1 s2.0 S0254058424002207 Main

Materials Chemistry and Physics 317 (2024) 129095
Contents lists available at ScienceDirect
Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys
Full Length Article
Evaluation of the tribological behavior of TiSiCN (a- SiCN/nc- TiSiCN)

nanocomposite coatings
C.H. Ortiz *, E. Hernandez-Renjifo , J.C. Caicedo
Tribology, Powder Metallurgy and Processing of Solid Recycled Research Group, Universidad Del Valle, Cali, Colombia
H I G H L I G H T S
• (a- SiCN/nc- TiSiCN) Nanocomposite Coatings.

• Nc-TiSiCN nanocrystals embedded in an amorphous SiCN matrix.
• A hardness of 32 Gpa and elastic modulus of 301 Gpa was obtained.
• Reduction of the wear effect as function of applied power.
A R T I C L E I N F O A B S T R A C T
Keywords: This research shows a detailed analysis of the tribological properties of a TiSiCN nanocomposite consisting of an
Nanocomposites amorphous matrix (a-SiCN) and nanocrystals (nc-TiSiCN). By means TEM it was possible to evidence the pres
Physical vapor deposition ence of two distinct phases, attributed to the nc- TiSiCN nanocrystals embedded in an amorphous SiCN matrix.
TiSiCN
Therefore, the scientific factors as the increasing of power applied to the Si3N4 target and the nc-TiSiCN
Tribological properties
nanocrystals embedded in an amorphous SiCN matrix that influencing the physical properties which generate
the increase of the mechanical properties of this type of coating. In this sense, the evaluation of the distribution of
elements presented by TEM-EDX. XRD results determined that by increasing the power applied to the Si3N4
target, a relaxation of the residual stresses within the crystalline structure was generated, which influenced in a
much more homogeneous and dense columnar growth, decreasing the roughness as determined by AFM. Me
chanical study determined the better hardness of 32 Gpa and the better elastic modulus of 301 Gpa for the 500 W
deposited coating. Tribological response concluded that the coating deposited with 500 W presented the best
response obtaining a friction coefficient close to 0.3. All the results obtained determined that the TiSiCN
nanocomposite coating deposited with a power of 500 W will be the best option to be implemented as a pro
tective coating on cutting tools.
1. Introduction Subsequently, coatings evolved to more complex system, such as

