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Tribology International 50 (2012) 16–25

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Tribology International
journal homepage: www.elsevier.com/locate/triboint

Adhesion and wear studies of magnetron sputtered NbN films


a,n a b
Kulwant Singh , N. Krishnamurthy , A.K. Suri
a FRMS, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India
b Materials Group, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India

article info abstract

Article history:
NbN films were deposited on MS, SS and HSS substrates by reactive DC magnetron sputtering. Effects of N 2 flow and
Received 2 May 2011
substrate biasing were studied on the deposition rate, crystal structure, surface hardness, adhesion and tribology. Scratch test
Received in revised form
was carried out for adhesion evaluation. Online recording of friction, depth of indentation and acoustic emission was carried
12 December 2011
out. Critical loads for cohesive and adhesive failures were observed. Tribological evaluation was performed on wear and
Accepted 29 December 2011
friction machine with reciprocating ball-on-plate configuration at 3and 6 N loads and at 5 and 15 Hz frequencies against hard
Available online 10 January 2012
chrome steel balls of 12.7 mm diameter. Coatings deposited at N 2/Ar flow ratio of 0.20–0.30 and at substrate bias voltage of
Keywords: 50 to 75 V showed higher hardness, better adhesion and low coefficient of friction.
Coating
Adhesion
Friction
& 2012 Elsevier Ltd. All rights reserved.
Wear

1. Introduction reported data on hardness, wear resistance, crystal structure etc. for sputtered
NbN and Nb2N thin films. Zhitomirsky et al. [21] prepared NbN coatings
Magnetron Sputtering, a physical vapor deposition technique, is widely using vacuum arc deposition and reported that the chemical composition and
used for deposition of compound coatings [1, 2]. Niobium nitride (NbN) films mechanical properties were affected by the nitrogen pressure and NbN
in the initial years were investigated more because of their superconducting coatings exhibit high scratch load and high microhardness.
properties rather than their mechanical properties. Early research towards
synthesis of NbN films was directed to increase their superconducting transi- NbN films can be used as wear resistant coatings due to its high hardness
tion temperatures [3, 4]. However, NbN films are attractive in wear and good wear resistance. NbN is considered to be suitable for applications in
applications too because of their good thermal expansion match with widely microelectronics and sensors, and in micromechanics and superconducting
used tool steels. Good mechanical properties coupled with chemical inertness, electronics. Due to their high critical current density, good mechanical
wear resistance, high melting point, temperature stability and high electrical properties and transition temperature between 16 and 17 K, NbN films could
conductivity make NbN films a suitable material for protective coating [5], be successfully used in several superconducting microelectronics
field emission cathode [6] and diffusion barrier in microelectronic devices [7]. applications.
NbN thin films have been prepared by various deposition techniques
including reactive magnetron sputtering [8–10], ion beam assisted deposition In the present study, NbN coatings have been studied on various steel
[11], pulsed laser deposition substrates. NbN films were deposited on mild steel (MS), stainless steel (SS)
and high speed steel (HSS) substrates by reactive DC magnetron sputtering at
various nitrogen (N2) flow rates and substrate biasing. Effect of N 2 flow and
[12] and cathodic arc deposition [13, 14]. After the introduction of substrate biasing was studied on deposition rate, crystal structure, surface
superlattice coatings, NbN was used as one layer component. Superlattice hard-ness, scratch adhesion and tribological aspects.
coatings such as TiN/NbN [15], TaN/NbN [16] and CrN/NbN [17] have been
investigated for use as hard, wear resistant and corrosion protective coatings.
All of these super-lattice films possess super-hardness effects, which exhibit 2. Experimental procedure
an anomalous increase in their hardness and wear resistance. However, there
is, only limited information on the tribological behavior of single-layer NbN
NbN films were deposited using a reactive DC magnetron sputtering on
coatings [18–20]. Singer et al. [18]
MS, SS and HSS substrates. A niobium (99.9% min purity) metallic target
160 mm diameter and 4 mm thick was mechanically clamped to a planar
sputter source mounted hor-izontally on the base of the chamber. The
6
n
Corresponding author. Tel.: þ91 22 25595378; fax : þ91 22 25505151 chamber was evacuated to a base pressure of 2 10 mbar. The distance
E-mail address: singhkw@barc.gov.in (K. Singh). between the
0301-679X/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.triboint.2011.12.023
K. Singh et al. / Tribology International 50 (2012) 16–25 17

