Wear 390391 (2017) 312321

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

Eect of oil temperature and counterpart material on the wear mechanism MARK
of ta-CNx coating under base oil lubrication

Xiaoxu Liu , Ryo Yamaguchi, Noritsugu Umehara, Motoyuki Murashima, Takayuki Tokoroyama
Department of Mechanical Science and Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464 8603, Japan

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

Keywords: Tetrahedral amorphous carbon nitride (ta-CNx), as an emerging and promising diamond-like carbon (DLC), has
ta-CNx better mechanical properties than amorphous carbon nitride (a-CNx) to ensure the sucient durability, and
Specic wear rate overcomes the limit of high internal stress of tetrahedral amorphous carbon (ta-C), which makes ta-CNx coatings
Oil temperature of great worth of research for the tribological and mechanical applications. In this study, we present the eects of
Counterpart material
oil temperature and counterpart material on the wear behavior of ta-CNx coatings under base-oil lubrication,
and further clarify the wear mechanism. ta-C and ta-CNx coatings with N/C atomic ratio of 2.2% and 11.0% were
deposited by an ion beam assisted ltered arc deposition (IBA-FAD) system, and the tribological tests were
performed using a ball-on-disk tribo-tester with ta-C and ta-CNx coated steel ball sliding against uncoated disk
under base-oil lubrication. The results show that nitrogen doping tends to decrease the hardness and Young's
modulus by reducing the sp3 structure. Sliding against steel disk, with increase of sliding distance ta-CNx shows
obviously distinct wear behavior compared to ta-C, much more slowly increasing wear volume, exhibiting ex-
cellent wear resistance. Increasing oil temperature from room temperature to 120 C results in rising wear rates
of all the three coatings, with totally worn out ta-C and much lower wear rate of ta-CNx, which decreases by
more than half than ta-C for high nitrogen content ta-CNx. However, as the counterpart material changed from
steel to alumina, the wear rate presents oppositely increasing tendency with N/C ratio, probably caused by the
change of deciding factor to hardness in this mechanical wear. It is found that the wear performance of ta-CNx
coating has a clear dependence on the oil temperature and counterpart material. Based on the results, the better
wear resistance of softer ta-CNx against steel could be attributed to the less tribo-chemical wear between carbon
and iron, due to the nitrogen doping partial passivation eect.

1. Introduction
Wear is an important reason for the failure of mechanical parts
causing substantial economic losses [1], and it is urgently needed to
reduce the friction in view of huge energy consumption of modern
society. Therefore, Diamond-like carbon (DLC) coating, due to the high
hardness, ultra-low friction and good wear resistance under dry or lu-
bricated contacts, is becoming an attractive and protective coating
widely used in the eld of mechanical components [24]. Among kinds
of DLC coatings, carbon nitride (CNx) has got a great deal of attention
since the calculation of -C3N4 bond strengths indicates the bulk
hardness could be close to that of diamond [5]. Recent years various
methods to fabricate CNx coating have been established [610],
meanwhile the unique low friction of CNx coating makes it even pro-
mising. Umehara et al. found the ultra-low friction of 0.01 in nitrogen
atmosphere [1113]. The low frictional performance of self-mated CNx
coating in inert gas environment [14] and CNx sliding against Si3N4 in
water have also been reported [15]. Moreover, under oil lubrication
CNx coating presents impressive low friction. In the study of Wsche
et al. [16], CNx coatings with the N content of 028 at% with hardness
from 8.02GPa to 16.97 GPa exhibit the much lower friction coecient
below 0.1 under paran oil lubrication compared to that in dry and
humid air. Chen et al. [17] have found CNx coatings show very low
friction coecients of 0.0420.070 under oil lubrication, much im-
proved friction properties from stainless steel and TiN lm. Based on
the previous results, the low friction mechanism of CNx is suggested to
be graphite-like structural transformation [18] and the passivation of
dangling bonds of CNx coatings with lubricant additives [19], while the
wear mechanism is mainly abrasive wear to the to the counter body as
the relatively high hardness of CNx [16].
However, amorphous CNx coating by the normal methods shows
relatively low hardness, with 422 GPa by Chemical vapor deposition
(CVD), 417 GPa by magnetron sputtering (MS) and 1020 GPa by Ion
Beam Assisted Electric Beam Deposition (IBA-EBD) [20]. For this

Corresponding author.
E-mail address: liu@mech.nagoya-u.ac.jp (X. Liu).

