Wear 422–423 (2019) 68–80

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Wear
journal homepage: www.elsevier.com/locate/wear

Tribological performance of titanium nitride coatings: A comparative study T

on TiN-coated stainless steel and titanium alloy
⁎
Magdalena Łępickaa, , Małgorzata Grądzka-Dahlkea, Daniel Pieniakb, Kamil Pasierbiewiczc,
Kamila Kryńskaa, Andrzej Niewczasb
a
Department of Materials and Production Engineering, Faculty of Mechanical Engineering, Bialystok University of Technology, Wiejska 45C, 15-351 Bialystok, Poland
b
Department of Mechanics and Mechanical Engineering, Faculty of Transport and Computer Science, University of Economics and Innovation, Projektowa 4, 20-209
Lublin, Poland
c
Department of Materials Science, Faculty of Mechanical Engineering, Lublin University of Technology, Nadbystrzycka 36, 20-618 Lublin, Poland

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

Keywords: Though TiN coatings are considered a reliable anti-wear solution, the recent studies show that the anti-wear
Hard coating capacity of the TiN-coated metallic materials can be limited by various factors. Therefore, in our study, the CAE-
Dry friction PVD TiN film was deposited on two popular metallic materials: 316LVM stainless steel and Ti6Al4V alloy. The
Wear-resistant coating surface roughness, mechanical properties, adhesion as well as anti-wear performance in tribological pair with Ø6
Titanium nitride
mm WC-Co ball of both bare and surface modified specimens were evaluated. According to the findings, the
elastic modulus mismatch between the coating and the substrate is one of the key factors that determine the
operational durability of the TiN-coated alloys. Moreover, the well-established H/E and H3/E2 quotients should
be treated with caution when the wear performance of a coated material is assessed.

1. Introduction the newly developed products by using mathematical models to predict

Introduced to the global market in the 1970s, thin films based on
the transition metal nitrides are one of the first commercially applied
anti-wear coatings [1]. Their undiminished popularity results from the
exceptional properties of the nitride-based films: high hardness, che-
mical stability, good corrosion performance, high melting point and
good electrical conductivity [2]. To this day, one of the most popular
and the most easily available anti-wear films are the yellow-gold TiN
coatings, which were invented shortly after the TiC films [3]. The ti-
tanium nitride that crystallizes in the B1 system [2] is a versatile ma-
terial with nitrogen content varying from 37.5% to 50% [4]. Nowadays,
titanium nitride is used primarily as a coating material in order to ex-
tend the service life of cutting tools made of high speed steels or sin-
tered carbides. Moreover, compared to the non-modified cutting tools,
the use of titanium nitride films allows to increase the cutting speed and
feed during machining [5]. A combination of high hardness with good
plasticity and sufficient corrosion performance in physiological fluids
made the titanium nitride coatings the number one choice in wear-re-
lated medical applications, e.g. orthopaedic implants [6–9]. Moreover,
TiN can also be used in stamping tools [3], bearings [3] or simply as a
decorative material [3,10].
In the recent years, a tendency to accelerate the R&D processes of
the materials’ behaviour in the actual working conditions has been
emerging. For example, predicting the wear performance of the tribo-
logical pair while using the well-established relationships between the
mechanical properties of the substrate and the coating was proposed. As
it was shown in the literature, when the hardness H and elastic modulus
E of the coating are known, it is possible to determine its susceptibility
to elastic strain to failure, as expressed by the H/E quotient [11], as well
as its resistance to plastic deformation defined by the H3/E2 ratio [12].
In general, in most engineering applications, the higher are the H/E and
H3/E2 coefficients, the greater the wear resistance the coating should
represent [11,12]. As demonstrated in the research by Musil and Jirout
[13], the high value of H3/E2 coefficient is primarily attributed to
fracture toughness of the thin films.
Low elastic modulus of the coating is particularly advantageous
when it is possible to match it with the underlying substrate. A small
Young's modulus of the material facilitates distribution of stresses at the
interface between the coating and the substrate, thereby reducing the
coefficient of wear K [14], which is determined by the friction track
length and the volume of the worn material. However, adjusting stiff-
ness of the components is difficult to achieve when a hard ceramic
coating is used. It is believed that the Young's modulus of a typical anti-
wear coating is usually three to four times higher than E of the

⁎
Corresponding author.
E-mail address: m.lepicka@pb.edu.pl (M. Łępicka).