target and the substrate was fixed at 60 mm. The sputtering pressure was kept Table 1
3 Wear Test Parameters.
at 5 10 mbar by admitting a stream of mixed gas of argon (Ar) and N 2 into
the chamber. Flow of Ar gas was fixed at 20 sccm while N 2 flow was varied Ball material AISI 52100 (Hardness RC 60)
from 0–14 sccm. Substrate biasing was kept constant at 50 V for coatings Substrate material Austenitic Stainless steel 304
Normal load 3N&6N
deposited at different nitrogen flow ratios. The power to the target was
Reciprocating freq. 5 Hz & 15 Hz
supplied through a stabilized d. c. power supply of 0–1000 V (maximum
Amplitude 1 mm
current value: 6 A). Substrate biasing was varied from 0 to 150 V in a step of Sliding Speed 10 mm/sec and 30 mm/sec
25 V, keeping the N2/Ar flow ratio constant at 0.20. Biasing was applied by Test duration 10 min & 30 min
means of a stabilized d. c. power supply of variable voltage (0–300 V) and Sliding distance 6.0 mtr to 54.0 mtr
current (0–500 mA). The rectangular samples of size 40 25 mm and 3 mm in Environment Dry Air
thickness were polished, cleaned thoroughly and degreased in alkaline
solution ultrasonically prior to the deposition.

20
Variation in nitrogen flow and substrate bias voltage was selected on the
basis of abundant literature available for the deposition of hard nitride 18
coatings. Most of the useful variation in the properties of various nitride

(nm/min)
coatings has been found to lie within a range of deposition parameters. To 16
No Biasing
keep the thickness of the coatings constant (for comparative evaluation of the

rate
14 -50V Biasing
coat-ings), deposition time was varied in such a way that the coating thickness
remains within 710%.

nDepositio
12
After deposition of coatings on samples, mass modifications were 10
evaluated. Thickness of the coatings was calculated by mass modification,
using the bulk density value. Actual coating thick-nesses were found out by 8
micro-abrasion (Ball-cratering techni-que) using a CSM Calotest instrument
by rotating AISI 52100 hard chrome steel ball against coated specimen using 6
suspension of diamond particles. The crystal structure of the films was
investi-gated by X-ray diffraction (XRD) using CuK a radiation. Surface
hardness was measured by a microhardness tester (Future Tech FM-7 model)
using Knoop indenter at a load of 25 gf. Five readings were performed for 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
each of the sample and the average values have been reported. Adhesion was N2/Ar
evaluated by a scratch tester (CSEM, Revetest). Critical loads for cohesive
(nm/min)

16
and adhesive failure for coatings on different substrates were observed. The
effect of N2 flow and substrate biasing on critical loads was investigated. N2/Ar = 0.20
Loading rates of 10 N/min, 30 N/min 50 N/min and 80 N/min were employed 14
on some of the samples to study the effect of loading rate on critical loads.
Loading rate did not give much impact on the variation in critical loads. To 12
study the effects of deposition parameters on Nb-N films during scratch tests,
a constant loading rate of 10 N/min and a constant scratching speed of 1.03
rate

mm/min was employed for all the tests. The scratch length was also kept 8
constant at 4 mm. The scratch indenter used was a
Deposition

10
6

200 mm tip radius Rockwell type diamond indenter. Friction force, depth of
indentation and acoustic emission signals for all the scratched samples were
recorded online. The scratch tracks were visualized in the optical microscopy
immediately after the tests to visualize the scratch patterns and pictures were taken 0 50 100 150
at different loads. The starting load in each test was 1 N while maximum load was
Substrate Biasing (-V)
varied from 10 N to 60 N. Tests were performed in a linearly progressive mode
from 1 N start load to a predefined maximum load. Fig. 1. Variation in deposition rate of Nb-N coating with (a) N 2/Ar flow ratio (Ar flow was fixed
at 20 sccm) and (b) substrate biasing (N2/Ar¼0.20).