multilayer coatings ([TiN/TiCrN] [4], [Al2O3/Si3N4] [9], [β-TCP/HA]
Hard coatings have been implemented on various engineering de [10] among other system, which are constituted by the consequent
vices such as cutting tools, because these devices are used in the trans stacking of individuals layers generating an interface between each
formation processes in the metalworking industry, so these cutting tools layer, and these interfaces act as barriers or obstacles to the passage or
are constantly exposed to highly aggressive conditions (high tempera movement of dislocations generating more resistant coating than indi
ture, corrosive environments, high friction, high thermo-mechanical vidual coatings [11].
loads), causing high wear on the cutting devices [1–4]. Currently, numerous researches have been reported on more ad
Thus, hard coatings have long been implemented as protective vances systems such as nanostructured or nanocomposites coating.
coatings in aggressive conditions. These coatings started with simple These nanostructures are constituted by the presence of nanocrystals
configurations such as individuals coatings based on transitions ele which are inside an amorphous phase, and these achieve an excellent
ments such as TiN [5], TiCN [6], NbCN [7], AlN [8] and others. tribological and mechanical behavior due to the restriction of the origin
* Corresponding author.
E-mail address: christian.ortiz.ortiz@correounivalle.edu.co (C.H. Ortiz).
https://doi.org/10.1016/j.matchemphys.2024.129095
Received 9 February 2023; Received in revised form 21 December 2023; Accepted 17 February 2024
Available online 23 February 2024
0254-0584/© 2024 Published by Elsevier B.V.
C.H. Ortiz et al. Materials Chemistry and Physics 317 (2024) 129095
and displacement of dislocations, which are hindered by the presence of wavelength (λ = 1.5406 Å). The appropriate parameters of the equip
refined grains and spaced between them, originating incoherent de ment were determined based on the ideal angle of incidence ranging
formations [5–7]. Therefore, having very small grains (nanocrystal) between 10◦ and 30◦ and with a counting time of 1 s for every step and a
increases the activity of the interfaces (nanocrystal/matrix), decreasing step size of 0.003. The thicknesses of the coatings were measured using
the ductility of the coatings, minimizing the failure energy due to the scanning electron microscopy (SEM) (JSM 6490 L V JEOL), with a
stacking [3,12]. In addition, these coatings are characterized by magnification interval between 525X and 24.000X and corroborated by
increasing the number of restrictions with a crystalline/amorphous profilometry. The EDS mapping of the present result was performed by
transition across the grain boundary, limiting the formation and prop TEM using the Convergent Beam Electron Diffraction (CBED) configu
agation of dislocations, generating more resistant coatings than con ration and the ZAF Routine was used, so a careful correction has to be
ventional coatings. done in all stoichiometric analysis because EDS has low reliability for
Nanocomposites coatings based on quaternary materials such as Nitrogen concentration. Therefore, EDS elemental concentration were
TiSiCN do not have detailed studies on the tribological and mechanical obtained using the ZAF correction method; because certain factors
properties. Currently, some studies on quaternary TiSiCN coatings related to the sample composition, called matrix effects associated with
deposited by reactive arc and cathodic arc techniques have been re (atomic number (Z), absorption (A) and fluorescence (F)), can effect the
ported. The research carried out by N. Marchin et al. [13], Johnson et al. X-ray spectrum produced during the analysis of electron microprobe and
[14], J. Lin et al. [15] and E. Thangavel et al. [16], have allowed therefore these effects should be corrected to ensure the development of
identifying its structural configuration and how these structural char a careful analysis. The correction factors for a standard specimen of
acteristics will influence the other properties and its response to known composition were determined initially by the ZAF routine. The
different applied external loads. In relation to the above mentioned, this relative intensity of the peak K was determined by dead time correction
research shows a detailed analysis on the crystal structure and specially and a referent correction for the X-ray measured. So, before each
the tribological and mechanical properties of the nanostructured TiSiCN quantitative analysis of an EDS spectrum a manual background correc
coating as a function of the power applied to the Si3N4 target during the tion and an automated ZAF correction were carried out. Thus, reducing
deposition process. This investigation aims to provide new knowledge the measurement uncertainty and bringing the results closer to real
on these nanostructured coatings and to determine mainly that this values. The chemical characterization and the bonding structure was
system presents suitable properties to be implemented as protective on analyzed by X-ray photoelectron spectroscopy (XPS, SAGE HR 100
cutting tools in the metalworking industry. (SPECSTM)). The excitation source is monochromatic Al Kα radiation
(hυ = 1486.6 eV) and the anode power is 150 W. All spectra are
2. Experimental Methodology collected at normal emission angle. The base pressure during spectra
acquisition is lower than 1.1 × 10− 9 Torr (1.5 × 10− 7 Pa). The analyzer
2.1. Coating deposition pass energy is set to 20 eV, which results in that the spectrometer energy
resolution determined from the FE cut-off of Ti and Si samples is 0.38 eV.
The coatings were prepared from PVD technique with r. f source and The XPS binding energy scale was referenced using the work function
different substrates were used such as silicon (100) wafer and steel HSS. method, in this sense in the literature is possible to find that the C 1s
The targets used in this study were TiC and Si3N4 with diameters of 2 peak corresponding to C single bond C/C single bond H bonds of
inch and thickness of 0.125 inch, a purity of 99.9% for both, purchased adventitious carbon (AdC), present on a majority of air-exposed sam
from Kurt J. Lesker Company. The silicon substrates were purchased ples, is most commonly employed for this purpose, irrespective of
from NanoInk Company, and Ar gas was obtained from AGA FANO S.A. whether samples are electrically conducting or not. Therefore, in this
Company. The substrates were ultrasonically cleaned in isopropanol and research in agreements with the G. Greczynsi and co-worked [17–19],
acetone for 15 min each. To guarantee optimum working conditions and the C 1s peak is closely correlated to the sample work function, such that
ensure a low level of contamination, a background pressure of 2.0 × the sum is constant, indicating that the electronic level of the AdC layer
10− 6 mbar was obtained, thus ensuring a high vacuum. The metallic align to the vacuum level, rather than to the Fermi level as commonly
substrate used in this study had a disk-type geometry with a diameter of assumed. This phenomenon can be understood given that the AdC layer
1 cm. The sputtering gas was Ar with 50 sccm with a total working is not an inherent part of the analyzed samples and that the interaction
pressure of 5 × 10- 3 mbar. An unbalanced r. f. bias voltage was applied, to the substrate is weak, showing in that a common Fermi level is no
which generated a negative signal fixed at − 20 V. During the deposition stablished at the interface. Thus a straightforward complementary
process for all coatings, an applied power of 400 W was maintained for measurement of enables using the C 1s peak of AdC for the purpose of
the TiC target, and for the Si3N4 target, a variation in its power of 400 W, BE-scale calibration for samples exhibiting decent electrical conductiv
450 W, 500 W and 550 W were applied, corresponding to 5.1 W/cm2, ity. This new practice resolves problems associated with the conven
5.7 W/cm2, 6.4 W/cm2 and 7.0 W/cm2 power densities. The substrate- tional method and allows for more reliable bonding assignments. Taking
target distance was 6 cm and a temperature of 250 ◦ c was maintained in account the last discussion the work function ɸSA for the carboni
thought the deposition. The heating process and its control is performed trides samples was 4.85 eV [17,20]. A local exploration of the micro
with an electrical resistance heating system inside the deposition structure was carried out through high resolution transmission electron
chamber. Finally, the substrate rotation system was maintained at a microscopy (HR-TEM, FEI Titan 3 60–300), an aberration-corrected
speed of 60 RPM for each coating. All the coatings obtained presented TEM operated at 300 kV. For performing TEM experiments, a
thicknesses of approximately of 2 μm, due to the increase in the power cross-sectional lamella was prepared by using a Helios Nanolab 600 dual
density applied to the Si3N4 Target, there was a variation in the depo beam system. Grain size and Roughness were measured on AFM (Asylum
sition rate (ʌ) of the coatings, therefore, by means of profilometry and Research MFP-3D®) micrographs by image processor (SPIP®) software.
SEM analysis of the cross-section, it was possible to determine the The hardness and elastic modulus, as well as the load-discharge curves
deposition rates (400 W, ʌ = 0.138 nm/s; 450 W, ʌ = 0.151 nm/s; 500 were determined by a nanoindentation instrument (Ubil-Hystron model)
W, ʌ = 0.155 nm/s and 550 W, ʌ = 0.158 nm/s), which was necessary to with a variable load Berkovich diamond indenter, a matrix measurement
maintain the same thickness for all coatings. of 9 points and a maximum load of 10 μN. To evaluate the tribological
behavior of TiSiCN coatings following ASTM G99- 17 [21], using the
2.2. Characterization techniques ball-on-disc (MT 4001-98 model) wear against hardened steel ball
(100Cr6), with a load of 5 N, with sliding distance of 500 m and angular
Structural study was carried out by X’pert PRO X-ray diffractometer speed of 160 rpm, without lubrication. Finally, the load capacity was
using a Bragg- Brentano configuration (θ/2θ) in high angle range, with a performed according to ASTM G171-03 [22,23], using a scratching
2
equipment (Microtest MTR2 model), the scratching length was 6 mm distortion of the crystalline structure. Subsequently, with the increase of
with a maximum load of 90 N and step of 1.97 mm/min, to determine the applied power to the Si3N4 target at 500 W, a displacement or
the critical load for coating failure. approach of the peaks of maximum intensity towards values where the
material is stress-free (dotted line) was evidenced. This behavior is
3. Results and discussion attributed to a relaxation of the compressive residual stresses within the
crystalline structure. Finally, when increasing from 500 W to 550 W, a