https://doi.org/10.1016/j.wear.2019.01.029
Received 23 October 2018; Received in revised form 6 January 2019; Accepted 7 January 2019
Available online 08 January 2019
0043-1648/ © 2019 Elsevier B.V. All rights reserved.
M. Łępicka et al.
substrate, e.g. steel [11]. For this reason, according to some researchers,
the parameter that more accurately describes wear resistance of the
surface-modified materials is the quotient Ecoating/Esubstrate. As shown in
the study conducted by Huang et al. [15] on the TiN- or TiAlN-coated
copper, high speed steel or tungsten carbide substrates, the greater is
the mismatch of Young's modulus between the substrate and the coating
(i.e. Ecoating/Esubstrate differs from 1), the greater is the observed wear.
Moreover, according to the authors [15], the value of Ecoating/Esubstrate
ratio remarkably influences friction coefficient (COF) of the tribological
pair. The WC-Co substrate, which is characterized by the highest load-
bearing capacity among tested substrates, exhibited the lowest COF for
both TiN and TiAlN coatings [15]. The influence of Ecoating/Esubstrate
coefficient on wear of hard ceramic coatings was examined also by
Avelar-Batista et al. [16]. Among the coatings: (Ti,Al)N, TiN and CrN
applied on AISI H13 steel, the greatest wear resistance was reported for
(Ti,Al)N coated steel due to the best match of Young's moduli between
the substrate and the coating (Ecoating/Esubstrate = 1.60).
TiN films are often used to enhance the wear capacity of two pop-
ular metallic materials: the corrosion resistant austenitic stainless steel
316L and the alpha-beta titanium alloy Ti6Al4V. In the literature there
are given multiple examples of successful surface modification of those
materials with the TiN films. In the wear tests conducted in dry sliding
conditions in the ball-on-disc configuration, where the counter-sample
was the WC-Co ball [17], compared to the non-coated material, the
wear resistance of the TiN-modified 316 L steel improved approxi-
mately 6.5-fold. According to Zhang et al. [18], the PVD deposited ti-
tanium nitride coatings improve the wear performance of 316L stainless
steel in the tribological pair with Si3N4 as well. Very enthusiastic re-
ports on the tribological performance of TiN coated 316L were pub-
lished also by Saravanan et al. [19] and Zuo et al. [20]. According to
Saravanan et al. [19], if the 316L austenitic stainless steel is coated with
TiN, under the load of 2 N compared to bare material its wear is re-
duced 6-fold, while under the load of 6 N wear of the tribological pair is
even 7 times smaller. Moreover, in comparison to the bare steel, after
titanium nitride deposition the average coefficient of friction (COF) is
reduced more than 7 times.
What is more, according to numerous reports, deposition of TiN
films on Ti6Al4V titanium alloy provides enhancement of its wear
performance as well. If the Ti6Al4V alloy is surface modified with PIII
(plasma immersion ion implantation) TiN, in tribological pair with SiC
not only substantial reduction of COF can be noticed, but the wear
performance of the frictional pair improves as well [21]. Moreover, the
results from the tribological study in which the CVD TiN was deposited
on the Ti6Al4V surface, are not less enthusiastic. According to the au-
thors [22], in the bovine serum lubricated conditions the TiN film
provides the best anti-wear performance among all tested coatings
(diamond-like-carbon, amorphous carbon and TiN). As presented in the
research paper by Wang et al. [22], in the tribological contact with
zirconia ball, after deposition of the DLC film wear of Ti alloy was re-
duced 2.5-fold, while after TiN deposition – it decreased 10-fold. Fur-
thermore, the study conducted by Varidaj and Kamaraj [23] showed
that the PVD TiN helps to improve the fretting wear performance of two
Ti-based alloys – Ti6Al4V and Ti6Al7Nb.
Nevertheless, though TiN is considered a versatile and a multi-
purpose coating, some cases of wear intensification of metallic sub-
strates after TiN deposition are also known. For example, though TiN
films are used in medical applications in order to enhance the tribolo-
gical performance of metallic materials, numerous examples of adverse
effect of the titanium nitride coatings on wear performance of implant
alloys have been reported. In the study conducted by Williams et al.
[24] two tribological pairs working in bovine serum lubricated condi-
tions were compared: (a) CoCrMo – CoCrMo and (b) TiN CoCrMo – TiN
CoCrMo. It was noticed that in case of TiN – TiN contact, the wear of
tribological pair was 4 times greater than that of the non-modified pair.
What is more, in the research by Fisher et al. [25] conducted on a hip
friction simulator, localized flaking and chipping of the TiN coating
69
Wear 422–423 (2019) 68–80
deposited on a hip implant head was reported. In the literature there
have also been given examples of localized flaking and, as a result,
increased surface roughness and wear of TiN coated implants made of
Ti6Al4V [26,27]. In addition, some cases of wear processes in-
tensification after deposition of TiN on other engineering metallic
materials are also known. When titanium nitride is deposited on TiAl
intermetallics [28], mild steels [29], low-alloy steels [30] or aluminium
1000 series [29], their wear performance strongly depends on the wear
test parameters, e.g. applied load.
Based on the provided literature review, it can be seen that the wear
performance of TiN-coated metallic alloys strongly depends both on the
substrate material and the friction conditions. Therefore, the aim of our
study was to experimentally test applicability of Hcoating/Ecoating,
Hcoating3/Ecoating2 as well as Ecoating/Esubstrate quotients in predicting wear
of TiN coated metallic substrates. For comparison purposes, two well-
known metallic materials which differ significantly in terms of their
mechanical properties – two-phase α + β Ti6Al4V titanium alloy and
316LVM austenitic stainless steel – were selected as the model materials
to be tribologically tested. In order to ensure impartial friction condi-
tions for both tested substrates, WC-Co sintered carbide was selected as
the counter material, as well as all friction tests were conducted in dry
conditions. As no electrolyte was used as a lubricant, we were able to
monitor also the durability of the examined film and to identify the
specific distance at which total failure of the coating was observed.
2. Experimental details
2.1. Materials
As noted in the Introduction section, TiN coating was deposited on
two metallic materials that differ significantly in terms of their me-
chanical properties: 316LVM stainless steel and Ti6Al4V titanium alloy.
Moreover, for the wear test purposes, ceramic balls made of WC-Co
were selected as the counter material.
In order to ensure uniformity of the films and repeatability of the
PVD process, the commercial anti-wear solution was selected for the
analysis purposes. This has been done to obtain credible analysis on the
impact of the mechanical properties of substrate and coating on wear
performance of the analysed film. Before the thin film deposition, the
substrates were carefully cleaned: degreased in an alkaline ultrasonic
bath, rinsed with de-ionized water, and dried using a vacuum drying
system. TiN coatings were deposited by the cathodic arc evaporation
(CAE-PVD) method from Ti target in an argon and nitrogen mixture.
Before deposition, the base pressure in the deposition chamber was