Tribological evaluation was performed in a Plint make (TE-70) wear and


friction machine with reciprocating ball-on-plate con-figuration. Coated 3. Results and discussion
samples were tested at 3 N and 6 N loads and at 5 and 15 Hz frequencies
against hard chrome steel balls (AISI 52100) of 12.7 mm diameter at room 3.1. Thickness
temperature. 5 and 15 Hz frequencies correspond to the sliding speeds of 10
and 30 mm/s, respectively. Two different durations of 10 and 30 minutes were It was intended to get the same coating thickness but, using different bias
selected for the wear tests. Wear test parameters are listed in Table 1. voltage values or different nitrogen flow values to see changes in the coating
Coefficient of friction and wear rate were studied with properties. Therefore, duration of coating deposition was varied to get
approximately same coating thickness. In the deposition using biasing there
respect to load and sliding speed for coatings deposited at various N2/Ar flow was a continuous ion bombardment at the substrate, causing the reduced
ratios. effective
18 K. Singh et al. / Tribology International 50 (2012) 16–25

deposition rate, which in turn reduced the coating thickness and therefore ion-bombardment at the substrate with higher energy ions takes place;
more time was required at higher bias voltages to get the same coating detaching the entrapped gas atoms and loosely bonded particles from the
thickness. Coating thickness of about 1.8 mm 710% was obtained for substrate. In most physical vapor deposition cases increased substrate biasing
coatings deposited at various parameters. A variation of 5–15% in the coating results in the reduction of deposition rate due to the ion-bombardment and
thickness was found in the calculated and actual values due to the density of densification effects [26, 27].
the coatings being lower than the bulk value.

3.3. X-ray diffraction


3.2. Deposition rate
X-ray diffraction patterns of Nb-N films deposited at various N2/Ar flow
3.2.1. Effect of nitrogen flow ratios are shown in Fig. 2. Coating deposited at N2/Ar flow ratio of 0.05
Deposition rates of Nb-N coatings have been plotted in Fig. 1a as a shows hexagonal b-Nb2N as the major phase with (101) preferred orientation.
function of N2/Ar flow ratio. Coatings were deposited without and with With increase in N2/Ar flow ratio
biasing. For biasing, a constant substrate bias voltage of
50 V was applied. Deposition rate of Nb-N films decreased with the
increase in N2/Ar flow ratio. Maximum deposition rate was

)
observed when there was no nitrogen introduced in to the chamber (N 2 ¼0). 2000
Without substrate biasing, deposition rate was 20 nm/min, which decreased to
8.4 nm/min when N2/Ar flow ratio was increased in steps from zero to 0.70.
Similarly deposi-tion rate for NbN coatings, deposited with substrate biasing

25
at -
1800

Surface (HKhardness
50V, was 16 nm/min; which decreased successively to 6.7 nm/ min with the
1600
increase in N2/Ar flow ratio from zero to 0.70.
Deposition rate reduced almost linearly in both the cases with every increase
in N2 flow. This was due to the well known effect of nitride formation at the
target called target poisoning, observed in many other studies [22–24]. 1400 Substrate biasing -50V
Further, it was seen that the reduction in deposition rate followed three
different linear paths in both the cases—with biasing or without biasing. The
three 1200
linear decrease in deposition rates corresponded to the transition of phases
from Nb to hcp b-Nb2N; hcp b-Nb2N to cubic d-NbN and cubic d-NbN to
0
hcp d -NbN as was revealed by XRD, discussed in the Section 3.3. 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
N2 / Ar
)