3.1. Structural characterization by X-ray diffraction (XRD) new displacement of the maximum intensity peak associated to the in
crease of the residual stresses cause by high ion bombardment corre
Fig. 1a shows X-ray diffraction patterns of TiSiCN coatings obtained sponding to a high power on the Si3N4 target is presented. Thus, it was
at different power values applied to the Si3N4 target, which were possible to determine that the coating deposited with 500 W presents
deposited on silicon substrates with (100) orientation. This quaternary lower residual stresses, which will directly influence is better surface
coating was indexed with two different files attributed to TiC and Si3N4 and mechanical properties, as corroborated in Figs. 6 and 9 [27,28].
compounds respectively, which correspond to the stoichiometries of the Subsequently, for a more detailed study on the influence of the
targets. These diffraction peaks are characteristic to the presence of applied power on the residual stresses. Fig. 2 shows the lattice parameter
distinct compounds, the Bragg peaks located in the (111), (200), (220), of the coatings obtained as a function of the applied power, the lattice
(311) and (222) planes for the angles 36.04◦ ; 41.98◦ ; 60.89◦ ; 72.67◦ and parameter were calculated by equations (1) and (2) respectively, where
76.08◦ are attributed to the TiC compound, which presents an FCC the values 2θ were obtained from the plane of maximum intensity (200).
structure with an Fm3m space group according to the JCPDF 00-001- In addition, the position where the material is stress free (a0 = 4.3102 Å)
2122 index file. The peaks (111), (200), and (220) also characteristic obtained from the international index files is indicated. These results
of Ti(C, N) phases as reported by N. Marchin et al. [13]. Moreover, the showed that the 500 W coating presented a lattice parameter much
presence of the Si3N4 compound as evidenced by the reflections in the closer to the stress-free position, indicating that this structure presented
characteristic planes (101), (301), and (321) for the angles 33.56◦ ; a lower amount of residual stresses compared to the other coatings [4].
52.13◦ and 70.11◦ respectively, which presents a hexagonal structure
with a P63/m space group corresponding to the JCPDF 00-009-0259 nλ = 2dsenθ (1)
index file, a phase related to this structure as evidenced by several re
searchers [12,24–26]. However, it is important to highlight that some
authors have reported some nanocrystalline phases associated with the
TiSiCN composite, which presents a direction (200) of a cubic TiSiCN
embryonic phase coming from the FCC structure of TiC [13]. Moreover
the TiSiCN cubic crystal present a lattice parameter of 4.2791 Å and the
interplanar distance of d(200) = 2.1395 Å, which is different from the
lattice parameter and the interplanar distance values for the TiC mate
rial (a0 = 4.6000 Å, d(200) = 2.3300 Å). Fig. 1b shows the magnification
of the maximum intensity peak corresponding to the 200 plane for all
coatings. In addition, the position where the structure is stress-free
(dotted line) according to the international files. These results showed
that all the peaks of maximum intensity are displaced from the
stress-free position, these displacement are attributed to the formation
of solid solutions, and to the mismatch generated by the change of
crystalline structure between the substrate and the coating [Si/TiSiCN],
which produces residual stresses within the coating structure, the
TiSiCN coating deposited with an applied power of 400 W presents a
shift to the right in relation to the stress-free position, this peak shift is
associated to the presence of compressive residual stresses within the
crystalline structure during the deposition process, which cause a Fig. 2. Lattice Parameter for TiSiCN nanocomposite.
Fig. 1. X-ray diffraction patterns for TiSiCN coatings: (a) diffraction patterns as a function of applied power on the Si3N4 target and (b) intensity maxima of all
coatings, for the (200) plane inscribed in a compressive stress region.
3
α0 Table 1
d = √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ (2) Variation of the atomic content and stoichiometric ratio in the TiSiCN coatings
h2 + k2 + l2
in relation to the applied power on Si3N4 target.
Atomic content (%) Stoichiometric ratio
3.2. Elemental composition by XPS Power (W) (Si3N4 target) Ti Si C N O (Ti/Si + N)
400 25 45 11 18 1 0.39
Fig. 3 XPS survey spectra for the TiSiCN coating are presented in 450 20 49 13 19 1 0.29
relation to the applied power variation on the Si3N4 target. So, for the 500 17 53 9 20 1 0.23
550 15 55 7 22 1 0.19
XPS analysis the binding energy scale was referenced by using the work
function method, in this sense in the literature is possible to find that the
C 1s peak corresponding to C single bond C/C single bond H bonds of determine the internal signals. Fig. 4a shows the high-intensity spectrum
adventitious carbon (AdC), present on a majority of air-exposed samples for the C (1s), so in agreements with the G. Greczynski, and co-workers
such as Ti–Si–C–N composite. In this research in agreements with the G. [20,32,33] the chemical state analysis in X-ray photoelectron spectros
Greczynski, and co-workers [4,19,29] the C 1s peak is closely correlated copy (XPS) relies on assigning well defined binding energy values to core
to the sample work function, such that the sum is constant, indicating level electrons originating from atoms in particular bonding configura
that the electronic levels of the AdC layer align to the vacuum level, tions. Taking into account the above, the signal C (1s) was fitted by three
rather than to the Fermi level as commonly assumed. In this research the internal Gaussian functions attributed to C–Ti, C–Si and C–N bonds in
AdC layer is not an inherent part of analyzed sample and that the agreement with the binding energies 282.13 eV, 283.84 eV and 286.21
interaction between the layer and the substrate is weak, so no Fermi eV respectively, as corroborated in the literature [33–35]. The assign
nevel is stablished at the interface. Therefore, a direct complementary ment of the BE value for the carbon signal (C 1s) form Ti–Si–C–N ma
measurement of the enables using the C 1s peak of the AdC present in the terial was performed taking into account the calibration of the chemical
Ti–Si–C–N nanocomposite, for the purpose of BE–scale calibration for identity of AdC, due to that a most disturbing consequence of the BE
samples exhibiting decent electrical conductivity. This new practice referencing problems outlined above is the fact that the reported binding
resolves problems associated with the conventional method and allows energies for primary core-levels of constituent elements in many
for more reliable bonding assignments. Taking in account the last dis technologically-relevant materials exhibit an unacceptably large spread,
cussion the Work function ɸSA for the carbonitrides samples was 4.85 eV which often exceeds the magnitude of related chemical shifts [13].
[30,31]. Fig. 4b present the high-intensity spectrum correspond to the N (1s)
From these spectra, the bonds present in the survey spectra can be signal, which was fitted by two Gaussian functions attributed to the N–Ti
analyzed. In this sense, intensity maxima (peaks) attributed to the sig and N–C bonds located at the binding energies 396.14 eV and 399.94 eV
nals of Ti 2s, O 1s, Ti 2p3/2, N 1s, C 1s, Si 2s, Si 2p and Ti 3p corre respectively, as shown in the literature [35–39]. Fig. 4c shows the
sponding to the binding energies 563.67 eV; 531.71 eV; 456.27 eV; high-intensity spectrum for the Si(2p) signal. Therefore, the Si (2p)
396.2 eV; 284.23 eV; 151.6 eV; 101.4 eV and 21.62 eV respectively. signal was fitted by four Gaussian signals, the first signals are associated
Therefore, through XPS spectrums for all the coatings, it was possible to with the Si–O and Si–N bonds, located with a binding energy of 104.4 eV
establish the stoichiometry and the variation of the elements present as a and 102.1 eV, respectively. Followed by the signal Si–C bond corre
function of the applied power as shown in Table 1 [32,33]. In this sense sponding to Si in the amorphous phase of the Si–C–N with the corre
in Table 1, the stoichiometric ratio (Ti/Si + N) was evidenced in relation sponding binding energy of 100.2 eV. And, Si–Si bond with a binding
to constituting TiN ad Si3N4 phases. Thus, sense was observed one energy of 98 eV, as corroborated in previous studies [30–32]. Subse
reduction of stoichiometric ratio when the Ti content was decreased and quently, Fig. 4d shows the high intensity spectra for the Ti (2p3/2)
the Si and N contents were increased, therefore, all TiSiCN coatings were signal, this spectra was fitted by four Gaussian signals corresponding to
sub-stoichiometric when the applied power was increase from 400 W to Ti2O3, Ti–C, Ti–N and Ti bonds at binding energies 463.5, 461.1, 456.1
550 W. and 454 eV, respectively, according to the literature [36–38]. The Ti
For a more detailed study of the bonds present in the obtained (2p3/2) signal was taken into account because it was the signal that
coatings, Fig. 4 shows the high resolution spectra for the C (1s), N (1s), Si presented the highest intensity in the survey spectrum observed in
(2p) and Ti (2p3/2) signals with the respective deconvolutions to Fig. 3. In addition, the characteristic orbital of Ti that facilitates the
formation of Ti–C, Ti–N and Ti–Ti bonds was also taken into account.
Therefore, the dominant Ti 2p3/2 peak a is attributed to regular Ti4+
ion. For TiSiCN sample, higher binding energy (BE) peak with position
corresponding well with that of Ti4+ in carbonitride system, is attrib
uted to Ti–O, Ti–C, Ti–N and Ti–Ti species (Fig. 4d). To rule out its origin
of air exposure, with enhanced surface sensitive to explore its distribu
tion. Moreover, the lower spectral weight for Ti–O species was obtained,
suggesting that they are not distributed on the surface, but formed
during sample synthesis process [37,38]. Finally, Fig. 4e present the
high-intensity spectrum correspond to the O 1s signal, which was fitted
by one Gaussian function attributed to the O–Ti bonds located at the
binding energies 532.51 eV, as shown in the literature [36–38]. So, the
presence of oxygen can be attributed to surface contamination phe
nomena of the sample and to the coatings processing associated with the
oxygen present in the sample which come from the oxidation of the Ti
targets.
Based on the compositional analysis presented in Fig. 3, it was
possible to determine the stoichiometric relationship between the ele
ments obtained, which were presented in Table 1. Elements such as Ti,
Si, C and N were identified in high quantities and a low concentration of
Fig. 3. XPS spectra for TiSiCN coating with different applied power on
oxygen, which is associated with a partial oxidation of silicon
Si3N4 target.
