O3 bilayer coating. The (Al0.25Cr0.75)2O3 tem­
formation negatively affecting the coating performance during appli­
plate layer is divided into two regions; region A, the fine grained nucleation
cation can be excluded. α-Al2O3 exhibits a rhombohedrally centered
zone and region B, exhibiting a columnar structure. Selected area electron
hexagonal lattice and belongs to the trigonal crystal system. However, diffraction patterns corresponding b) to the template layer region A, c) region B
for the deposition of α-Al2O3 by PVD substrate temperatures of ~ 700 ◦ C and d) to the top (Al0.85Cr0.15)2O3 layer [282].
are required [277,278], which is too high for e.g. high-speed steel,
where temperatures below 600 ◦ C are necessary to avoid softening of the
which favors the nucleation of the metastable κ-phase. κ-Al2O3 exhibits a
substrate. Thus, alternative approaches have been sought, resulting in
primitive orthorhombic structure and transforms into the stable α-Al2O3
the application of templates and stabilizers, where up to now mainly
at elevated temperatures. The transformation is accompanied by a vol­
α-Cr2O3 (eskolaite) is used, which is isostructural with α-Al2O3. Eklund
ume shrinkage of ~ 7%, leading to a secondary crack network in addi­
et al. [279] used α-Cr2O3 as template for the epitaxial growth of α-Al2O3
tion to the primary thermal crack network, which deteriorates the
during sputter deposition. They a pronounced influence of the texture of
coating performance and should thus be avoided [8,182,284–286]. In
the α-Cr2O3 template layer on the nucleation of the α-Al2O3. While for a
addition to the often high temperatures arising in cutting applications,
dominating [10‾1‾4] texture, extensive growth of the α-Al2O3 occurred
mechanical activation and stress introduced during cutting can trigger
at 450 ◦ C, only limited nucleation of α-Al2O3 took place for a [0001]
the transformation [287,288]. The thermal conductivity of κ-Al2O3 is
textured α-Cr2O3 template. Other authors pursued a slightly different
significantly lower compared to α-Al2O3, providing a more efficient
approach, where α-Cr2O3 is used as stabilizer. There, an α-(AlxCr1-x)2O3
thermal barrier to the substrate during high speed cutting [8,289]. The
solid solution is synthesized at temperatures between 300 and 550 ◦ C
deposition of κ-Al2O3 requires sophisticated process control, otherwise
[280–283]. However, in order to obtain coatings with high crystallinity,
κ → α transformation might already occur during the deposition process
the ion bombardment has to be optimized similarly to γ-Al2O3 [283].
[290].
Pohler et al. [282] combined the template layer (also called seed layer)
For the synthesis of α-Al2O3 by CVD, an oxidation step after the
with the stabilizing approach, which allowed to obtain crystalline
deposition of the TiCxN1-x base layer, leading to the formation of a Ti(C,
α-(AlxCr1-x)2O3 coatings with Al contents as high as x = 0.85. In order to
N,O) bonding layer, followed by a nucleation step is necessary [284].
realize that, they deposited α-(AlxCr1-x)2O3 template layers with low Al
The large grain sizes and high porosities often reported in older publi­
contents (x = 0.25 and 0.5), followed by α-(AlxCr1-x)2O3 layers with
cations for CVD α-Al2O3 coatings [8,182,285,286] are a result of insuf­
higher Al contents. They observed a fine grained nucleation zone
ficient process control, since in these early attempts the coatings
(Fig. 30a and b, region A) in their coatings, followed by a transition to
nucleated as κ-Al2O3 and the investigated α-Al2O3 coatings were ob­
competitive growth (Fig. 30a and c, region B) and finally the evolution
tained by κ → α transformation [284,291]. The nucleation step not only
of a columnar structure. The fine grained zone is governed by grains
determines the modification of the Al2O3, but is also the key to a tailored
exposing low surface energy facets and its thickness increases with
crystallographic texture [284,292]. α-Al2O3 exhibits highly anisotropic
increasing Al content in the coating. In the competitive growth regime, a
properties, which is shown by the calculated elastic modulus and
preferred (110) orientation evolves which is then retained. The
measured hardness and elastic modulus in Fig. 31a and b [293,294].
columnar structure is promoted by higher Cr contents and more pro­
Ruppi [292] performed turning tests applying tools coated with differ­
nounced ion bombardment. Pohler et al. observed that it is essential to
ently oriented α-Al2O3 and observed the lowest wear and longest service
reach the columnar growth regime before the high Al containing layer is
lifetime (Fig. 31c and d, respectively) for the 0001-oriented coating. A
deposited to enable local epitaxy and thus utilize the template effect
superior cutting performance of 0001-oriented α-Al2O3 coatings was
[282].
also reported by M'Saoubi et al. [295]. In a recent work, Shoja et al.