3.2.2. Effect of substrate biasing 2400


Biasing the substrate causes continuous ion bombardment at the substrate.
This imparts energy and improves not only adhe-sion but also coating density
[25]. However, deposition rate gets reduced. Fig. 1b shows deposition rate 2200
plotted against the sub-strate bias voltage keeping the flow ratio of nitrogen
(HK25

constant (N2/Ar¼0.20). The deposition rate decreased from 15.9 nm/min to 2000
6.0 nm/min when the bias voltage was increased from 0 to
Surfacehardness

1800 N2 /Ar = 0.20


150 V. Decrease in deposition rate with the increase in sub-strate biasing
was due to the ion-bombardment effect at the substrate. With every increase
in substrate biasing increased 1600

1400

0.70 1200
0.60
0 25 50 75 100 125 150
0.50
Substrate Biasing (-V)
0.40
Fig. 3. Surface hardness of Nb-N as a function of (a) N2/Ar flow ratio (Ar flow
0.30 ¼ 20 sccm) and (b) substrate biasing (N2/Ar¼0.20).

0.20
0.10 Table 2
Surface hardness of NbN coating on MS, SS and HSS
0.05 substrates at a load of 25gf.
N2/Ar
Substrate HK25
MS 1084
SS 2040
HSS 2620
Fig. 2. X-ray diffraction patterns of Nb-N coatings at various N 2/Ar flow ratios (substrate
biasing was fixed at 50 V).
K. Singh et al. / Tribology International 50 (2012) 16–25 19

to 0.10 the major phase becomes cubic d-NbN with preferred orientation of 0
and the major phase present was hcp d -NbN phase. Similar changes in the
0
(111). At N2/Ar flow ratio of 0.30 hexagonal d -NbN phase appears, though hardness with the variation in N 2 have been reported by Zenghu et al. [28].
the major phase is still cubic d-NbN but now with preferred orientation of Grain size also influences the hardness of the materials. Hardness changes as
0
(200). With further increase in N2/Ar flow ratio the hexagonal d -NbN phase per the Hall-Petch relationship. Grain size has been found to increase with the
increases and becomes major phase at N 2/Ar flow ratio of 0.70. Similar phase increase in the partial pressure of nitrogen [30], [31, 32]. The decrease in
hardness at higher partial pressures of nitrogen could be attributed due to the
changes with increase in N2 flow were observed by Zenghu et al. increase in grain sizes.
[28] and Wen et al. [29]. In all the coatings, substrate peaks were identified
as the major peaks. Table 2 shows the hardness of NbN coating deposited at N2/Ar ratio of
0.20 and 50 V substrate biasing on MS, SS and HSS substrates. HSS substrate
showed the maximum hardness of 2630HK25.
3.4. Hardness

3.4.1. Effect of nitrogen flow


Knoop microhardness values for Nb-N coatings on SS, taken at a load of 3.4.2. Effect of substrate biasing
25gf, have been plotted as a function of increasing N2/Ar flow ratio in Fig. 3a Fig. 3b shows the surface hardness of NbN coatings on SS substrate
(substrate biasing was kept constant at deposited at various substrate bias voltages, keeping N 2/Ar flow ratio constant
50 V). Surface hardness was found to increase rapidly with the increase in at 0.20. Hardness increased continu-ously with the increase in substrate bias
N2 flow. This was due to the compound formation. Surface hardness reached voltage to 150 V. The increase in hardness was due to the increased ion
a maximum value of 2040 HK at a N2/Ar bombardment on the substrate with every increase in substrate biasing that led
flow ratio of 0.20 and then decreased with the further increase in N 2/Ar flow. to the increased coating density. Hardness of the coating increased
The variation in the hardness of the coating was accompanied with the consistently from 1692HK25, for coating deposited at zero biasing, to
observed changes in the crystalline struc- 2346HK25 for coating deposited at substrate biasing of 150 V. Work by Kim
ture of the coating. From the XRD spectra it can be seen that the maximum et al. [9] showed the similar results, where hardness increased consistently
hardness obtained, for coatings deposited at N2/Ar flow ratio of 0.2, with the increase in substrate bias potential up to 200 V; this was attributed to
corresponds to FCC structure. At lower N 2 flow, the low hardness was due to the development and refinement of dome structure with the
the presence of b-Nb2N phase [18]. When N2/Ar ratio was higher than 0.20,
the hardness decreased