4
Fig. 4. XPS High resolution spectrum for (a) C 1s, (b) N 1s, (c) Si, (d) Ti 2p3 and (e) O 1s signal.
(substrate). Subsequently, Fig. 5 shows a decrease in the intensity of the authors such as A.O. Eriksson et al. [35], have synthesized this quater
Ti and C peaks and an increase in the Si and N peaks, evidencing a nary TiSiCN coating by other methods obtaining similar bonds to those
variation of the species present in the plasma and an increase in the Si obtained in this research [35,36].
and N content within the TiSiCN coatings. This increase in the Si and N
content is attributed to an increase in the applied power to the Si3N4
target, which causes a higher intensity and density of the bombardment 3.3. Scanning electron microscopy by SEM and EDX study
of Ar + atoms with a higher kinetic energy to impact the target surface.
Thus, a higher amount of Si and N sputtered particles are generated, Fig. 6 shows the SEM micrograph of the surface and cross-section of
which will be deposited on the surface of the substrate (HSS steel and the TiSiCN coatings as a function of the power applied on the Si3N4
silicon). This increase of the bombardment intensity and a higher target, deposited on silicon substrate. From these micrographs it was
amount of sputtered particles will influence the morphological, me possible to evidence a contrast difference associated to a change in the
chanical and tribological properties as a corroborated in Figs. 8, 10 and electron density between the substrate-coating, thus the substrate pre
12, respectively [40]. On the other hand, the presence of the O (1s) sents a dark contrast due to its low electron density and a bright contrast
signal is attributed to environmental contamination of the coating, some due for the TiSiCN coating. In addition, it was possible to identify a
columnar and ordered growth for all coatings, this ordered growth is
5
the position of minimum energy that increase diffusivity and grain size
in agreement it he literature [22,23,26,29]. Thus, in the crystalline zone
corresponding to the nano-crystal, the crystalline plane in the direction
(200) can be observed, referring to nc-TiSiCN, as evidenced by XRD
analysis (Fig. 1). Therefore, in the quaternary phases of the nano
composite obtained by XRD, it can be suggested that in the solid solu
tions the Ti, Si atoms are in coordinates (0,0,0), on the other hand the C
and N are located in coordinates (1/2,1/2,1/2), simulating a NaCl type
structure. Furthermore, the widening of the XRD (200) peak, as a result,
a nano-grained microstructure is produced in solid solution. In this
research was categorized a refinement structural system for TiSiCN with
the interplanar distance of d(200) = 2.1395 Å in agreement with the
literature [22,23,26,29], so in the quaternary material, the intensity of
the (200) plane indicates that Wyckoff 4 b sites are occupied by C and N
atoms, Wyckoff 4a sites are occupied by Ti and Si atoms randomly.
Moreover, the interface between the amorphous zone of the matrix and
the nanocrystal is denoted in Fig. 8b, therefore, the number of
nano-crystals and geometric configuration defines the variation of the
Fig. 5. Atomic content variation in the TiSiCN coatings. mechanical properties such as shown via TEM results.
On the other hand, the high vacuum conditions in the processing of
associated with high atomic bombardment of the atoms on the substrate the coatings, it can be observed from the XPS results that the oxygen (O)
surface during the deposition process, and that this ordered growth is content is very low but there is presence of this element, therefore, it is
much more evident for the coating deposited with 500 W, since this possible that O has been added at the grain boundaries or modified the
coating presented a lower amount of residual stresses, which favors a stoichiometry of the TiN and Si3N4 phases, however no strong evidence
denser and more compact coating, obtaining a surface with lower of significant phase modification was witnessed in the XRD results. Then
roughness and smaller grain size, as previously corroborated. considering the above, as well as the XPS results, the cross-sectional EDS
Finally, the thickness of the coatings was determined, obtaining an results reveal a low oxygen contribution, which may affect the stoichi
average constant thickness for all coatings of 2 ± 0.02 μm. This constant ometry of the grain boundaries in the nanocomposite, since the grain
thickness is due to the fact that most of the deposition parameters were boundaries are symmetry breaking zones where O can interact with the
similar and for the change in power applied, the deposition rate of each phase and adjust with the amorphous nature of a-SiCN as observed in the
coating was calculated, as mentioned in the experimental section. In this TEM results. Moreover, from diffraction TEM results (Fig. 8a) was
way, all the coatings were deposited at similar conditions, with the possible to observe that the coating obtained with 500 W presented a
purpose that all coatings will have similar thickness, since some research lattice parameter (a0 = 4.3071 Å) much closer to the stress-free position
such as those done by Karol Kyziol et al. [40], Grzegorz Greczynski et al. (a0 = 4.3102 Å), indicating that this structure presented a lower amount
[18] and Yinghe Ma et al. [41], conclude that the variation of the of residual stresses compared to the other coatings such as was analyzed
deposition parameters and mainly the thickness of the coatings, will in XRD results.
modify the properties of the coatings. In this sense, the complete structural information can be extracted
Fig. 7 shows a compositional analysis by EDX on the cross section of from the selected area electron diffraction (SAED) patterns, as shown in
the coating (Fig. 7a) in order to differentiate and evidenced between the Fig. 8a and b. These SAED patterns are representative of the diffraction
deposited coating (TiSiCN), which is corroborated by the EDX spectrum patterns obtained from selected regions (Fig, 8) in the TiSiCN coating.
(Fig. 7b), where peaks attributed to Ti, Si, C and N. And, Fig. 7c shows The patterns demonstrate the crystalline structure for the TiSiCN ma
the EDX spectrum for silicon substrate, indicating the presence of a high terial with preferential growth in the (200) crystallography direction.
intensity peak corresponding to the silicon, and another peak with a low Moreover, in Fig. 8b the structural arrangement for the a-SiCN matrix is
intensity attributed to oxygen, due to the partial contamination of the shown by the ring-shaped diffraction of light with small amorphous ring,
substrate in a low proportion as was evidenced. which indicates that the growth exhibited for nanocomposite is associ
ated to the symmetry breaking. The diffraction pattern for nano
composite is shown in Fig. 8, where the transition is clear according to
3.4. Transmission electron microscopy (TEM) the ordered structure for the TiSiCN where the diffraction patterns have
high intensity and the diffraction rings for the a-SiCN matrix. The results
Fig. 8a shows the HR-TEM micrographs of a nanocomposite coating obtained for the multilayers by XRD also indicated the nanocomposite
recorded in cross-sectional configuration. The absence of diffraction effect caused by the reflection of X-rays at high and low angles around
contrast in much of these HR-TEM images indicates the coating is mainly the Bragg peaks of the crystal structure. The textured nanocomposite
constituted by an amorphous matrix, which can be associated with the grew in the (200) direction perpendicular to the substrate surface and
continuous a-SiCN composite [42,43]. The formation of a halo ring in a the relationship nc-TiSiCN(200)/a-SiCN, as shown by the (200) direc
fast Fourier Transformed (FFT) image certifies the amorphous character tion in the TiSiCN crystal zones according to the TEM results.
of the coating. However, we achieve detecting small regions that exhibit Finally, with the information obtained from XRD and HR-TEM, Fig. 9
a noisy diffraction contrast due to presence of nanocrystals that should shows the maximum intensity peak corresponding to the (200) plane for
correspond to the nc-TiSiCN system. According to the HR-TEM image the coating obtained with 500 W. The correlation between the XRD and
shown in Fig. 8b, the nc-TiSiCN nanocrystals have an irregular shape, HR-TEM results can be observed in Fig. 9. From this pattern it was
with an average size of around 6 nm, and they are dispersed along the possible to identify the contribution of the two different phases, modi
amorphous matrix. Thus, the TEM allowed resolving the expected fying its path and the degree of crystallinity as evidenced. Considering
nanocomposite system and confirmed quite precisely by the previously the above, a pseudo-Voigt deconvolution was performed, consisting of a
designed nominal configurations (associated with deposition condi Lorentzian fit associated to the crystalline phase of nc-TiSiCN and a
tions). The amorphous nature of the coating is linked to the use of a Gaussian fit corresponding to the amorphous phase of a-SiCN. Thus, in
deposition temperature, due to that this phenomenon is attributed to the the Lorentzian fit, a wide distribution of different intensity values is
mobility of the atoms in the plasma on the surface material, which favors analyzed for a reduced variation of the diffraction angles 2θ referred to a
6
Fig. 6. Cross-section micrograph for TiSiCN coatings as a function of applied power: (a,b) 400 W, (c,d) 450 W, (e,f) 500 W and (g,h) 550 W.
crystalline behavior. On the other hand, the Gaussian fit was analyzed stoichiometry close to the phase of a-SiCN such as Si42C39N20. Taking in
with a wide distribution of close intensity values for a wide variation of account the last results, is possible to analyzed that solubility isotherms
the diffraction angles 2θ referred to an amorphous behavior as observed for the ternary system SiCN and the quaternary reciprocal system TiSiCN
in the results of the SAED patterns obtained by HR-TEM. On the other determined at temperatures above 1273.15 K and 1400 K respectively
hand, Fig. 9b based on Transmission Electron Microscopy (TEM) results, by an isothermal dissolution method. In the ternary phase diagram,
two regions can be stablished, one amorphous and the other crystalline. there are 3 more important solubility branches corresponding to the
So, in the amorphous region, an EDX analysis was carried out and solid phases SiCNx(s), Si3CN4(s) and SiCN(s). In the quaternary equi
chemical elements such as Si, C and N were observed, which can be librium phase diagram, there a 3 more important solubility co-saturated
associated with the phase of a-SiCN. In this sense, from the EDX spec lines corresponding to the solid phases TiSiCN(s), TiN + Si3N4+SiC(s),
trum of the amorphous zone, it was possible to determine a and SiCNx + TiN(s). This report describes that coating present the