[296] concentrated on the investigation of the interface between the Ti
7.2. CVD Al2O3 coatings
(C,N,O) bonding layer and the α-Al2O3 layer and its influence on the
development of the texture. They deposited one coating showing a
In general, CVD Al2O3 coatings are deposited on TiCxN1-x base layers,

21
N. Schalk et al. Surface & Coatings Technology 429 (2022) 127949

Fig. 31. a) Orientation dependent elastic modulus of α-Al2O3 determined from single crystal elastic constants, calculated using DECcalc [293]. b) Hardness and
elastic modulus determined on epitaxially grown CVD α-Al2O3 coatings [294]. c) Evolution of flank wear during steel turning of differently oriented CVD α-Al2O3
coatings, adapted after [292]. d) Mean tool live times for differently oriented CVD α-Al2O3 coatings in steel turning [292].

(011‾0) texture and two (0001) textured coatings, where one was grown
applying an additional H2S catalyzing step. Significant diffusion of W
and Co from the cemented carbide substrate through the TiN diffusion
barrier layer and the entire MT-TiCxN1-x layer was detected. The authors
suggest that the presence of these diffused elements might negatively
affect the nucleation and early growth of α-Al2O3. All investigated
coatings exhibited pores at the interface between the Ti(C,N,O) bonding
layer and the α-Al2O3 layer. While the number of pores was comparable
for the two differently oriented coatings, it was almost doubled in case of
the coating deposited with H2S present as catalyst during the nucleation
step of α-Al2O3. However, H2S facilitated the earlier development of the
desired (0001) texture during growth.
Gassner et al. [183] studied the thermal crack network in industrially
applied CVD α-Al2O3 in different conditions: i) as deposited, ii) wet
blasted, iii) annealed, iv) wet blasted and annealed and v) wet blasted
and applied in face turning of 42CrMo4 work piece material. CVD hard
coatings are frequently subjected to a post deposition blasting treatment,
on the one hand to smoothen the surface and on the other hand to
introduce compressive stress into the surface near zone [34–36,169]. In
Fig. 32a, a scanning electron micrograph of the surface of an as depos­
ited α-Al2O3 is presented, where the thermal cracks are clearly visible. In
the wet blasted state (Fig. 32b), the cracks are still visible, but appear
closed. After annealing of the as deposited coating for 15 min at 1000 ◦ C
(Fig. 32c), the cracks appear brighter, which is an artifact caused by an
increased negative electrical charge at the edges of the cracks in the
scanning electron microscope. Annealing of the wet blasted coating
(Fig. 32d) results in reopening of the cracks. Fig. 32e shows a cross-
section of the wet blasted coating, where on the right hand side,
marked by red arrows, a crack can be seen which appears closed in the
surface near region. The cross-section is superimposed by the residual
stress depth gradient determined by X-ray nanodiffraction, which evi­
dences that the region where the crack appears closed coincides exactly
with the region where compressive stress is introduced into the coating.
In the cross-section of a wet blasted coating after application in steel
turning, shown in Fig. 32f, the crack is open again. In addition, this crack
is partially filled, visible as bright rims within the crack, with Ti stem­
ming from the TiCxN1-x base layer and with Mn stemming from the work
piece material [183]. However, obviously the temperatures obtained
during application are sufficient to result in relaxation of the introduced
stress and thus in reopening of the cracks, which makes alternative ap­
proaches to reduce or avoid cracks, like discussed above in subsection
5.2 for the TiCxN1-x base layer, even more interesting [246].
7.3. Summary and comparison PVD and CVD Al2O3 coatings
Different polymorphs of Al2O3 are typically synthesized by PVD and
CVD. Using PVD, commonly α- and γ-Al2O3 are grown [275,277,278],
which exhibit a fine grained structure and often also amorphous phase
fractions [271–275,279,282]. Using CVD, predominantly α- and κ-Al2O3
coatings are deposited [8,290,292], which are characterized by much
larger grains with sizes in the low μm range [36,246]. In the scarce
literature, where the residual stress state of PVD Al2O3 coatings is
studied, typically low tensile stress is observed as a result of the rather
high deposition temperatures [282,283,297]. Also CVD Al2O3 coatings
generally exhibit tensile residual stress as a result of the high necessary
deposition temperatures [183,246,292]. For PVD γ-Al2O3 coatings
hardness values between ~ 14 and ~ 19 GPa and for PVD α-Al2O3
coatings values between ~ 20 and ~ 27 GPa have been reported
[275,277,278], while for CVD α-Al2O3 coatings values between ~ 25
and ~ 29 GPa can be found in literature [291,298,299]. CVD κ-Al2O3

22
N. Schalk et al.
coatings exhibit a hardness of ~ 24–25 GPa [291,300]. PVD γ-Al2O3
coatings are stable up to ~ 1150 ◦ C [275] and CVD κ-Al2O3 up to ~
1050 ◦ C [182], at higher temperatures they transform into the stable
α-phase. Al2O3 coatings are effective oxidation barriers.