20µm

Fig. 4. Scratch patterns for NbN coating on MS (N2/Ar ¼0.20, Vb ¼ 50 V) at various loads (a) 2 N; (b) 7 N—cracks; (c) 12 N—cracks and chippings; (d) 16.5 N—cracks, chippings, pile-up; (e) 20 N
—partial delamination and (f) 30 N—complete delamination.
20 K. Singh et al. / Tribology International 50 (2012) 16–25

increase in bias potential up to 200 V. An increased substrate bias voltage sides, pores, chipping, partial and complete delamination of the coating as the
þ
raises the kinetic energy of the Ar ions and niobium particles. A load increased. Prominent difference was visible with respect to the coating
bombardment of the growing film with highly energized niobium particles on different substrates. MS samples showed the poor adhesion as cracks,
þ
and Ar ions caused a dense struc-ture. As a result, the hardness of the film chipping, delamination etc. took place at much lower loads, while HSS
increased. sample showed the best adhesion among the three substrates—showing these
phe-nomena occurring at much higher loads. Fig. 7 shows the typical online
3.5. Scratch adhesion test recorded graphs for loading, friction, depth of indentation and acoustic
emission during scratch test for NbN coating on MS,
In order to have a real observation during scratch tests, the horizontal
displacement rate i.e scratch speed (1.03 mm/min) and the load rate (10 SS and HSS. Online recording of all the coated and scratched samples was
N/min) were kept same for all the tests. Several types of observations were performed. However, only typical spectrum from one of the tests on each
revealed as the scratch progressed from 1N start load to predefined maximum substrate has been reproduced here. From these spectra, the depth of
load in a linearly increasing mode. These were—top layer removal, pile-up on indentation and coefficient of friction data was evaluated. Acoustic emission
the sides, visibility of small cracks to long wide cracks, pores, chip-ping, signals corroborated the critical loads for various types of observations as
delamination of the coatings etc. Fig. 4 shows the scratch patterns for NbN revealed in the microscope (Figs. 4–6).
coating on MS sample taken at the loads of 2, 7, 12, 16.5, 20 and 30 N. Fig. 5
shows the scratch patterns for NbN coating on SS taken at the loads of 1, 12,
22, 28, 32 and 38 N. Fig. 6 shows the scratch patterns for NbN coating on 3.5.1. Critical loads
HSS taken at the loads of 1, 27, 36, 45, 53 and 60 N. The scratch photographs Two critical loads Lc1 and Lc2 have been defined for the failure of the
were taken at many similar loads; however pictures with similar observations coatings. Lc1 the first critical load corresponds to the initial cohesive failure
(at different loads) have only been depicted here. These figures show the top of the coating such as appearance of first cracks or pores within the coating.
layer removal, cracks, pile-up on the And Lc2, the second critical load corresponds to adhesive failure of the
coating i.e. first observation of adhesive failure such as chipping, partial
delamination, pores

Fig. 5. Scratch patterns for NbN coating on SS (N2/Ar ¼0.20, Vb ¼ 50 V) at various loads (a) 1 N—start; (b) 12 N—Segregation, cracks, pores; (c) 22 N—chippings, pores, pile-up; (d) 28 N—
chippings, pile-up; (e) 32 N—partial delamination and (f) 38 N—complete delamination.
K. Singh et al. / Tribology International 50 (2012) 16–25 21

20µm

Fig. 6. Scratch patterns for NbN coating on HSS (N 2/Ar ¼0.20, Vb ¼ 50 V) at various loads (a) 1 N—start; (b) 27 N—Segregation, cracks, pores; (c) 36 N—chippings, pores, pile-up; (d) 45 N—
chippings, pile-up; (e) 53 N—partial delamination and (f) 60 N—Severe delamination.