10−3 Pa. The process was conducted at a temperature of ca. 350 °C,
under a working pressure in the range from 0.1 to 0.2 Pa.
2.2. Film characterization
The roughness of both non-modified and TiN-coated specimens was
examined using the Hommel-Etamic T1000 (Jenoptic, Germany)
roughness meter. The measurements were taken in accordance to the
ISO 4288:2011 [31] standard. Each measurement was replicated 10
times for each type of a tested sample. The mechanical properties
(hardness, Young's modulus) of substrates and coating were studied
using the Ultra Nanoindentation Tester (CSM Instruments, Switzerland)
equipped with a Berkovich indenter (0.8 mN load). The hardness and
elastic modulus were calculated from the load-displacement (L-D)
curves according to the Oliver Pharr method [32]. The theoretical
Poisson ratio values used in calculations were as follows: (a) 316LVM:
0.30, (b) Ti6Al4V: 0.31, and (c) TiN: 0.20 [33]. The loading and un-
loading times were 150 s. In order to assess the tendency to creep of the
examined materials, hold time of the peak force was set to 5 s. In each
sample group, nanoindentation measurements were replicated 20
times. The adhesion of the coating to both substrate materials was ex-
amined using the Micro Scratch Tester (Anton Paar GmbH, Germany)
M. Łępicka et al.
Fig. 1. Schematic representation of the ball-on-disc wear test system.
according to the ASTM C1624–05(2015) [34] standard. In the scratch
testing, a diamond Rockwell C indenter (120° conical tip, 100 µm ra-
dius) was pulled over the surface of the TiN coated specimens with
normal load that was progressively increasing from 1 to 30 N. The
loading rate was 11.6 N/min and the stylus progressive speed was
2 mm/min, while the total scratch length was 5 mm. For each sample
group, scratch test was replicated 10 times. Optical (OM, MCT, Anton
Paar GmbH, Germany) and scanning electron (SEM, Phenom G2 Pro,
Phenom-World B.V., Holland) microscopy examination was carried out
for the coatings after each scratch testing in order to determine the
cracking pattern of the film and the critical cracking loads (Lc). The Lc1
load corresponded to the cohesive failure (occurrence of the first cracks
on the surface), Lc2 – the first symptoms of adhesive failure (spalling or
chipping), Lc3 – total exposure of the substrate material.
2.3. Wear test
The tribological test was conducted on a CSM Intruments
(Switzerland) microtribometer in a ball-on-disc configuration (Fig. 1).
The disc was working in a rotating mode, while the Ø6 mm WC-Co ball
was fixed. The sliding velocity was 10 cm/s and the diameter of the
wear track equalled 6 mm. Sliding conditions were selected with regard
to the information presented in the book “Coatings Tribology: Proper-
ties, Mechanisms, Techniques and Applications in Surface Engineering”
by Holmberg and Matthews [10]. Though AISI 52100 bearing steel is
often used as the counter-material in wear tests, in our preliminary
studies we observed severe adhesive wear in the tribological pair
bearing steel vs. Ti alloys. Therefore, selection of the WC-Co ball as the
counter-material resulted both from our own observations and litera-
ture review.
In wear tests, a total of 24 discs was used (6 discs per each group).
Therefore, 6 replications of tribological tests for each tested pair were
done. Prior to the tribological tests, all of the specimens were carefully
cleaned with acetone, isopropanol and dried. The test was conducted
under dry sliding conditions in room temperature (21 °C) and ambient
humidity. For all the samples, the normal load of 10 N was used. In
order to determine the resistance of the TiN coatings to being worn out,
the electrical resistance and coefficient of friction of the tribological
pair was controlled during the whole test. To detect all the subtle
changes in the registered signals, the frequency of data acquisition was
set to 10 Hz. After the wear tests, the morphology of the wear tracks
was assessed by SEM (Phenom G2 Pro and Phenom XL, Phenom-World
B.V., Holland) and the basic elemental analysis of the wear track was
done using the built-in EDS detector. The cross-section of the wear track
was measured by a contact profilometer (Veeco Instruments Inc., USA).
70
Wear 422–423 (2019) 68–80
The wear rate of the examined materials was calculated using the fol-
lowing formula:
V mm3
W= [ ]
PL Nm (1)
3
where V is the volumetric wear [mm ], P is the applied load [N] and L
is the total sliding distance [m].
2.4. Statistical analysis
For all the presented numerical data, a post-hoc two-tailed Student's
t-test was conducted assuming unequal variances between the analysed
groups (α = 0.05). Moreover, statistical power analysis (Pwr = 1-β,
where β is the probability of the type II error) of the collected data was
done using the free G*Power software [35]. The statistical power
threshold was set at 0.90. Therefore, the probability of rejecting the H0
hypothesis that the sample means are equal given that the statistically
significant difference was really there equalled 90%.
3. Results
3.1. Surface characterization
Fig. 2 presents results of the roughness measurements conducted on
both bare and TiN-modified samples. For each of the given parameters:
Ra, Rt, Rz, 10 measurements were taken, based on which the average
values and the standard deviations were calculated. According to the
presented data, for both 316LVM stainless steel and Ti6Al4V ELI im-
plant alloy a difference in surface roughness after TiN film deposition
can be seen. There is a statistically significant difference in Ra, Rt and
Rz parameters between the non-modified specimens and the TiN-coated
ones. In case of both 316LVM steel and Ti6Al4V ELI alloy, the greatest
difference between the bare and coated specimens can be seen for the
Rt parameter, which denotes the total height of the roughness profile –
that is, the difference in height between the highest peaks and the
deepest valleys within the evaluation length. The change in roughness
corresponds to change in surface morphology after TiN deposition.
According to the other authors, TiN coating obtained by the cathodic
arc evaporation method can have some surface defects which affect the
surface roughness of the material [36].
3.2. Coating thickness
In order to evaluate thickness of the TiN coating deposited on
316LVM stainless steel and Ti6Al4V ELI titanium alloy, metallo-
graphically prepared cross-sections of the surface modified samples
were used. Measurements were taken using the scanning electron mi-
croscope.
As it can be seen in Fig. 3, the analysed TiN coating was a mono-
layer of uniform thickness. According to data presented in Table 1,
there was no statistically significant difference in TiN thickness be-
tween the titanium alloy and the samples made of stainless steel.
3.3. Nanoindentation
Fig. 4 shows the load-displacement (L-D) curves obtained in the
nanoindentation tests. As it can be seen, during the pause of 5 s both
substrate materials exhibited tendency to creep, as the displacement of
the diamond indenter was growing under the constant maximum load.
On the other hand, the TiN coating presented no creep. It is a valuable
information e.g. for the self-locking screw joints designers, as the non-
rotational loosening effect of the screws is often caused by creep of the
mating materials [37]. As shown in Fig. 4, under the load of 0.8 mN the
maximum penetration depth for bare 316LVM stainless steel achieved
value of 55 nm.
To overcome problems associated with the small permanent indent
M. Łępicka et al. Wear 422–423 (2019) 68–80