7
Fig. 7. Compositional study on the cross-section of TiSiCN coating deposited with 500 W (a) Cross-sectional SEM (b) EDX analysis for TiSiCN coating and (c) EDX
analysis for substrate.
equilibrium solid phases SiCN and TiSiCN however for TiSiCN phase evidenced. By XRD it was possible to determine the contribution of two
have been found to exist in this quaternary system. Therefore, the phase signals associated to the crystalline contribution and the to the amor
field of TiSiCN(s) overlaps with the phase fields of TiN + Si3N4+SiC(s), phous contribution by means of deconvolution using a pseudo-Voigt
and SiCNx + TiN(s), which indicated that TiN + Si3N4+SiC(s), and type adjustment.
SiCNx + TiN(s) are metastable phase; TiSiCN(s) is a relatively more
stable phase in the quaternary systems. A Pitzer-Simonson-Clegg ther
3.5. Residual stress measurement by profilometry
modynamic model was used to simulate the properties of the ternary and
quaternary systems and to predict the solubility phase diagram of the
In order to calculated the residual stresses present in the obtained
quaternary system. Many results showed in the literature of the
coatings, the Stoney model was used. The coating-substrate systems can
modeling are in reasonable agreement with the experimental data
present a measurable deflection with a determined radius. This bending,
[44–46].
known as curvature, can be calculated by means of a profilometer,
performing a long sweep to minimize the influence of roughness in this
3.4.1. Elemental composition for TEM-EDX analysis
sweep (profile), and measuring the height of the parabola which is the
Fig. 10 shows the results obtained by TEM-EDX to determine the
result of the curvature generated by the deposition of a coating on the
distribution of the elements present in the coating. Fig. 10a shows the
substrate surface. Therefore, this bending (curvature) can be concave
surface EDX image of the coating obtained with 500 W, where the two
attributed to tensile stresses, or convex indicating compressive stresses.
analysis zones in this study were evidenced (spectrum 1 and spectrum
In this sense, Fig. 11a shows the profiles obtained with a length of 3 mm
2). Fig. 10b shows the EDX spectrums obtained from the different zones.
for all TiSiCN coatings as a function of the applied power, where a
Spectrum 1 corresponding to the amorphous phase (a-SiCN), presents
convex curvature associated to compressive stresses is evidenced, which
elements such as Si, C and N, and spectrum 2 shows an increase in the
are in agreement with the results obtained by XRD (Fig. 1b). For this
Titanium content, associated to the presence of nc-TiSiCN nanocrystals,
analysis, the silicon substrates have an approximate thickness of 0.3
where elements such as Ti, Si, C and N were obtained. Subsequently,
mm, which can easily generate a curvature by the incorporation of
Fig. 10c presents a composition map attributed to the atomic distribu
coatings on it surface due to the low thickness of this substrates and
tion of the elements present, where different colorations associated to
these residual stresses can be estimated by the Stoney equation (Eq. 3)
each of the elements (Ti, Si, C and N) were evidenced. Finally, a low
[47–49].
intensity peak corresponding to O was evidenced, which is corre
sponding with the oxidation of the substrate (silicon 100). Ef
νh
2
From the SAED-TEM images it was possible to analyze the different σ = 1− (3)
6Rt
phases, the crystalline phase with their atomic planes observed by
HRTEM and amorphous phase where neither continuity of the atomic Where σ is the intrinsic residual stress in the coating, Ef is the reduced
planes nor structural coherence is perceived, also the crystalline phases elastic modulus (Youngs modulus) of the coatings, h is the substrate
were identified with the indexation of the intensity maxima (spots) by thickness, ν is Poisson modulus of the substrate, R the curvature radius
diffraction and the amorphous zone with the dispersion ring, by TEM- and the t are the coating thickness. From equation (3), it is observed that
EDS the chemical composition of both phases was analyzed and in the the intrinsic residual stress (σ) is intimately related to the curvature
amorphous phase no contribution of the Ti chemical element was radius (R).
To determine the residual stress in TiSiCN coatings, silicon wafer of
8
Fig. 8. TEM images of the cross-section for the individual TiSiCN layer deposited with 500 W: (a) HRTEM exposing the nc-TiSiCN crystal, and the amorphous area of
the a-SiCN matrix and (b) Nanocomposite configuration with nc-TiSiCN crystals and a-SiCN amorphous matrix.
350 μm thick were used, with the known Young’s modulus (Ef = 162.91 shows the stress relief as a function of applied power in agreement with
Gpa) and the Poisson’s modulus (ν = 0.223). The residual stress in XRD results within the compressive regimen changes from high
TiSiCN coatings is shown in Fig. 11b, and reveals a progressive change in compressive stress to low compressive stress. Also, the stress reduction
relation to changes in the applied power. Thus, it is possible to observe of around 78 % can be explain by the presence of interface within the
two different zones (compressive and tensile stress), and that the coating nanocomposite systems and their increasing influence when increasing
deposited with lower power density (400 W) presented the highest the applied power to Si3N4 target [47,49].
amount of compressive residual stresses, as corroborated by the
diffraction patterns (displacement of the peak of maximum intensity 3.6. Surface characterization
towards higher angles), indicating a 5.23 Gpa, and that these residual
stresses decrease considerably as the power density increases up to a 3.6.1. Atomic force microscopy
value 1.14 Gpa, approaching the stress-free zone for the coating The study of the surface characteristics was performed by AFM.
deposited with 500 W, as evidenced in the structural analysis (Fig. 1b). Fig. 12 shows the 3D profiles for all the coatings obtained in a study area
There results corroborated the structural study, where the coating pre of 2 μm × 2 μm, on Silicon substrate, with the purpose of determining
sents a crystalline structure with lower residual stresses and will posi the roughness and grain size, statically supported in the SPIP software.
tively influence the rest of the properties. In the AFM 3D profiles for the individual layers, it was possible to
However, by increasing the power density to 550 W it was possible to determine that all the coatings presented circular grain morphology
observe again the increase of compressive residual stresses. This with a tendency to reduce as the power applied to the Si3N4 target is
behavior is associated to high transfer energy during the deposition increased. On the other hand, a more homogeneous morphology could
process, which causes a high mobility in the nucleation of the nano be observed on the nc-TiSiCN coatings surface deposited at 500 W about
crystal with respect to the matrix, generating again an increase in the the other coatings. The morphology changes can be explained by the
compressive stress. Taking into account the last discussion, Fig. 11b effect of ion bombardment of from Ar + atoms on the Si3N4 target, which
9
increases the energy of the spacing present in the plasma and these
spices are directed to the surface of the substrate with higher energy. In
this sense, the surface of the layers is modified as an effect of the
bombardment, due to the increase in the atomic energy absorbed on the
substrate, causing nucleation points and causing a decrease in grain size.
However, when applying a power higher than 550 W to the Si3N4 target,
an increase of roughness and grain size is observed again, which may be
associated to an excessive energy input corresponding to the re-
sputtering phenomenon [26,37].
Fig. 13a–b presents the analysis of roughness and grain size respec
tively for all coatings as a function of the power applied to the Si3N4
target. In Fig. 13a–b, it was determined that increasing the applied
power from 400 W to 500 W presented a decrease of 30.7 % and 13.1 %
for roughness and grain size, respectively. Subsequently, when
increasing the applied power from 500 W to 550 W, an increase of 5.6 %
and 2.9 % was observed for roughness and grain size, respectively. This
behavior in the surface properties is attributed to the residual stresses as
shown in Fig. 1b, where it was possible to determine that the residual
stresses in comparison to the other coatings, and that by increasing again
the applied power from 500 W to 550 W it was possible to evidence
again the presence of residual stresses within the crystalline structure.
Finally, by means of this superficial analysis, it was determined that the
coating deposited with 500 W, presented a lower amount of residual
stresses (Fig. 1b), which generates a more orderly and regular growth,
obtaining a denser structure and causing a decrease in surface rough
ness, as well as a much smaller grain size. Taking into account the above,
it was thus determined that the surface of the TiSiCN coating deposited
with 500 W presents a higher amount of grains in the analysis area thus
generating a higher grain edge density, being these grain edges obstacles
or impediments to the movement of dislocations, which may influence
the physical properties of the material. Therefore, these morphological
characteristics affect the mechanical and tribological properties in the
nc-TiSiCN system [43,44].
3.7. Mechanical properties
Fig. 9. Correlation between XRD and HR-TEM results, where a crystalline The load-depth curves obtained from the nanoindentation test can be
phase (nc- TiSiCN) and an amorphous phase (a-SiCN) were evidenced and (b) seen in Fig. 14 for the different coatings. Fig. 15 shows the mechanical
TEM-EDS spectrum of the amorphous zone, with the stoichiometry close to the behavior of the surfaces, evidencing that the TiSiCN coating deposited at
phase of a-SiCN such as Si42C39N20. 500 W presents a reduction in depth of 23.5% in relation to the TiSiCN
coating deposited at 400 W, a reduction of 18.9% in relation to the
TiSiCN coting deposited at 450 W, and 12.8% in relation to the TiSiCN
Fig. 10. Compositional Analysis (a) TEM-EDX Imagen (b) Distribution of the elements present and (c) Spectrum EDS.
10
Fig. 11. Intrinsic residual stress measurements by profilometry: (a) Surface profiles and (b) Compressive stress values as a function of the applied power.
Fig. 12. Atomic force microscopy (AFM) images for individual TiSiCN coatings as a function of the applied power (a) 400 W, (b) 450 W, (c) 500 W, and (d) 550 W.
Fig. 13. Influence of applied power on the morphology of TiSiCN coatings: (a) Roughness vs. applied power, (b) Grain size vs. applied power.
11
compressive stress relief generated during the deposition process when