or some such phenomena, where substrate beneath coating gets exposed. Lc 1 from 8.2 N to 9 N and further to 9.5 N with the similar increase in applied
and Lc2 for NbN coatings on various substrates are listed in Table 3. Lc1 and loading rates. For SS sample, Lc 1 changed from 15 to 17 N and Lc 2 from 22
N to 24 N, when the applied load rate was increased successively from 10
Lc2 for coatings on MS samples were observed to be between 6–8 N and 9–
12 N loads, respectively. HSS coated substrates showed the maximum critical N/min to 80 N/min. For HSS coated sample, the Lc 1 shifted from 15 N to
15.5, 16 and 17 N when the load rate was increased from 10 to 30, 50 and 80
loads - Lc1 ranged from 14 to18 N and Lc2 varied from 24 to 36 N.
N/min, respectively. Lc2 for coating on HSS sample was found to increase
from 34 N to 34.5, 35 and 36 N, respectively, for the similar increase in
applied loading rates.
3.5.2. Coefficient of friction
Coefficient of friction (m), as observed in the scratch adhesion tests,
increased with the increasing load. Table 4 lists the m value at different loads
for the three types of substrates. The variation in m was more pronounced for
3.5.4. Depth of penetration
NbN coatings on MS and SS substrates, while for HSS coated samples, the
variation in m was least. m varied from 0.23 to 0.45 for MS samples, 0.25–0.40 Depth of penetration has not much relevance here. Depth of penetration
for SS samples and 0.12 to 0.22 for HSS samples with the increase in load from 20 depends on how hard is the base substrate. Depth of penetration includes
to 60N. This was expected since HSS is harder than MS or SS. At any particular elastic as well as plastic deformation during loading. After unloading most of
load, m was found to vary within a very limited range for coatings deposited at it (elastic portion) is recovered. The combined value of elastic and plastic
various N2/Ar flow ratios. For example, for NbN coatings on SS sample, m varied suppression at 30N applied load showed that HSS samples had the least value
while MS samples showed the maximum value. At 30N load, on an average,
from 0.22 to 0.25 at 30 N load for coatings deposited at different N 2/Ar flow ratios.
MS samples had 20–30 mm depth of penetration, SS samples had 12–25 mm
depth of penetration and HSS samples had 6.5–10 mm depth of penetration.
However, the length tra-velled by the indenter before the Lc 2 value reaches
(i.e. adhesive failure of the coating) could be of more relevance. The
maximum scratch lengths sustained by the MS, SS and HSS substrates were
3.5.3. Effect of loading rate observed to be 0.8 mm, 1.5 mm and 3.6 mm before the Lc2 value reached.
Effect of loading rate on Lc 1 and Lc2 was found to have little impact. Lc 1
was found to shift from 7 N at 10 N/min to 7.5 N at 30 N/min and further to
8.2 N at 50 N/min. Similarly Lc2 shifted
22 K. Singh et al. / Tribology International 50 (2012) 16–25

Table 3
Critical loads for NbN coating on various substrates.

Critical Load MS SS HSS

Lc1 (N) 6–8 8–15 14–18


Lc2 (N) 9–12 12–25 24–36

Table 4
m at different loads for NbN coating on MS, SS and HSS during scratch test.

Load(N) MS SS HSS

20 0.23 0.20 0.12


30 0.28 0.25 0.15
40 0.35 0.30 0.18
60 0.45 0.40 0.22

Table 5
Effect of biasing on critical loads during scratch test for
Nb-N coatings on SS.

Biasing ( V) Lc1 Lc2


0 6.5 10.5
25 10.5 20
50 12.0 24
75 15.6 26
100 7.0 11

Table 6
Effect of N2 flow on critical loads during scratch test for
Nb-N coatings on SS.

N2/Ar flow ratio Lc1 Lc2

0.10 11 18
0.20 12 24
0.30 11 25
0.40 10 20
0.50 8 20
0.60 8 18
0.70 7 14

on SS substrate, led to the consistent increase in Lc 1 and Lc2. Further


increases in the bias voltage decreased adhesion. The Lc 1 and Lc2 values were
found to be 14.6 and 26 N, respectively for coatings deposited at 75 V
biasing. However, at 100 V, Lc 1 and Lc2 both dropped drastically to 7 and 11
N, as shown in Table 5.The reason for this behavior could be cited to the
generation of excess compressive stresses due to the bombard-ment by high
energy ions, and the consequent detrimental of the coating adhesion.

