Characterization of TiN coating deposited by cathodic

arc evaporation under various process parameter

conditions

Arti Sahu1, Sudarsan Ghosh1, Sivanandam Aravindan1

1
Indian Institute of Technology, Delhi
110016, India
1
artisahu311aug@gmail.com

Abstract. In this study, the deposition of TiN coating was done on Ti-6Al-4V
alloy substrates by using the cathodic arc evaporation technique under varying
process parameters conditions to improve Ti alloy's surface properties (hardness
and wear resistance). The aim was to investigate the effect of various process
parameters on the microstructure and mechanical properties of TiN coating. The
Coating morphology, phases, and chemical composition were examined by field
emission scanning electron microscopy (FESEM), X-ray diffraction (XRD),
and energy dispersive X-ray spectroscopy (EDX), respectively. Nano hardness
of the coating was investigated with the diamond Berkovich indenter using the
Oliver and Pharr method. Moreover, the surface roughness of the coatings was
measured by SPM images in a Nano-indentation hardness tester. The coefficient
of friction (COF) of the coated surface was examined by a reciprocating ball on
plate wear test using an alumina ball as the counter surface. Coating deposited
at higher bias voltage and temperature (80 V and 350°C) shows high hardness,
good surface finish, and low COF as compared to the coating deposited at lower
bias voltage and temperature (0 V and 150°C)

Keywords: Cathodic Arc Evaporation, Titanium Nitride, Ti-6Al-4V alloy,

Nano-hardness, COF.

1 Introduction

Ti-6Al-4V (grade 5) is the most versatile and widely used Ti alloy in several indus-
tries such as aerospace, automobile, chemical, and biomedical industries as it attrib-
utes the combination of favorable properties i.e. high strength-to-weight ratio, high
corrosion resistance, low density, lightweight, and good biocompatibility and biologi-
cal neutrality [1]. Due to its excellent corrosion resistance properties, the Ti-6Al-4V
alloy is the ideal material for use in vessels, tanks, and piping systems across various
chemical processing industries [2]. However, Ti-6Al-4V alloy has poor tribological
characteristics and low hardness which leads to severe abrasive wear, adhesive wear,
high friction coefficient, and seizure; hence, it is restricted in wear resistance applica-
tions [3]. Although the Ti-6Al-4V alloy exhibits favorable corrosion resistance char-
acteristics, it is susceptible to corrosion and erosion when exposed to adverse condi-
2

tions [4]. Primarily, the wear characteristics depend on the surface layer instead of the
bulk material. Therefore, several surface treatments and modifications have been
conducted to improve the tribological performance of Ti alloy while without any sur-
face modification it is nearly impossible to use Ti alloy in wear resistance application.
For a long time, various research groups have utilized different surface modification
techniques to improve the surface properties of Ti-6Al-4V alloy, expanding its poten-
tial applications [5]. Hard ceramic coating deposition has been considered as an effi-
cient way to enhance the surface properties of Ti alloy.
Thus, transition metal nitrides (TMNs) are the best-suited candidates as they pos-
sess refractory nature with exceptionally high hardness [6]. Among hard protective
coatings, TiN is the most widely used due to its superior hardness and wear (abrasive
wear and adhesive wear) resistance, high-temperature oxidation and corrosion re-
sistance, and exquisite erosion resistance properties [7, 8]. The Cathodic arc evapora-
tion technique is also a widely used Physical vapor deposition (PVD) technique in
which an electric arc is used to evaporate the target material; it provides high deposi-
tion rate with excellent adhesion, and it is mostly used as hard, wear-resistance coat-
ing for mechanical application [9].
Despite a lot of work that has been done on TiN coating’s fabrication and charac-
terization, it is still required to examine the effect of the different set of process pa-
rameters i.e. low (10 min, 0 V, 150°C), medium (20 min, 50 V, 250°C) and high (30
min, 80 V, 350°C) on TiN coatings quality which were fabricated by cathodic arc
evaporation technique. This study investigates the positive and negative effects of
changing certain process parameters in cathodic arc deposition of TiN coatings by
characterizing them using various standard techniques.