8. Future challenges for the hard coatings community
Humankind is presently faced with never seen challenges to combat
climate change and to maintain the high level of living of a constantly
increasing number of humans in a world of limited resources. The
awareness for our environment has grown appreciably and led to the
development of strategies to save it, like the European Green Deal
dominating the recently released highly ambitious Horizon Europe
program [301] with a strong focus on research and innovation to meet
the UN's Sustainable Development Goals (SDGs) [302]. In particular, a
stated target of the SDGs is to decouple economic growth from resource
use and environmental degradation. Since the very first appearance of
23
Surface & Coatings Technology 429 (2022) 127949
Fig. 32. Scanning electron micro­
graphs of the surfaces of CVD α-Al2O3
coatings in a) as deposited, b) wet
blasted, c) annealed and d) wet blasted
and annealed state. Scanning electron
micrograph of a cross-section prepared
by focused ion beam milling of a CVD
α-Al2O3 coating e) after wet blasting,
superimposed with the stress depth
gradient determined by synchrotron X-
ray nanodiffraction (the red arrows
indicate the crack, which appears
closed in the surface near region) and f)
after face turning of 42CrMo4 work
piece material, where the crack is open
again, adapted after [183]. (For inter­
pretation of the references to colour in
this figure legend, the reader is referred
to the web version of this article.)
hard coatings in the late 1960s, ambitions of industry to further improve
these coatings were fueled by the aim to increase productivity and
competitiveness of manufacturing processes; later-on also by the need to
reduce the use of coolants and lubricants and to save resources by pro­
longing the lifetime of tools. This early and continuing success of hard
coatings represents a significant contribution to the SDGs, e.g. by
reducing energy consumption of cutting processes. While this motiva­
tion will without doubt remain, the nowadays available fundamental
science basis is presently used to add more and more functionalities to
these coatings. However, in the future the hard coatings community, i.e.
both academia and industry, has – driven by the necessary political
regulations – as any other production-related community to significantly
intensify its efforts to reach the SDGs. In the following paragraphs, we
will shortly address some of these future issues.
• Towards designed multifunctionality: There are already consid­
erable efforts to design multifunctional hard coatings, since it has
N. Schalk et al.
become apparent that a high hardness alone is not sufficient to
obtain a long tool lifetime, but only few of them have already found
their way into industrial applications yet. While self-hardening (e.g.
age hardening of Ti1-xAlxN based coatings) is in the focus of research
since nearly two decades [67], sophisticated coating architectures to
achieve damage-tolerant coatings being able to stop cracks have
been suggested in the last decade [7,101]. The logical continuation is
the development of coatings with self-healing abilities, which is,
however, still in its infancy [303]. Surface self-organization mecha­
nisms during tribological sliding contacts are not only esteemed a
promising strategy towards self-healing of surface cracks, but at the
same time for adding self-lubrication functionalities, making the
coated product thus more environmentally friendly [303]. In addi­
tion, thermal management abilities have received increasing interest
in the last years, considering that the conventionally demanded low
thermal conductivity of hard coatings might result in high peak
temperatures in the contact to the chip in cutting and distinct ther­
mal gradients, suggesting that a tailored thermal conductivity
allowing heat isolation along the coating thickness and heat distri­
bution within the coating plane might be more favorable [133]. A
recent approach are autonomously self-reporting hard coatings,
where microstructural changes are monitored by in-situ measure­
ments of meaningful properties, like the electrical sheet resistance to
track the progresses of oxidation [304]. An innovative design for a
future hard coating for metal cutting applications should combine all
these functionalities.
• Towards digitalization of coatings and deposition processes:
Simulation guided or at least assisted design of hard coatings with
enhanced performance is already well established practice, which
also contributes to conserving resources. However, the current
approach needs to be promoted and developed further. Currently,
there is a huge gap between turn-key solution for standard applica­
tions, which can be treated by semi-skilled workers, and individual
coating concepts, where specifically trained academics are needed.