3.5.6. Effect of N2 flow


Fig. 7. Online recorded graphs for loading, coefficient of friction, depth of indentation and Nb-N coatings deposited on SS at N2/Ar flow ratios of 0.10 to 0.70
acoustic emission during scratch test for NbN coatings (N2/Ar (keeping the biasing voltage constant at 50 V) were evaluated for scratch
¼0.20, Vb ¼ 50 V) on (a) MS, (b) SS and (c) HSS. adhesion. Results with respect to critical loads are shown in Table 6. Coatings
deposited at N2/Ar flow ratios of 0.20 and 0.30 showed better adhesion with
higher critical loads—Lc1 was 11–12 N, and Lc2 was 24–25 N. These coatings
had also shown the higher hardness. At higher flow rates, critical loads
3.5.5. Effect of biasing decreased. Zhitomirsky et al. [21] had shown similar
Increase in biasing voltage up to 75 V (in a step of 25 V), keeping other
factors constant during deposition of Nb-N coating
K. Singh et al. / Tribology International 50 (2012) 16–25 23

results, where critical load as well as hardness initially increased with the worn out slowly by abrasive removal as the wear test progressed. m varied
increase in the nitrogen pressure and then decreased gradually with the further from 0.45 (for coatings deposited at N 2/Ar flow ratio of 0.20) to 0.52 (for coatings
increase in nitrogen.
deposited at N2/Ar flow ratio of 0.30 and 0.40) and further to 0.55 (for coatings
deposited at N2/Ar flow ratio of 0.60). Fig. 9 shows the variation in m with sliding
3.6. Wear tests time at 5 and 15 Hz frequencies (keeping other factors constant) for Nb-N coatings
deposited at N2/Ar flow ratio of 0.50. It can be seen from the graph that with the
3.6.1. Coefficient of friction increase in frequency from 5 to 15 Hz, coefficient of friction increased from 0.5 to
Typical graphs of coefficient of friction (m) with respect to wear time for 0.55 m for coatings deposited at different N 2/Ar flow ratios are plotted against
NbN coatings deposited on SS at 0.20, 0.30 and 0.40 of N2/Ar flow and tested load (at sliding speeds of 10 and 30 mm/s) and against sliding speed (at 3 and 6 N
loads) in Figs. 10 and 11, respectively. Coefficient of friction decreased with the
at 3 N load and 15 Hz frequency are shown in Fig. 8. During the initial
increase in load and increased with the increase in sliding speed. Havey et al. [19]
ramping, friction fluctuates. This was due to the interaction of coating and the
had shown the steady value of m as 0.6 for NbN coatings against Si3N4 ball and
ball material. In the initial periods, m increased to a peak value and then
0.7 against SS ball in a ball-on-flat tribometer. Fontalvo et al. [20] observed the
reduced gradually to a lower stable value. High initial m was due to the mean value of m as 0.8 for alumina ball tested against NbN coating tested at room
adhesive wear taking place between the ball and the coated plate that led to temperature in a ball-on-disk tribometer. They cited the reason for the observed
the transfer of material from ball to the coated surface. The friction reduced as higher m value that the coating might had worn out during the tests and
the material transfer from the ball stabilized after a large area of the coated consequently concomitant higher amount of produced wear debris interacted with
sample was covered with the transferred material from the ball. After certain the surfaces in contact.
duration, this transfer covered the test area and then abrasive wear takes
place. The stable value of friction increased after some time as the test
progressed. During the steady state, the transferred material
In the present study, coatings deposited at N 2/Ar flow ratios of 0.20 and
0.30 showed the lowest values of m ranging between
0.38 to 0.41 tested at 6 N load and 5 Hz frequency.