Fig. 2. The surface roughness parameters measured for bare and TiN-modified 316LVM and Ti6Al4V, number of test replications n = 10.

the contact area A, the unloading stiffness S (S = dF/dh), the di-

mensionless parameter β which is a constant dependent on the indenter
geometry, and the reduced elastic modulus Er, as shown in Eq. (3):
2
S = β Er A
π (3)

The reduced elastic modulus Er is defined by (4):

1 1−ν 2 1−νi2
= −
Er E Ei (4)

When calculating reduced elastic modulus, the occurrence of elastic

displacements in both diamond indenter and the examined material is
taken into account. Therefore, the reduced elastic modulus is calculated
Fig. 3. Cross-section of the TiN-modified Ti6Al4V sample. based on the Poisson ratio ν and the sample elastic modulus E, as well as
on the Poisson ratio of the diamond indenter νi = 0.07 [32,38] and its
elastic modulus Ei = 1140 GPa [32,38].
Table 1
According to the results presented in Table 2, the nanohardness and
TiN coating thickness measurements (mean ± SD); number of
elastic modulus of the deposited TiN coatings are few times greater than
test replications n = 8.
those of bare alloys. Fig. 5 presents the results of the statistical analysis
TiN coating thickness [μm] conducted on the nanoindentation data collected for all considered
materials. According to the provided information, there is a statistically
316LVM stainless steel Ti6Al4V alloy
1.48 ± 0.03 1.46 ± 0.03 significant difference in hardness and elastic modulus between the non-
coated samples and their coated equivalents. What is more, no statis-
tically significant difference was observed between the TiN-coated
specimens. Due to that, it can be assumed that in the measurements that
we took, the effect of substrate on the measured mechanical properties
of the coating was negligible.
What is more, a statistically significant difference is observed also in
hardness and Young's modulus of both substrates – 316LVM stainless
steel and Ti6Al4V ELI titanium alloy (Fig. 5). According to the data
presented in Table 2, 316LVM steel is characterized by the higher
Young's modulus than Ti6Al4V ELI alloy. On the other hand, Ti6Al4V
alloy is harder than bare stainless steel. Nevertheless, findings obtained
in the hardness measurements should be interpreted with caution. In
contrary to the traditional hardness measurement techniques, e.g.
Vickers hardness measurements, where hardness of the material is
calculated i.a. from the dimensions of the permanent indent impression,
Fig. 4. The load–displacement curves of bare substrates and TiN coated spe- in the Oliver-Pharr nanohardness measurements, hardness of the ma-
cimens obtained in the nanoindentation measurements. terial is calculated based not only on the applied maximum normal load

Table 2
impression, in the nanoindentation measurements, hardness of the
The mechanical properties of tested materials determined in nanoindentation
material is calculated using the assumed contact area A. The contact tests (mean ± SD): Wtotal – total work done, Welastic – elastic work done, number
area A is calculated from the value hc, which is the contact depth with of test replications n = 20.
an indenter under the maximum load Fmax [32]. Thus, the hardness H is
Material H [GPa] E [GPa] Wtotal [pJ] Welastic [pJ]
calculated from the Eq. (2):
316LVM 7.5 ± 0.7 231.7 ± 21.4 20.9 ± 1.4 5.0 ± 0.4
Fmax
H= Ti6Al4V 9.6 ± 1.1 137.0 ± 13.5 21.0 ± 1.7 8.7 ± 0.7
A (hc ) (2) TiN 316LVM 27.4 ± 4.0 417.9 ± 65.0 8.8 ± 0.8 6.0 ± 0.3
TiN Ti6Al4V 27.0 ± 3.7 418.9 ± 66.6 9.0 ± 0.9 6.0 ± 0.8
According to Oliver and Pharr [32], there is a relationship between