the applied power was increased can contribute to the increase of the
hardness for the 500 W and such as observed from X-ray results (Fig. 1b).
So, the nc-TiSiCN coating deposited with 500 W presents better me
chanical properties such as hardness (H) and reduced elastic modulus
(Er).
From the nanoindentation results, the resistance to plastic defor
mation (H3/E2) and the elastic recovery (R) were determined as a
function of the applied power on the Si3N4 target. The elastic recovery of
the coatings was calculated using the following equation [46,47].
δmax − δp
R= (Eq. 4)
δmax
Where δmax is the maximum displacement and δP is the residual

displacement. The data for Eq. (4) were taken from the load-depth
curves presented in Fig. 14. Fig. 16a–b shows the values obtained for
the plastic deformation resistance (H3/E2) and elastic recovery (R) for
Fig. 14. Load-depth curves for individual nc-TiSiCN coatings as a function of the different coatings, which determined that the highest plastic defor
the applied power. mation resistance (H3/E2) and elastic recovery (R) were obtained for the
nc-TiSiCN coating deposited at a power of 500 W, which is mainly due to
coting deposited at 550 W. This behavior can be explained by properties factors such as the characteristics of the nc-TiSiCN nanocrystals
such as hardness which increases the resistance of the material to be observed by TEM (Fig. 8) and their mechanical properties such as
penetrated. Therefore, the mechanical properties such as hardness (H) hardness and reduced elastic modulus, which was analyzed above
and elastic modulus (E) were analyzed by Oliver and Pharr method Fig. 15. Finally, it was possible to observed that the generation of a
presented in Fig. 15a–b respectively [43]. The mechanical properties continuous amorphous a-SiCN phase and a discrete nc-TiSiCN phase,
increase can be related to morphology, size and quantity of the with fusiform grain morphology where inhabiting the crystalline phase
nc-TiSiCN nanocrystals observed by TEM (Fig. 8). In that sense the observed by TEM, was responsible for an increase in the mechanical
nanocrystals character restricts the dislocations movement, this modi properties such as hardness from 27 to 32 GPa and elastic modulus of
fying the amount of the amorphous phase, this phenomenon has been from 290 GPa to 301 GPa was evidenced.
reported by Y. Wang et al. [39]. For the same material deposited at 500
W [39,45]. Finally, was possible to observe the evolution in the me 3.8. Tribological properties
chanicals properties as function of preparation conditions in the coat
ings, in agreements of Ya-jun Zheng and co-workers [46]. Fig. 17a presents the friction coefficient in the dry environment of
Fig. 15a–b shows the results of hardness (H) and reduced elastic the interaction between steel counterpart (100Cr6) and the surface of
modulus of (Er) for all coatings deposited on silicon (100) substrate as a nc-TiSiCN coatings deposited on an HSS steel substrate at different
function of the applied power on the Si3N4 target. In this research, it powers. The friction coefficient results in dry environment presented
could be determined that the nc-TiSiCN coating deposited at 500 W two characteristic stages, typically occurring during the Pin-On-Disk
presents a higher resistance to be indented compared to nc-TiSiCN test. In stage I, a rapid increase of friction coefficient is evident for all
coatings deposited at powers of 400 W, 450 W and 550 W respec surface due to interaction produced by the direct contact between the
tively. This behavior can be attributed to factors such as the character counterpart and the coating. This rapid increase is related to the surface
istics of the nc-TiSiCN nanocrystals observed by TEM (Fig. 8) and a characteristics (roughness) of the coatings, since being in contact with
smaller grain size, as observed in the AFM results (Fig. 11), since pre the counterpart, these roughness are deformed, producing wear parti
senting a greater amount of nanocrystals with less irregular morphol cles on the surface, and these particles will harden and oxidize,
ogies, greater amount of grain edges, these edges act as impediments or increasing the friction at the contact point for all surfaces, so a surface
obstacles to the sliding of the dislocations, so a greater amount of energy more irregular surface as the coating obtained with 400 W, will generate
will be required to overcome these obstacles [22,38]. In addition, the a higher amount of abrasive particles on the surface [43]. Subsequently,
Fig. 15. Mechanical properties of the nc-TiSiCN layer as a function of the applied power on the Si3N4 target: (a) Hardness and (b) Elastic Modulus.
12
Fig. 16. Mechanical properties for TiSiCN coatings: (a) plastic deformation resistance (H3/E2) and (b) elastic recovery (%R).
Fig. 17. Tribological properties of TiSiCN coatings deposited with different powers of 400 W, 450 W, 500 W, and 550 W, in dry environment: (a) friction coefficient
as a function of sliding distance from Pin-on-Disk test and (b) friction coefficient as a function of applied power.
Stage II, known as the settling period (running-in), it was possible to Where: μ is the friction coefficient, Ck is a constant of the test, R(s,a) is the
observe a stabilization of the friction coefficient values for all surfaces. roughness of the coating, σt(H,Er ) is a variable that depends on the me
This settling of the values is associated with the constant passage of the
chanical properties of the system such as hardness (H) or elastic modulus
counterpart, which deforms the asperities increasing the real contact
(Er).
area, so that the contact surface increase is able to withstand the external
Fig. 18 presents SEM micrographs for all wear surfaces of nc-TiSiCN
load applied by the counterpart and avoid the deformation of the surface
coatings deposited on HSS steels in a dry environment as a function of
[50].
applied power. The SEM micrographs were used to determine the
Considering to the above, Fig. 17b presents the value of the friction
mechanisms present on worn surfaces after performing the pin-on-disk
coefficient for all surfaces as a function of the power applied to the Si3N4
test. By means of SEM micrographs, it was possible to mainly evidence
target. The trend presented by the coatings is related to the frictional
abrasive wear, which is generated by the deformation of the asperities
model proposed by Archad [51], which relates the surface and me
due to the continuous passage of the counterpart on the surface. These
chanical properties of the coatings, as shown in Eq. (5). Thus, the value
abrasive particles were deformed and adhered to both surface of the
of the friction coefficient is directly related to the roughness and is
tribological pair (counterpart-coating) generating a plowing and wear
inversely proportional to the mechanical properties such as hardness
mechanism on that surface. On the other hand, adhesive wear was
and elastic modulus redecided (H, Er). Therefore, the coating deposited
generated in certain areas of the counterpart (pin 100Cr6), which
with 500 W presents a structure with lower residual stresses compared
plastically deformed and adhered to the surface of the nc-TiSiCN
to the others (Fig. 1b), and this decrease in residual stresses caused a
coating. In the SEM micrographs of the wear tracks produced in the
more ordered growth resulting in a more regular and uniform surface
tribological test, it could be seen that for the uncoated HSS steel sub
(low roughness). In addition, this ordered structure generates a better
strate (Fig. 18a), the predominant surface wear mechanisms are abrasive
distribution of TiSiCN nanocrystals within the amorphous matrix
and adhesive. This is due to its low mechanical properties and a rela
(SiCN), and this change of coherence between amorphous matrix and
tively high friction coefficient compared to the TiSiCN coating, which
nanocrystals (symmetry breaking), restricts the passage of dislocations,
produces a large number of particles on the surface that are deformed
acting as obstacles increasing the failure energy in these specific zones,
and hardened by plastic deformation. In addition, the constant passage
thus, a greater amount of external energy is required to cause defor
of the counterpart removes and deforms the asperities associated with
mation and generate wear on the study surface.
the roughness of the HSS steel, so that the contact area increases and the
Ff R(s,a) number of wear particles decreases. Subsequently, this increase in the
μ= = Ck (Eq. 5)
Fn σt(H,Er ) contact area generates micro-welds, which are detach during the
tribological test and produce a removal of material [47–49,52,53]. On
13
coating deposited with 500 W presents lower amplitude and penetration