Here, the development of digital twins [305] and in further conse­
quence expert systems for the respective deposition processes will be
necessary to bridge this gap and enable the fast and easy further
development, adjustment and optimization of deposition processes,
without the immediate need of highly trained experts. Adding
multifunctional properties to more and more complex hard coatings
will also necessitate the digitization of our traditional approaches for
coating development, to benefit from the ever increasing flood of
available data. Modern data management systems, e.g. based on the
FAIR Guiding Principles [306] (where FAIRness of data implies that
there are findable, accessible, interoperable and reusable), could in
the future enable machine learning from a wealth of theoretical and
experimental data humans would never be able to overlook.
• Towards energy-efficient deposition processes: Most often simply
ignored, coating deposition machines consume a lot of energy to
synthesize a very small volume of coating material [307,308].
Gassner et al. [307] have compared both, energy consumption and
material fluxes in PVD and CVD processes, using visualization by
Sankey diagrams. Normalization of the obtained data with respect to
coating thickness and number of tools per coating batch allows to
compare the efficiency of different deposition processes. In addition
to visualization of energy consumption and material fluxes, the au­
thors suggest to consider possibilities to increase the energy effi­
ciency of deposition processes with their inherent characteristic high
energy consumption (e.g. to heat the substrates or to run power
supplies for evaporation/sputtering) in next generation's coating
facilities. For example, the use of heat exchange modules for waste
heat recovery offers presently unused potentials to enhance the en­
ergy efficiency of deposition systems and thus to contribute to the
SDGs.
• Towards sustainability of coating materials: As most targets used
for PVD processes contain a significant fraction of leftover valuable
24
Surface & Coatings Technology 429 (2022) 127949
material, they are increasingly recycled, which is encouraging
considering the impending scarcity of resources and problematic
origin of critical elements. However, while steel and cemented car­
bide substrates are also already commonly recycled, with conse­
quently comprehensive literature available [309–313], concepts for
detaching of hard coatings from their substrates and making them
reusable are currently essentially missing. Coated cemented carbide
scraps can be recycled [314], where, depending on the coating ma­
terial, the involved elements might in the best case be favorable
alloying elements for the cemented carbides, but they can also form
harmful defects which necessitates decoating [314]. Such decoating
processes prior to recycling cause additional costs; furthermore,
chemicals are needed, which have to be treated/disposed afterwards
and the decoated material currently goes into waste [315]. In the not
too far future, reasonable concepts for recycling of coated tools as
complete as possible to enable their reuse within a circular economy
will be indispensable. Novel approaches in the alloying design and
architecture of coating and substrate materials, focusing on avail­
ability of critical resources, easy detachability of coating and sub­
strate materials, and their recyclability need to become high priority
already in the coating development phase; they – assisted by future
deposit return systems for the used resources at the end of the life­
time – will be the backbone of a responsible development, produc­
tion and use of coated tools.
9. Conclusions
This work presents a review of the current state-of-the-art of hard
coatings for metal cutting applications, focusing on widely used and
well-established hard coatings applied in the metal cutting industry and
taking into account similarities and differences of coatings grown by
PVD and CVD techniques. Economic and ecological considerations of the
machining industry result in an ongoing increase of cutting velocities
and feed rates and the reduction of the use of coolants and lubricants
with simultaneous demand for longer tool lifetimes, which necessitates a
continuous further development of the applied hard coatings. Tradi­
tionally, the required good wear resistance was often equated with high
hardness and possibly good thermal and oxidation stability. Nowadays,
additional properties are required to meet the ever increasing demands
and endure the harsh conditions the cutting tools are exposed to.
Modern hard coatings need to be multifunctional and exhibit also
properties such as an increased cracking resistance or a sophisticated
thermal management, which is often realized by complex coating ar­
chitectures. The design of such tailored multifunctional properties has
been enabled by the considerable progress of advanced characterization
methods in the last decade. For future further development of hard
coatings, a combination of theoretical and experimental approaches is
needed, where the coherency of novel coating designs with the UN's
Sustainable Development Goals will play a central role.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors would like to thank Yvonne Moritz and Christina Kainz
for fruitful discussions and figures. The financial support by the Austrian
Federal Ministry for Digital and Economic Affairs, the National Foun­
dation for Research, Technology and Development and the Christian
Doppler Research Association is gratefully acknowledged (grant number
CDL-ACCT). The authors gratefully acknowledge the financial support
under the scope of the COMET program within the K2 Center “Integrated
Computational Materials, Process and Product Engineering (IC-MPPE)”
N. Schalk et al. Surface & Coatings Technology 429 (2022) 127949

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