71
M. Łępicka et al.
Fig. 5. Results from the t-Student (α = 0.05; number of test replications
n = 20) analysis done for the hardness and Young's modulus measurements: a)
hardness, b) elastic modulus. Inside the table cells the statistical power of the t-
test is given.
Fmax, but also on the hc value (contact depth with an indenter under the
maximum load) – in other words, elastic deformation of the material is
also taken into account. As a result, Ti6Al4V alloy, which is char-
acterized by a statistically significant higher rate of the elastic de-
formation than the stainless steel (Table 2), can also be characterized by
the higher hardness.
3.4. Adhesion strength
Adhesion strength of the TiN coating deposited on Ti6Al4V alloy
and 316LVM stainless steel was investigated using the micro-scratch
technique in the PLST (progressive loading) mode with Fmax = 30 N.
The critical normal loads (Lc) were determined while observing the
scratch channels by OM. SEM examinations of the scratch channels
were conducted as well in order to determine the main deformation
mechanisms of the coating that take place during the scratch testing.
The results obtained during the scratch test resemble findings pre-
sented in our previous paper, where the TiN-coated ground 316LVM
stainless steel was analysed [39]. For both types of TiN coated speci-
mens, four main cracking deformation regimes were registered. It
should be emphasized that though both substrates are characterized by
different mechanical properties, the differences between the critical
failure loads of the coating were noted, but the main deformation re-
gimes remained the same. The cohesive failure of the TiN coating
started from its parallel cracking (Fig. 6a). Immediately after the first
parallel cracks, the angular cracks appeared in the film (Fig. 6b). The
observed cracks were the actual response of the coated system to the
intensifying normal load – as the load was progressing, the parallel and
angular cracks were getting thicker and longer. In the meanwhile, in the
back of the moving diamond stylus, tensile stresses were intensifying.
As a result, third regime of deformation started – the ductile semi-cir-
cular through-thickness cracking (Fig. 6b). Though the failure area re-
mained localized and did not propagate beyond the scratch groove
(Fig. 6b), the number of the semi-circular cracks was growing rapidly as
soon as the first crack appeared. As it can be seen in Fig. 6b, formation
of the first semi-circular cracks leads to immediate adhesive failure of
the coating, which corresponds to the critical load Lc2. Spalling of the
coating is an effect of superimposition of the compressive stresses in
front of the intender which is pulled over the examined sample surface
and the tensile stresses that are generated in the rear of the stylus.
According to Kataria [40], spalling is caused by the cross-influence of
both cohesive and adhesive damaging action of the coating. As it can be
72
Wear 422–423 (2019) 68–80
Fig. 6. Cracking pattern (a–d) of the TiN-coated 316LVM steel.
seen in Fig. 6c, though at the beginning spalls are relatively small and
randomly distributed over the scratch channel, they have a tendency to
group in bigger agglomerates. As the normal load was increasing, de-
struction of the coating progressed, as evidenced by the extensive
growth of the spalling regions (Fig. 6d). With intensification of the
coating spalling process, the amount of hard debris originating from the
coating was growing, as shown in Fig. 6d. Some of the hard particles
were trapped between the indenter and the examined material surface,
causing ploughing of the material (Fig. 6d). In case of both 316LVM
steel and Ti6Al4V titanium alloy, ploughing damage led to total ex-
posure of the substrate and removal of the coating from the surface of
the metallic substrate.
Values of the critical loads registered during the scratch tests are
presented in Table 3. As it can be seen in Fig. 7, for the cohesive failure,
no statistically significant difference in Lc1 load was observed for both
types of the analysed samples. Nevertheless, a difference in the scratch
resistance of the TiN coated materials is observed for the Lc2 critical
load (Fig. 7). The resistance to adhesive failure (Lc2) of the TiN coating
was greater for the samples in which 316LVM stainless steel was used as
a substrate material. On the other hand, though in the t-test statistical
difference in the total failure of the coating (Lc3) was observed between
the TiN coated Ti6Al4V alloy and stainless steel, we failed to reject the
H0 hypothesis that the sample means are equal due to low statistical
power of the test (0.66). Therefore, it cannot be claimed that in scratch
testing the substrate material influences the resistance of the coating to
total failure.
3.5. Wear behaviour of bare and TiN coated materials
In this study, a CSM Instruments microtribometer was used to
evaluate the wear behaviour of TiN coated 316LVM stainless steel and
Ti6Al4V ELI titanium alloy. During the examinations, values of the
Table 3
Critical loads registered during the scratch testing: Lc1 – first symptoms of co-
hesive failure (angular or parallel cracking), Lc2 – beginning of adhesive failure
(buckling, chipping, spalling, etc.), Lc3 – total failure of the coating or massive
exposure of the substrate (mean ± SD), number of test replications n = 10.
Material Lc1 [N] Lc2 [N] Lc3 [N]
TiN 316LVM 2.3 ± 0.8 6.9 ± 1.5 17.1 ± 1.7
TiN Ti6Al4V 2.0 ± 0.7 4.6 ± 1.3 19.3 ± 2.1
M. Łępicka et al.
Fig. 7. Results from the t-Student (α = 0.05; number of test replications
n = 20) analysis done for the critical loads. Inside the cells the statistical power
of the t-test is given.
coefficient of friction and the contact resistance were registered at the
frequency of 10 Hz, whereas the volumetric wear of the examined
materials was assessed after the wear tests. For 316LVM stainless steel,
the aimed wear distance equalled 2500 m, what corresponds to 132,189
revolutions in the proposed ball-on-disc configuration. In wear tests of
the Ti6Al4V alloy, the distance of friction was reduced due to intensive
wear of the examined material that was revealed in the pilot study.
Therefore, for comparison purposes, the wear rate K was calculated
according to Eq. (1). In Eq. (1), the relationship between the volumetric
wear, normal force and total sliding distance is used.
Fig. 8 presents the fluctuations of the coefficient of friction (COF)
registered for both bare 316LVM stainless steel and Ti6Al4V titanium
alloy during 2500 m of friction. It can be noticed that in case of 316LVM
stainless steel, the COF value stabilizes at a high level after approxi-
mately 100 m of friction. The COF value is fluctuating, but its upper
limit is ca. 0.92. The observed fluctuations in COF might be caused by
the mixture of lubricating effect of the transfer layers, adhesive wear of
the substrate and its abrasive wear. Signs of abrasive wear (arrows),
which has been caused by the presence of high amounts of oxidized
wear debris in the friction zone, can be seen in Fig. 9. In the wear
channel abrasive grooves, agglomerates of the oxidized wear debris as
well as tribofilms that were spontaneously formed as a result of cross-
interaction between the substrate and the wear products, are present.
Compared to 316LVM steel, wear of bare Ti6Al4V alloy proceeded
differently. Despite the lower values of coefficient of friction (Fig. 8),
severe wear of the titanium alloy was registered. After achieving only
half of the planned friction distance, the width of the friction channel
reached 3.5 mm (Fig. 10a), while for the 316LVM steel the width of the
friction channel was 2 mm after 2500 m of friction. Due to that, in order
to avoid wear seizure of the tribological pair Ti alloy – WC-Co ball, the
total distance of friction was limited to 1250 m.
In case of Ti6Al4V alloy, radially arranged agglomerates of wear
debris are present in the wear track (Fig. 10a). Micrographs taken on
the worn surface (Fig. 10b) show that the main wear mechanism that
occurs during dry friciton in the tribological pair Ti gr. 5 disc vs. WC-Co
Fig. 8. COF values registered in dry conditions for bare substrate materials
under normal load of 10 N.
73
Wear 422–423 (2019) 68–80
ball is the adhesive wear. As a result of the applied normal load, as-
perities that were initially present at the surface of the examined
sample and the counter-specimen became plastically deformed and
soon after that – micro-welding of both materials took place. While
relative displacement between the ball and the disc was constantly
present, the micro-welds were subsequently fractured and delamination
of the softer material – in this case Ti alloy – occurred (Fig. 10d). During
constant friction, some of the wear products were removed from the
contact zone (Fig. 10c), but in most cases – wear debris rapidly oxidized
in the friction zone (Fig. 10b). As a result of formation of the oxide-rich
tribolayers, intermittent decrease in the fricitonal forces was observed
(Fig. 8). Nevertheless, in contact with the hard WC-Co ball, tribofilms
were rapidly damaged and subsequent exhibition of the bare substrate
material occurred. Again, high reactivity of bare Ti alloy led to adhesive
welding between the examined material and the counter-specimen,
which resulted in the subsequent fracture of the micro-welds. This wear
mechanism is reflected also in fluctuations of the coefficient of friction
(Fig. 8). The observed wear mechanism leads to catastrophic failure of
the examined material in a relatively short time.
Because the friction distance differed substantially between
316LVM stainless steel and Ti gr. 5 titanium alloy, linear wear of both
materials cannot be compared. Due to that, wear rate coefficient K (Eq.
(1), Section 2.3) was introduced. It turned out that the wear rate of bare
Ti6Al4V alloy was approximately 4 times greater for the non-modified
316LVM steel than for the Ti alloy.
Tribological examinations were conducted also for the samples that
were surface modified with the titanium nitride coating. The dynamics
of COF registered for bare and TiN coated 316LVM stainless steel are
presented in Fig. 11. For TiN coated steel, stable increase in COF values
from 0.6 to 0.7 in the first 700–800 m of the wear test is observed,
followed by its sudden decrease. After the first 1000 m of friction, dy-