in the worn track. This wear behavior is due to the nanocomposite
characteristics which are consisting by nc-TiSiCN nanocrystals and an
amorphous a-SiCN matrix, the mechanical and morphological properties
previously described, which minimize deformation of the surface micro-
irregularities affecting the contact area in the wear process, thus mini
mizing the volume removed from the coating as described in Fig. 18d.
3.9. Wear rate analysis
To determine the amount of wear produced during the tribological

test in a dry environment, a quantification of the wear rate was made
from the pin-on-disk test (Figs. 17 and 19). Taking into account the data
obtained from the profilometry test, the wear rate was determined for all
the dry environment surfaces obtained during the tribological test and
calculated from the following equation [54].
V
k= and S = 2.π.r.n (Eq. 6)
F.s
where (k) is the wear rate, (F) is the applied force, (V) is the track vol
ume, (S) is the perimeter of the wear track, (n) is the number of cycles or
turns of the test, (r) is the radius of the wear track cycles.
To satisfy the terms expressed in equation (6) it is necessary to
determine the volume of the wear track, therefore, Fig. 20a–b shows
width and depth values from the wear track generated during the
tribological test for TiSiCN individual’s coatings deposited as a function
of the applied power (400 W, 450 W, 500 W, and 550 W). The results
show a geometrical reduction in the wear tracks when the mechanical
properties improve, such as the elastic modulus (Fig. 15) and the plastic
deformation resistance (H3/E2) (Fig. 15), thus reducing the micro-cracks
production and minimizing delamination mechanisms. In that sense, the
coatings obtained with lower power deposition (400 W) presented
higher track widths (1100 μm) and track depths (1.1 μm) values,
compared to the TiSiCN coating deposited at 500 W, which presented
lower track widths (350 μm) and track depths (0.65 μm) values.
Fig. 20a–b presents a reduction of 68 % in the width and 40 % in the
depth values of the wear tracks concerning the coating obtained at 400
W. Taking the above into account, can be determined that the wear rate
results for uncoated steel substrate and all nc-TiSiCN coatings deposited
as a function of the applied power on the Si3N4 target vary with the lost
volume of each material. Therefore, in Fig. 20c the volume loss for the
substrate and all coatings were determined taking into account the track
widths and the track depths results (Fig. 20a–b). So, Fig. 20c shows a
significant reduction of the wear volume as a function of the applied
power, which is consistent with the mechanical properties evolution and
of the friction coefficient reduction. In this sense, Fig. 20d shows a wear
Fig. 18. SEM micrographs of the wear tracks of the TiSiCN coating as a func rate decreasing as a function of the applied power on the Si3N4 target
tion of the applied power on the Si3N4 target: (a) HSS steel, (b) 400 W, (c) 450 and an increase for the nc-TiSiCN coating deposited at a power of 550 W.
W, (d) 500 W, and (e) 550 W. The maximum reduction of the wear rate corroborates that the nc-
TiSiCN coating deposited at 500 W presented a higher wear resis
the surfaces of steels coated with TiSiCN in a dry environment (Fig. 18b, tance. This behavior it was attributed to the nanostructural modification
c, 18d, and 18e), it was determined that the predominant wear mech of the [nc-TiSiCN]-[a-SiCN] nanocomposite, the lubricating behavior
anisms on these surfaces were adhesion and abrasion although more that provides from carbon that can be caused by the formation of
reduced with the uncoated steel, this change of behavior to the HSS steel amorphous silicon carbon-nitride and carbon in the form of graphite and
substrate is due to the change of the mechanical properties surfaces and is also related to the increase in mechanical properties, reduction of the
surface morphologies in the coatings which provide a greater resistance friction coefficient, and the wear rate reduction [25,50,51].
to be deformed, generating a lower amount of removal and wear of the
material, where the TiSiCN coating deposited with an applied power of
3.10. Scratch test analysis
500 W a lower wear track was found.
The 3D profiles of all the wear tracks obtained by profilometry are
To determine the critical load at which the nc-TiSiCN nanocomposite
shown in Fig. 19, in that sense, the profilometry results corroborate the
coating can be delaminated from the substrate as a function of the ad
wear analysis associate to wear tracks observed by SEM (Fig. 18a), for
hesive properties, the scratch technique was used. Fig. 21 shows the
uncoated HSS steel substrate and for all nc-TiSiCN coatings deposited at
different tests results in relation to the applied power on the Si3N4 target.
different applied powers, such as 400 W, 450 W, 500 W and 550 W.
The adhesion properties are characterized by two concepts, critical load
Considering the above, the profilometry images show that the nc-TiSiCN
at which the cohesive failure occurs (LC1), is the moment where the first
14
Fig. 19. 3D profile images of the wear tracks of the nc-TiSiCN coating as a function of the applied power on the Si3N4 target: (a) HSS steel, (b) 400 W, (c) 450 W, (d)
500 W, and (e) 550 W.
Fig. 20. Measurements of wear tracks after pin-on-disk testing for TiSiCN coatings deposited as a function of power applied on the Si3N4 target: (a) Depth in the wear
track, (b) width of the wear track, (c) volume lost and (d) wear rate variation.
15
Fig. 21. Scratch test curve for all nc-TiSiCN coatings deposited as a function of applied power on the Si3N4 target.
cracks appear, on the other hand, there is the critical load at which the significant reduction in the scratch resistance (Lc2), which can be
adhesive failure occurs (LC2) and is related to the first delamination at attributed to the reduction of the mechanical and tribological properties
the crack edge. So, the loads were found in the regions of the scratch evidenced above. However, a maximum critical load of 62.4 N was
curve where the friction coefficients were stabilized and the load be observed for the nc-TiSiCN coating obtained at 500 W, representing an
comes independent of friction. The first detected zone refers to the load increase of 57.4 % in relation to the critical load for the coating grown at
at which cohesive failure occurs (LC1) and the second stabilization zone 400 W. This behavior is attributed to the characteristics of the [nc-
refers to the load at which adhesive failure occurs (LC2) [55,56]. TiSiCN]-[a-SiCN] nanocomposite structures found by XRD (Fig. 1) and
Fig. 22 shows the increase of the critical load (LC2) for all the nc- TEM (Fig. 8), also to the increase of mechanical properties determined
TiSiCN coatings deposited as a function of the applied power on the by nanoindentation (Figs. 18 and 19) and tribological properties
Si3N4 target. In Fig. 22 it can be analyzed that the coating deposited at analyzed by pin-on-disk test (Fig. 19).
500 W presents the highest Lc2 at which the adhesive failure occurs, In this sense the symmetry breaking in the amorphous crystalline
which indicates that the nc-TiSiCN coatings obtained with 500 W pre interface of the nanocomposite together with the increase of the nano
sents better coating adhesion and less coating delamination, compared crystals generation with the applied power produced an evolution in the
to the coatings obtained with 400 W, 450 W and 550 W. In this sense, it tribological properties evidenced by friction coefficient decreasing in
can be analyzed that the layer grown with a power of 550 W shows a relation to uncoated HSS steel in this sense, the nanocomposite obtained
with a power of 500 W exhibited the best performance showing the
lower friction coefficient of 0.31 and lower critical load of 62.4 N, with
lower wear rate. Finally, was possible to observe the evolution in the
physical properties as function of preparation conditions in the coatings,
in agreements of Q. Li and co-workers [56].
In Fig. 23a, b, 23c, and 23d, the scanning electron microscopies at
1000× magnification, of the scratch traces for the nc-TiSiCN nano
composite coatings deposited at different applied powers on the Si3N4
target are presented. To observe the critical load effect and cohesive
(LC1) and adhesive (LC2) failures on the coatings surfaces, the SEM mi
crographs present that the increasing in the critical loads was made
when the applied power was increased until a maximum value where a
reduction begins. These tribological effects observed by SEM micro
graphs complement those evidenced in Figs. 19 and 20. Taking into
account that the increase in the elastic recovery and the increase in the
elastic deformation resistance, act as a block to crack propagation, so a
higher load must be applied to generate cracks and detachment of the
coating (adhesive failure) of the substrate/coating system (HSS/
TiSiCN).
Fig. 22. Lc2 for all nc-TiSiCN coatings deposited as a function of the applied
power on the Si3N4 target.
16
coatings obtained as a function of applied power. Through this analysis,