3.6.2. Wear rate


Due to the transferred material from ball to the coated surface, it was
difficult to measure the wear of the coated plate. Therefore, wear of the
counter body (ball) was measured. Wear volume of the ball was calculated by
measuring the wear scar diameter and using formula–

4
V ¼ pd =64r

Fig. 8. Coefficient of friction (m) Vs sliding time for NbN coatings deposited at Fig. 9. Coefficient of friction Vs sliding time for NbN coatings (N 2/Ar ¼0.50) wear
N2/Ar flow ratio of (a) 0.20, (b) 0.30 and (c) 0.40; wear tested @ 3N and 15Hz for 600 s. tested at (a) 5 Hz and (b) 15 Hz; (Load¼ 6 N).
24 K. Singh et al. / Tribology International 50 (2012) 16–25

Sld. Speed 10 mm/s N2/Ar Fig. 12 shows the variation in wear rate of the ball with respect
0.7 to sliding speed at 3 and 6 N loads, while Fig. 13 shows the wear
rate with respect to load at 10 and 30 mm/s of sliding speeds.
0.6 0.10 Coatings deposited at N2/Ar flow ratio of r0.10 yielded the
lowest ball wear rate; this was due to the metallic nature of the
0.5 0.20
coating and presence of Nb2N phase. Nb2N phase has been found
µ

0.30
0.4 0.40 3N N2/Ar

/N.M
0.3 0.50 8
0.60 0.10
7

Wear Rate x10- 4mm 3


0.2 6 0.20

2.5 3.5 4.5 5.5 6.5


0.30
Load in N 5 0.40
Sld. Speed 30 mm/s N2/Ar 4
0.7 0.50
3
0.60
0.6 2
0.10 10 15 20 25 30 35
5
0.5 0.20 Sliding Speed in mm/Sec
N2/Ar
µ

0.40 8 6N

Wear Ratex10 -4 mm3 /N.M


0.4 0.50 0.10

7
0.3 0.60 6 0.20

0.30
0.2 5 0.40
3.5 4.5 5.5 6.5
2.5 7
4 0.50
Load in N
Fig. 10. Coefficient of friction (m) Vs load at (a) 10 and (b) 30 mm/s sliding speed 3 0.60

for coatings deposited at various N2/Ar flow ratios. 2


5 10 15 20 25 30 35
3N N2/Ar Sliding Speed in mm/Sec
0.7
Fig. 12. Ball wear rate Vs sliding speed at (a) 3 N and (b) 6 N load for coatings
0.6 0.10 deposited at various N2/Ar flow ratios.

0.5 0.20 Sld. Speed 10mm/Sec


0.40
N2/Ar
µ

8
Wear Rate x10 -4mm 3 /N.M

0.4 0.50

0.3 0.60 7 0.10

0.2 6 0.20

5 15 25 35 0.30
5 0.40
Sliding Speed in mm/sec
6N 4 0.50
N2/Ar
0.7 3 0.60

0.6 0.10 2
0.5 0.20 2.5 3.5 4.5 5.5 6.5
0.40 Load (N)
µ

0.4 0.50 8 Sld. Speed 30mm/Sec


/N.M

N2/Ar
0.3 0.60 0.10
7
-4 mm 3

0.2 6 0.20
5 15 25 35
0.30
Wear Rate 0x1

Sliding Speed in mm/sec 5 0.40

Fig. 11. Coefficient of friction (m) Vs sliding speed at (a) 3 N and (b) 6 N load for
4 0.50
coatings deposited at various N2/Ar flow ratios.
3 0.60

Where, V¼wear volume (mm 3 ), d¼wear scar diameter (mm) and 2


2.5 3.5 4.5 5.5 6.5
r¼ball radius (mm). Wear rate was calculated by the formula – Load (N)
Wear rate ¼ Wear volume=ðload sliding distanceÞ
Fig. 13. Ball wear rate Vs load at sliding speed of (a) 10 and (b) 30 mm/s for coatings deposited
Sliding distance was measured in mm. at various N2/Ar flow ratios.
K. Singh et al. / Tribology International 50 (2012) 16–25 25

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[3] Dawson-Elli DF, Fung CA, Nordman JE. IEEE Transactions on Magnetics 1991;27:1592.
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