namics of the µ fluctuations were similar to the ones observed for the
uncoated steel – changes in COF value were observed, but the average
value remained stable up to the end of observations. Attention is paid
particularly to the significant reduction in COF value after TiN coating
deposition – as presented in Fig. 12, the average COF value calculated
from the batch of the examined samples was approx. 25% lower than
for the bare steel.
The aforementioned reduction in coefficient of friction after approx.
800 m of friction (Fig. 11) can be the proof of the coating failure and the
substrate exposure. This fact is confirmed by the sudden change in
contact resistance of the tribological pair (examined material vs. WC-Co
ball – Fig. 13). After the coating failure, the reduced electrical re-
sistance is observed during few hundred revolutions due to subsequent
exposure of the metallic substrate. Then, short-time transients in the
contact resistance are registered. Rapid increase in contact resistance is
observed, which is immediately followed by its reduction. This phe-
nomenon corresponds to the natural passivation of the stainless steel in
ambient conditions, growth of oxygen-rich tribofilm in the contact area
of the wear track, its following failure and once more, exposure of the
bare substrate. This is reflected in rapid changes in COF values
(Fig. 13). At the same time, oxygen-rich tribofilms caused not only
increase in value of the contact resistance, but also decrease in friction
forces. Damage of the tribofilm promoted adhesion between the sub-
strate and the counter specimen, what resulted in rapid increase in COF
value accompanied by the reduction of the contact resistance.
Formation of the tribofilm in the contact zone between the TiN
coated 316LVM and WC-Co ball is confirmed also by the microscopic
observations (Fig. 14). The EDX analysis of the wear track proved the
high level of oxygen in the tribofilm – the atomic concentration of
oxygen was almost equal to the iron content (39.2% vs. 42.3%). What is
more, small amount of tungsten originating from the counter-specimen
has been also detected, mostly in the regions characterized by the
higher oxygen content. Despite that, wear of the counter-specimen was
negligible.
Nevertheless, it should be emphasized that though TiN coating was
M. Łępicka et al.
Fig. 9. SEM micrographs of wear track obtained for 316LVM after 2500 m of friction under the load of 10 N.
worn out from the substrate due to friction, the tribofilm that has been
formed maintained its protective function. In order to assess wear of the
analysed materials, wear tracks were analysed using the contact profi-
lometry technique. In the Fig. 15a wear tracks of the TiN-coated and
bare 316LVM obtained after 2500 m of friction are presented. Com-
pared to the non-coated steel substrate, worn profile registered for the
TiN coated 316LVM is much shallower. For bare steel, the depth of the
worn profile was approx. 180 µm, while for the titanium nitride mod-
ified steel – it equalled only 6 µm. For the TiN coated steel, furrows that
were caused by the abrasive wear of substrate due to presence of hard
particles of the coating in the contact zone are visible only in higher
magnifications (Fig. 15b).
Compared to the stainless steel, wear resistance of the TiN coating
deposited on a titanium substrate was significantly lower. In Fig. 16,
comparison in the operational durability of the TiN coating on both
substrates – stainless steel and titanium alloy, measured by the friction
distance or the revolutions number to the substrate exposure, has been
presented. There is a statistically significant difference in the opera-
tional durability of the TiN coating on both aforementioned substrates.
For TiN deposited on Ti6Al4V ELI, the mean friction distance to the
total substrate exposure is approx. 9 times lower than that of the
316LVM steel (Fig. 16).
Micrographs obtained after wear tests for TiN coated Ti6Al4V tita-
nium alloy after 263.7 m of friction are presented in Fig. 17. A complete
exposure of the substrate can be seen, as well as high amount of the
wear products agglomerated alongside the wear track is present. High
amount of wear products present even after a short wear distance is
caused by the natural tendency to oxidation of titanium and its alloys. A
naturally formed oxide passive layer is usually only few nanometers
thick [41,42] and comprises of TiO2 [41], Ti2O3 and TiO [43]. Since
titanium is characterized by the high reactivity with the oxygen-rich
environment, immediate oxidation of both bare substrate and the wear
debris occurs. The subsequent wear of the oxidized tribofilm is the
reason of presence of high amounts of the wear debris in the proximity
to the wear track.
Right by the edge of the wear track, numerous cracks of the hard
TiN coating are present (Fig. 17e). Due to displacement of the ball with
reference to the examined disc, various types of stresses are generated
in both coating and substrate. In the areas adjacent to the contact
surface, the rotary motion of the sample causes coating deformation
mechanisms well known from the scratch tests – cracking of the coating
due to the tensile stresses [39]. In the back of the counter-specimen,
tensile stresses that are parallel to the wear track are generated. On the
other hand, in front of the ball, at the interface between the examined
disc and the counter-specimen, bending stresses occur. Their presence
causes the co-occurrence of the tensile stresses perpendicular to the
wear track. As a result of stresses co-occurrence in the overlapping
74
Wear 422–423 (2019) 68–80
areas, cohesive cracking of the coating occurs. The inclination of the
cracks with respect to the wear track is dependent on the super-
imposition of those stresses.
On the worn surface, tribofilms as well as channels that were formed
as a result of ploughing are present. As presented in the work by Guo
et al. [44], brittle cracking of the film can induce cracking of the ductile
substrate as well at a considerably low strain level. Nevertheless, in our
study only cohesive cracking of the tribofilm took place, while the
substrate material remained undamaged. Ploughing wear was caused
by the wear debris that was trapped between the ball and the disc, as
shown in Fig. 17c. However, the most severe damage was done by the
agglomerates of the detached parts of a hard TiN coating (Fig. 17d). A
particle that originated from the titanium nitride coating with a dia-
meter of several micrometers can be seen e.g. in Fig. 17c. A similar wear
mechanism of TiN coated Ti6Al4V was presented also in the work by
Wan et al. [21].
However, it should be emphasized that the presence of the tribofilm
in the friction zone was beneficial not only for the 316LVM steel, but
also for the Ti6Al4V titanium alloy. Compared to bare titanium alloy,
TiN coated material is characterized by more than 2 times smaller wear
coefficient K (Fig. 18).
As presented in Fig. 18, compared to bare metallic materials, surface
modification with TiN of both 316LVM stainless steel and Ti6Al4V alloy
results in significant reduction of wear. Nevertheless, both substrate
materials undergo different wear mechanisms in dry sliding conditions.
As a result, wear coefficient of the bare Ti alloy is more than 4 times
greater than that of bare 316LVM steel.
4. Discussion
As presented in the study, no statistically significant difference was
observed in the mechanical properties of the TiN coating deposited on
two metallic materials – 316LVM stainless steel and Ti6Al4V alloy. Due
to that, it can be assumed that the quality of the TiN coating obtained
on both substrates was comparable. Nevertheless, though it might seem
that titanium nitride should be characterized by greater adhesion to the
Ti substrate due to similarity of the elemental composition of both
materials [45], and therefore – greater resistance to wear could be
expected, in tribological tests the TiN coated Ti alloy was outperformed
by the 316LVM stainless steel. Because of that, it can be assumed that
the wear performance and adhesion strength of the titanium nitride
coatings to the metallic alloys might greatly depend not only on the
surface topography and applied surface preparation routine, but also on
the mechanical and chemical properties of the substrate and the film
itself.
There have been numerous studies that focused on the relationship
between the mechanical properties of the substrate and the coating and
M. Łępicka et al.
Fig. 10. SEM micrographs of wear track obtained for Ti6Al4V alloy after 1250 m of friction under the load of 10 N.
the resulting wear performance. In numerous research papers, it has
been shown that the greater are the values of the Hcoating/Ecoating (strain
to failure) and the Hcoating3/Ecoating2 (plasticity index) ratios, the better
ought be the wear performance of the coating [11,12]. Nevertheless, as
shown in our study, the Hcoating/Ecoating and Hcoating3/Ecoating2 ratios fail
when the wear performance of one coating deposited on different
substrates is assessed. In our case, the values of both Hcoating/Ecoating and
Hcoating3/Ecoating2 ratios were the same for the coating deposited on two
different substrates, while the tribological performance of TiN differed
significantly. Moreover, in some papers it has been noticed that the
anti-wear capacity of the ceramic coatings depends not only on the
strain to failure ratio or the plasticity index pf the film, but on the
75
Wear 422–423 (2019) 68–80
mechanical properties of the substrate material as well. In the work by
Huang et al. [15], where the wear performance of TiN and TiAlN
coatings was discussed, it was stated that for a typical ceramic coating,
its wear performance increases with the increase of hardness end elastic
modulus of the substrate material. However, our findings show that for
the TiN-coated systems, this statement is not entirely true. In our re-
search, as in the paper by Huang et al. [15], the nanoindentation
technique was used to assess the mechanical properties of the substrate
and the coating. It is well-known that the results obtained in the na-
noindentation measurements depend on numerous intrinsic and ex-
trinsic factors, e.g. the applied load. However, it has to be noted that in
our case, as discussed in the Results section, the Ti alloy exhibited
M. Łępicka et al. Wear 422–423 (2019) 68–80