it was possible to show that the same trend was maintained, where the
coating deposited with 500 W presented a higher hardness and lower
wear rate. This mechanical and properties behavior is related to the
surface characteristics, since having a much more homogeneous surface
with higher hardness, as previously presented, generates lower amounts
of wear particles, which directly influence the surface wear of the
coatings.
Fig. 25 shows the variation of hardness, wear rate and size of the
nanocrystals as a function of process variables such as applied power
onto Si3N4 target (Fig. 25a–b). In that sense when the size of the discrete
phase or the crystals size is very low between 5 nm (400 W), the
continuous phase (amorphous) tends to be larger; therefore, the me
chanical properties e.g. hardness tend to decrease. However, when the
crystal size is higher 8 nm (550 w), the mechanical properties tend to
increase when the material is subjected to applied load. In addition,
when the crystal size is very low the plastic deformation or cracks
progress easily due to the reduced crystal size, since the nanocrystals act
as zones of high symmetry dissipating the crack energy and increasing
the mechanical properties, which will be reflected in a better perfor
mance of mechanical devices coated with the Ti–Si–C–N nanocomposite.
4. Conclusions
Fig. 23. Scanning electron microscopy on the scratch traces for all TiSiCN
Structural study by TEM-EDX and XRD allowed to identify that the
coatings deposited as a function of the applied power on the Si3N4 target: (a)
TiSiCN coating is composed of an amorphous phase consisting for [a-
400 W, (b) 450 W, (c) 500 W, and (d) 550 W.
SiCN] and nanocrystals consisting for [nc-TiSiCN], and the distribu
tion and coherence of these nanocrystals lead to increased surface,
3.11. Merit index
mechanical and tribological properties.
Surface analysis by AFM determined a decrease of 13.4 % and 30.7 %
In order the correlate the obtained properties, Fig. 24a–b show a
for grain size and roughness when comparing the coating deposited with
direct correlation between two different properties as a function of the
400 W with the 500 W. Subsequently, the generation of a continuous
applied power, where it was possible to show at which power the best set
amorphous a-SiCN phase and a discrete nc-TiSiCN phase, with fusiform
of properties was obtained. Fig. 24a shows the correlation between the
grain morphology where inhabiting the crystalline phase observed by
lattice parameter and hardness, as well as the value of the theorical
TEM, was responsible for an increase in the mechanical properties such
lattice parameter (dotted line), where the material is stress free. From
as hardness from 27 to 32 GPa and elastic modulus of from 290 GPa to
these results, it was possible to show that the coating deposited with 500
301 GPa was evidenced.
W, presented a lattice parameter closer to the stress-free position and
The merit index analysis, which correlated the structural properties
with the higher hardness obtained (32 Gpa), this behavior is attributed
with the mechanical and tribological response, showed that the coating
to the fact that this structure presented a lower amount of residual
obtained with a power of 500 W, presented the lowest residual stresses,
stresses during the deposition process, which generated a coating with a
with the lower modification of the lattice parameter, which influenced a
more orderly and dense growth than the others, influencing its surface
more orderly growth, which increased the mechanical and tribological
properties such as roughness and grain size. And where these surface
properties. Finally, the merit index indicated that this coating (deposited
properties influenced the resulting mechanical properties of the coating,
with 500 W) presented the best set of properties and will be indicated to
since having a smaller grain size, a higher grain edge density was ob
be implemented as protective coating on engineered devices.
tained, which act as impediments to the passage of dislocations through
the coating, which causes an increase in mechanical properties. Fig. 24b
shows the direct comparison between hardness and wear rate for the
Fig. 24. Merit Index for (a) Structural and mechanical properties and (b) Mechanical and tribological properties.
17
Fig. 25. Merit Index for the process variables and the future applications in the industrial field: (a) mechanical properties and nanocrystal size and (b) tribological
properties and nanocrystal size as function of applied power on Si3N4 target.
CRediT authorship contribution statement [9] C.H. Ortiz, E. Hernandez-Rengifo, A. Guerrero, W. Aperador, J.C. Caicedo,
Mechanical and tribological properties evolution of [si3n4/al2o3]n multilayer
coatings, Tribol. Ind. 43 (1) (2021) 23–39, https://doi.org/10.24874/
C.H. Ortiz: Conceptualization, Formal analysis, Investigation, ti.952.08.20.01.
Methodology, Supervision, Writing – original draft, Writing – review & [10] C.H. Ortiz, W. Aperador, J.C. Caicedo, Physical properties evolution of β-tricalcium
editing. E. Hernandez-Renjifo: Formal analysis, Investigation, Meth phosphate/hydroxyapatite heterostructures in relation to the bilayer number, Thin
Solid Films 752 (April) (2022) 139256, https://doi.org/10.1016/j.
odology. J.C. Caicedo: Conceptualization, Supervision, Writing – orig tsf.2022.139256.
inal draft. [11] W. Aperador, J.C. Caicedo, C. España, G. Cabrera, C. Amaya, Bilayer period effect
on corrosion–erosion resistance for [TiN/AlTiN]n multilayered growth on AISI
1045 steel, J. Phys. Chem. Solid. 71 (12) (Dec. 2010) 1754–1759, https://doi.org/
10.1016/j.jpcs.2010.08.019.
Declaration of competing interest [12] D. Rafaja, et al., Some consequences of the partial crystallographic coherence
between nanocrystalline domains in Ti–Al–N and Ti–Al–Si–N coatings, Thin Solid
The authors declare that they have no known competing financial Films 514 (1) (2006) 240–249, https://doi.org/10.1016/j.tsf.2006.02.092.
[13] N. Marchin, F. Ashrafizadeh, Effect of carbon addition on tribological performance
interests or personal relationships that could have appeared to influence of TiSiN coatings produced by cathodic arc physical vapour deposition, Surf.
the work reported in this paper. Coating. Technol. 407 (Feb. 2021) 126781, https://doi.org/10.1016/j.
surfcoat.2020.126781.
[14] L.J.S. Johnson, L. Rogström, M.P. Johansson, M. Odén, L. Hultman, Microstructure
Data availability evolution and age hardening in (Ti,Si)(C,N) thin films deposited by cathodic arc
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The authors do not have permission to share data. 10.1016/j.tsf.2010.08.150.
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Materials Chemistry and Physics 317 (2024) 129095

Contents lists available at ScienceDirect

Materials Chemistry and Physics

Full Length Article

Evaluation of the tribological behavior of TiSiCN (a- SiCN/nc- TiSiCN)

• (a- SiCN/nc- TiSiCN) Nanocomposite Coatings.

1. Introduction Subsequently, coatings evolved to more complex system, such as

3.2. Elemental composition by XPS Power (W) (Si3N4 target) Ti Si C N O (Ti/Si + N)

3.7. Mechanical properties

compressive stress relief generated during the deposition process when

Where δmax is the maximum displacement and δP is the residual

coating deposited with 500 W presents lower amplitude and penetration

3.9. Wear rate analysis

To determine the amount of wear produced during the tribological

coatings obtained as a function of applied power. Through this analysis,

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