2 Materials and methodology

For TiN coating deposition, firstly, Ti-6Al-4V alloy (90 wt% Ti + 6 wt% Al + 4 wt%
V + 0.25 wt% (max) Fe) substrates were prepared by cutting samples of dimensions,
10×10×2 mm using the wire EDM. Subsequently, the samples underwent grinding
using SiC papers ranging from grit 320 to 2000, followed by fine polishing using a
2μm diameter alumina paste to achieve a mirror-like surface finish. Afterwards, sub-
strates were cleaned in ultrasonic bath using acetone, isopropyl alcohol (IP) and de-
ionized (DI) water respectively, for 15 minutes each to remove any organic com-
pounds and thin oxide layer. Following this, the samples were dried using hot air to
eliminate any remaining moisture.
After preparing the substrate, TiN coatings were grown on Ti alloy substrates by
using cathodic arc deposition method in the Hind High Vaccum (HHV) PVD dual-
chamber setup. Samples were loaded in the chamber by maintaining the target sub-
strate distance of 15 cm. Therein, high vacuum was created to the pressure of 5×10-6
mbar which is called base pressure. Thereafter, the Argon and Nitrogen gases were
introduced into the chamber at 60 sccm and 45 sccm, respectively. By varying process
parameters, i.e., deposition time, temperature and bias voltage, three coatings were
prepared named as C1, C2 and C3 at constant catode current (85A). The details of
process parameters used for the coating deposition are mentioned in Table 1.
 3

The comprehensive characterization of all three coatings was done by examining the
coating morphology, phases, and chemical composition using field emission scanning
electron microscopy and energy dispersive X-ray spectroscopy (EDX) using a Jeol
JSM7800F Prime Field Emission Scanning Electron Microscope (FESEM) and X-ray
diffraction (Model: Ultima IV, Rigaku at 30 kV, 20 mA with CuKα radiation), respec-
tively. A commercially available Nano-indenter (INDUSTRON NANOGURU
NG50), which can also capture image of the surface using scanning probe microsco-
py, was used for hardness test of the coatings. Nano hardness and young’s modulus of
the coatings were determined by load displacement curve (P-h curve) using Oliver-
Pharr method. Surface roughness of the coatings was measured by SPM images taken,
in a Nanoindentation hardness tester. The coefficient of friction (COF) of coating
surface was examined by a reciprocating ball on plate wear test using Rtech-Multi
Function Tribometer. An alumina ball of 6 mm diameter was used as the counter-
surface with 5 N load and 1 mm/s sliding speed.

Table 1. Detail of various process parameters conditions.

Parameters C1 C2 C3
Substrate Temperature (°C) 150 250 350
Bias Voltage (V) 0 50 80
Deposition Time (min) 10 20 30

3 Results and discussion

X-ray diffraction analysis of the TiN coating was done using the grazing incidence
angle technique to reduce the substrate peaks in the XRD pattern.

Fig. 1. XRD pattern of C1, C2 and C3 coating compared with JCPDS file No. 00-038-1420.
4

XRD pattern of the all three coatings and their comparison with the TiN JCPDS file
are shown in Fig. 1. It is observed that most of the TiN peaks matched with
JCPDS/ICDD No. 00-038-1420 and coatings have fcc crystal structure with preferen-
tial growth of crystal plane TiN [200] and TiN [111], which is evident the most de-
sired TiN coating structure.

C1 micro and nano droplets

959 nm
pits
porous with
open columnar
structure

(a) (d)

C2 micro-droplets

1.35μm

porous struc-
ture

(b) (e)

C3

2.48μm
micro droplets

dense structure

(c) (f)
Fig. 2. FESEM images of the cross-section of C1, C2 and C3 coatings are represented as (a),
(b) and (c) respectively and FESEM images of the top surface of the C1, C2 and C3 coatings
are represented as (d), (e) and (f) respectively.
 5

At higher substrate temperature the nucleation and growth condition of coating

changes, which causes growth in the crystalline nature of the coating hence XRD
patterns of C2, C3 coatings exhibit TiN peaks of higher intensities as compared to C1
coating. Moreover, the preferred orientation of the coatings mainly depends on pro-
cess parameters; hence, the XRD pattern of C2 and C3 coating shows the predomi-
nant orientation [200] due to used high negative bias voltage [10].
FESEM images of the cross-section of TiN coatings are shown in fig. 2. These mi-
crographs unveil that TiN coating at low temperature (150°C) and 0 V bias voltage
has the porous and open columnar structure. Whereas, with increased temperature and
bias voltage (350°C and 80 V), the porous and columnar structure transformed into
dense structure with fewer defects. FESEM images of the cross-section of the coat-
ings show that they do not have any delamination and cracks at the interface, which
confirms adequate adhesion between coating and substrate. Fig. 2 (d), (e) and (f)
show the FESEM images of the surface morphology of the coatings C1, C2 and C3
respectively. It is observed that a large number of micro and nano-size droplets over
the coated surface are visible, which is due to the deposition of micro particles of
target material which is considered the major drawbacks of the cathodic arc evapora-
tion technique [11]. These micrographs also reveal that TiN coating deposited at low
bias voltage and temperature has more surface defects (pin holes. microdroplets, and
non-uniformity) than a coating deposited at high bias voltage and temperature. Coat-
ing thickness was measured approximately in the range of 1-2.5 μm shown in fig. 2
(a), (b) and (c). It is observed that coating thickness mainly depends on deposition
time; it increases with deposition time, and the highest coating thickness was attained
in 30 minutes of deposition time i.e. 2.48 μm.