Fig. 11. COF values registered in dry conditions for bare and TiN-modified
316LVM stainless steel under normal load of 10 N.
Fig. 13. COF vs. contact resistance at the friction distance of 2500 m – TiN
316LVM.
higher hardness than the 316LVM steel, while the wear performance of
the TiN coated Ti6Al4V was more than two times lower than that of the
presented in Fig. 10. Similar findings were presented e.g. in the work by
TiN-modified 316LVM steel. This indicates that in dry sliding condi-
Cassar et al. [48]. However, after coating with TiN, the prevalent wear
tions, not only the mechanical properties of the substrate and coating
pattern in tribological pair with WC-Co changes from severe adhesive
should be taken into account, but the chemical reactivity of the coating
wear to a mixture of adhesive wear and ploughing, as presented in
material and the substrate as well.
Fig. 17. Ploughing wear of the substrate material is caused by the hard
In the work by Saravanan et al. [19], it was shown that the surface
particles of the damaged film that were entrapped in the WC-Co ball.
morphology of the wear track, as well as the tribological performance
Furthermore, apart from the earlier discussed Hcoating/Ecoating and
of TiN coated 316LVM steel depend on the friction conditions applied in
Hcoating3/Ecoating2 quotients, the elastic recovery of the coating Ie is also
the wear test. With the increase of the test load, the abrasive wear
recognized as a good indicator of the expected performance of the
mechanisms intensify. In our research, after 2500 m of dry friction the
coating under normal load [13]. While 1 – Ie = Ip, where Ip is the % of
316LVM substrate is covered in oxygen-rich tribofilm. According to
the plastic response in the total deformation of the coating, when the hc
Saravanan et al. [19], at greater distances of dry friction the tribofilm is
and hp values are known, using the relationship (5):
formed due to plastic deformation of the substrate material as well as
due to the temperature rise in the contact region. It is highly likely that hp
Ip = *100%
the oxidation of both 316LVM stainless steel and Ti6Al4V alloy was hc (5)
intensified by the temperature rise in the friction contact. This reveals
that in further analyses, temperature measurements in the contact re- it is possible to determine the percentage share of the plastic de-
formation in the total deformation of the tested material. As it might be
gion should also be considered.
Moreover, as suggested by the other authors, selection of the expected, for hard ceramic coatings, the Ip increases as the plasticity
index decreases [13]. According to Musil and Jirout [13], an increased
counter-sample material also greatly influences the main wear patterns
observed in the tribological pair. For example, as presented in Fig. 9, tendency to crack under normal load is typical for coatings character-
ized by the Ip ≥ 50%. In our case, the Ip value was 56.6%. This might
the prevalent wear mechanism observed in the tribological pair con-
sisting of WC-Co – bare 316LVM stainless steel was the mixture of ad- explain the low resistance to cohesive cracking (Lc1 load) of the coating
registered during the scratch tests (Table 3) and therefore, high sus-
hesive and abrasive wear. Those results are in agreement with the
works by Dong et al. [46], Kayali [17] and Kayali et al. [47]. Moreover, ceptibility to brittle cracking of the film.
Moreover, according to our results, in scratch tests there was no
after coating stainless steel with TiN the wear pattern remained the
same – a co-occurrence of both adhesive and abrasive wear was ob- statistically significant difference in the Lc1 value for the TiN coating
deposited on both substrates (Fig. 7). Due to that, it can be assumed that
served (Figs. 14 and 15). Nevertheless, though the wear mechanism
didn’t change substantially, TiN film enhanced overall wear perfor- the resistance to cohesive cracking of a thin film depends mainly on the
intrinsic properties of the coating, while the mechanical properties of
mance of the coated steel (Fig. 18). On the other hand, in contact with
WC-Co, Ti6Al4V alloy undergoes severe adhesive wear, as it was the substrate material are negligible. The influence of intrinsic prop-
erties of the TiN films on their fracture toughness was thoroughly

Fig. 12. The average COF values registered during the wear studies, number of test replications n = 6.

76
M. Łępicka et al.
Fig. 14. SEM micrographs of wear track obtained for TiN coated 316LVM steel after 2500 m of friction under the load of 10 N.
Fig. 15. Cross-sections of worn profiles for bare and TiN modified 316LVM
stainless steel.
Fig. 16. Operational durability of the TiN coatings deposited on 316LVM
stainless steel and Ti6Al4V titanium alloy; number of test replications n = 6.
discussed in the work by Zhang et al. [49]. As stated by the authors, the
residual stress level of the film and its resulting mechanical properties
are strongly influenced by the coating thickness. In our case, no sta-
tistically significant difference in coating thickness deposited on two
substrates was observed. Nevertheless, as presented by Zhang et al.
77
Wear 422–423 (2019) 68–80
[49], the greatest influence of TiN film thickness on the residual stress
levels is observed if the coating is thinner than 1 µm due to the “atomic
shot peening” effect which occurs at the beginning of PVD deposition
processes. Therefore, further work in establishing the effect of the re-
sidual stress levels of the thin films and their resulting anti-wear per-
formance is advised.
Furthermore, in scratch tests, a statistically significant difference
between both coated substrates was observed for the Lc2 (adhesive
failure) critical load. An interesting relationship between the Lc2 value
and the wear performance of both coated systems was noticed – the
greater the resistance to adhesive cracking (Lc2) of the coating assessed
by the scratch test, the better its wear resistance in dry sliding condi-
tions. However, one should remember that the tests were done on a
small sample (2 types of the substrate materials) and therefore, no r-
Pearson correlation coefficient can be calculated. For this reason, it
could be interesting to repeat the research using a greater number of
tested substrate materials and to determine the correlation coefficient
between the Lc2 value measured in the scratch tests and the wear re-
sistance of the TiN coated systems.
In the recent years, some interesting improvements of the CAE-PVD
TiN deposition method have been proposed by the other authors. For
example, an extensive work on the relationship between the deposition
parameters and the properties of CAE-PVD TiN films has been presented
in the works by Sobol et al. [50,51]. Moreover, TiN-rich films can be
obtained on titanium alloys by the plasma nitriding methods [52].
Nevertheless, in our study, in order to ensure repeatability of the de-
position process with regard to the aim of the research, a well-estab-
lished commercial TiN film that has been extensively used for many
years in various industrial applications has been selected for the ana-
lysis purposes. Therefore, one should be aware of the limitations of our
work that are set by the presented approach. Despite this, our example
indicates that though in many cases assessment of the anti-wear prop-
erties of the coatings using the mechanical properties of the substrate
and the thin film might provide good results, it should always be treated
with caution. If, like in our case, the coating is being worn out during
the test and the intensity of wear is determined by the physicochemical
properties of the examined materials, e.g. their susceptibility to interact
with ambient air, segregation of the wear products or the intermittent
lubricating effect of the wear debris, the discussed coefficients should
not be treated as the main determinants of the anti-wear performance of
the coated systems [53].
5. Conclusions
In this study, titanium nitride coatings were deposited on two model
metallic materials: 316LVM stainless steel and Ti6Al4V titanium alloy.
M. Łępicka et al. Wear 422–423 (2019) 68–80

Fig. 17. OM (a) and SEM (b)–(e) micrographs of wear track obtained for TiN coated Ti6Al4V alloy after 263.7 m of friction in dry conditions.

Fig. 18. Wear rates K of the examined materials, number of test replications n = 6.

78
M. Łępicka et al.
The surface roughness, mechanical properties, adhesion as well as anti-
wear performance in tribological pair with WC-Co ball of both bare and
surface modified specimens were evaluated. Under the given set of data
obtained in tribological tests conducted in ball-on-disc sliding condi-
tions against a WC-Co ball, the following conclusions on the effect of
metallic substrates on the tribological performance of TiN coatings can
be drawn:
1. The anti-wear performance of CAE-PVD deposited TiN coatings
highly depends on the mechanical properties of the underlying
substrate material. As presented in the study, it seems that the
elastic modulus mismatch between the substrate material and the
coating is one of the most important factors that determine the tri-
bological performance of titanium nitride films. Moreover, it has
been shown that though it is meaningful to assess the mechanical
properties of both substrate and coating while examining wear,
many other factors, e.g. chemical reactivity of the tested materials,
should also be taken into account.
2. Though in case of both substrate materials, 316LVM stainless steel
and Ti6Al4V titanium alloy, the TiN coating was worn out during
the wear test, the tribofilms that were formed on the surface of the
substrate maintained their protective function – for both substrate
materials, an improvement in wear coefficient K was observed.
Moreover, even if the coating was worn out during the tribological
test, the coefficient of friction remained reduced until the end of the
measurement. Therefore, it can be stated that the tribofilms that
were formed during dry friction reduced the friction forces in the
tested systems.
3. In wear tests conducted in dry conditions, a particular attention
should be paid to the chemical reactivity the coating and the sub-
strate material. As provided in the findings, if the titanium nitride
coating is being worn out from the substrate surface during the wear
test conducted in ambient conditions, the oxidation processes of the
wear debris and the wear track take place. Though some of the
oxide-rich transfer layers promote the anti-wear capacity of the
metallic alloys, if those are worn out, in case of 316LVM stainless
steel the abrasive wear is dominant, while for the Ti6Al4V alloy –
the adhesive wear takes place.
Acknowledgements
The work was supported by the National Science Centre
(Poland) within the PRELUDIUM 13 grant proposal, project no. UMO-
2017/25/N/ST8/02270.
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