Fig. 3. Atomic concentration (at %) of Titanium and Nitrogen elements for C1, C2 and C3
coatings.

The coating composition was investigated by EDX analysis and it is revealed that all
the three TiN coatings have atomic stoichiometry with atomic concentration % of N 2
6

in the range of 49.95%–54.24% (7.2 - 7.9 % error). Fig. 3 illustrates the atomic con-
centration (at %) of titanium and nitrogen elements w.r.t to all the three coatings C1,
C2 and C3 with their respective % error.

(a) (b)

Fig. 4. (a) Hardness (H) and reduced elastic modulus (ER) of C1, C2 and C3 coatings (b) The
p-h curve of all four hardness measurements of coating C3.

Hardness test was done in the Nano indentation hardness tester with a diamond
Berkovich indenter of 200 nm radius. The depth of indentation was taken 100 nm as it
should be less than or equal to 1/10 th of the coating thickness to avoid the substrate
effect. Multiple indentations were made on various areas of the coated surface in or-
der to prevent the hardness measurement errors. The p-h curves of all measurements
done on coating C3 are shown in Fig. 5, where the maximum indentation load was
around 8 mN at 100 nm indentation depth. The coating's average Nano-hardness is in
the range of 19 HV to 25 HV, which increases with substrate bias voltage and coating
thickness. Maximum hardness and reduced elastic modulus are 24 HV and 374 HV
respectively. Variation in hardness and young’s modulus w.r.t. coating C1, C2 and C3
are represented in Fig. 4. C3 coating shows the sudden increase of elastic modulus
value, which causes the increment in hardness of the coating. Average surface rough-
ness (Ra) was determined from SPM images which are in the range of 65-102 nm,
which is similar to reported values by ref. [13]. Coating with more defects showed
higher average surface roughness
The wear test results are influenced by the hardness and surface quality of the
coating. Maximum COF of the coating was found 0.34 (for C1 coating) because of
more surface defects, whereas C3 coating exhibits the less COF (0.29) because of
smooth surface with minimum defects. Variation in the average surface roughness
(Ra) and COF w.r.t. coating C1, C2 and C3 is shown in Fig. 5. From the graph it is
observed that C2 coating has less COF as compared to C3 coatings. Although C2
coatings exhibit higher surface roughness compared to C3 coatings, they demonstrate
lower wear and a reduced coefficient of friction (COF). This could be attributed to the
fact that C2 coatings possess lower hardness than C3 coatings, leading to reduced
abrasive wear.
 7

Fig. 5. Average surface roughness (Ra) and coefficient of friction (COF) of C1, C2 and C3
coatings.

4 Conclusions

From the comprehensive characterization of TiN coatings C1, C2 and C3 deposited at

different sets of process parameter conditions, i.e. low (10 min, 0 V, 150°C), medium
(20 min, 50 V, 250°C) and high (30 min, 80 V, 350°C) following conclusions can be
made. XRD pattern shows the preferred orientation [200] for the coatings (C2 and
C3) deposited at higher negative bias voltage. Depending on the deposition time,
coating thickness varied from 1 to 2.5 μm. TiN coating (C3) deposited at high tem-
perature and bias voltage has fewer defects (micro droplets and pits) as compared to
C2 and C3; therefore, it has the highest hardness (24 GPa) among all of the three coat-
ings. Also, FESEM micrographs of cross-sections of the coatings show that coatings
exhibit open columnar structure at low temperatures (150°C) and zero voltage,
whereas dense structures are seen at higher temperatures (350°C) and bias voltages
(80 V). The coating’s average nano-hardness is in the range of 19 HV to 24 HV,
which increases with substrate bias voltage and coating thickness. Coating with more
defects shows higher average surface roughness.

Acknowledgements

I would like to thanks Ms. Priyanka Saini for assisting me in Nano-indentation hard-
ness test and the Central research facility (CRF) and Nano research facility (NRF) of
IIT Delhi for providing characterization facilities.
8

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