http://dx.doi.org/10.1016/j.wear.2017.08.012
Received 11 April 2017; Received in revised form 23 August 2017; Accepted 24 August 2017
Available online 01 September 2017
0043-1648/ 2017 Published by Elsevier B.V.
X. Liu et al.
purpose, nitrogen is doped into tetrahedral amorphous carbon (ta-C),
DLC with high sp3 bonding ratio up to 80% [2], to fabricate tetrahedral
amorphous carbon nitride (ta-CNx) by ltered cathodic vacuum arc
(FCVA) system, as FCVA is eective with highly ionized plasma of en-
ergetic carbon ions among all the deposition methods [21]. Hence, ta-
CNx coating could have better mechanical properties than amorphous
CNx, and also overcome the limit of residual stress of ta-C coating [22],
making ta-CNx with great potential for the application of mechanical
sliding parts. The studies of ta-CNx so far are mainly about the depos-
iting parameters and material properties [9,2325]. There are few
about the tribological properties of ta-CNx coatings, especially under oil
lubrication. Recently in our group ta-CNx coatings have been success-
fully deposited, and markedly low wear rate of high nitrogen ta-CNx in
oil was found [26]. With the increase of N/C ratio, ta-CNx is more in-
clined to transit from boundary lubrication to mix lubrication during
the friction process, favoring the better tribological performance.
However, the wear mechanism of ta-CNx coating in oil has not been
fully claried, especially the reason why the softer ta-CNx coating
shows better wear resistance than ta-C. Meanwhile, as the practical
application condition might be more complicated, it is quite sig-
nicative to study the experimental condition eects, such as the oil
temperature and counterpart material, on the ta-CNx tribological
properties, furthermore to comprehensively reveal the wear mechanism
of ta-CNx coating.
In this study, we focus on the clarication of wear mechanism of ta-
CNx coatings under base-oil lubrication. Firstly, ta-CNx coatings with
various N/C ratios are fabricated with IBA-FAD method, and the ni-
trogen doping eects on the mechanical properties and microstructure
are studied. With ball-on-disk friction tests, the eects of sliding dis-
tance, oil temperature, and counterpart materials on wear behavior of
ta-CNx under base-oil lubrication have been investigated, respectively.
Furthermore, the wear mechanism of ta-CNx coatings, especially the
reason of excellent wear resistance of softer high nitrogen content ta-
CNx coating will be claried.
2. Experimental
2.1. Coating deposition and characterization
ta-CNx coatings with various contents of nitrogen were deposited on
8 mm high carbon high chrome bearing steel (GCr15) ball substrates
using IBA-FAD system depicted in Fig. 1. For more detail information of
the ta-CNx coating deposition refer to the earlier study [27]. The
Fig. 1. Schematic diagram of IBA-FAD system.
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Wear 390391 (2017) 312321
nitrogen content of coatings were controlled by the nitrogen gas ow
rate before ionization and measured after deposition by X-ray photo-
electron spectroscopy (XPS) operated with Al K X-ray source (25 W,
15 kV) to ascertain the atomic composition. According to the previous
study [27], as the nitrogen mass ow rate increasing to 20 sccm, cor-
responding to nitrogen partial pressure of 0.08 Pa, the N/C ratio has
linearly reached the maximum value of approximately 11%. Therefore,
in this study nitrogen gas ow rate was set as 0, 5, 20 sccm to re-
spectively fabricate ta-C, low N content ta-CNx, and high N content ta-
CNx, for the next friction test. Hardness and Young's modulus char-
acterizations of the ta-CNx coatings and counterpart disks were made
using nano-indentation with a Berkovich indenter (Elionix ENT-1100a),
while the thickness and roughness Ra were evaluated from surface
proler (Mitsutoyo S-3000). Raman spectroscopy measurement (Jasco
NRS-1000 and Renishaw) was performed in the wave ranges of
6002200 cm1 on the coatings for the calculation of ID/IG ratio and G
peak position by tting to the disorder (D) peak and graphite (G) peak
[28]. XPS measurement was also performed on the coatings for eva-
luation the chemical bonding states with sp3/sp2 ratio calculation with
the deconvolution method referred to [29]. The C 1s and N 1s envelopes
were conducted with a mixture of Gaussian and Lorentzian line-shapes.
Meanwhile, for the fracture toughness measurement according to
the method [30], various nitrogen content ta-CNx coatings were also
deposited on (100) single silicon substrate, with nitrogen mass ow rate
of 0, 5, 15 and 30 sccm. The thickness, N/C atomic ratio, Hardness and
Young's modulus were measured with the same method of the coatings
on steel substrate. Fracture toughness tests were performed using a
Vickers indenter with loads ranging from 50 to 300 g. The indentation
axis was normal to the [001] Si direction. The Vickers indenter and Si
substrate were aligned such that radial cracks that formed in Si were
along the (011) and (011) planes. The crack length was observed by
eld emission scanning electron microscopy (JEOL, JSM-7000FK), and
determined by averaging the data of four indents made at every load.
2.2. Tribological experiments
To realize the boundary lubrication, with the practically harsh
mechanical condition, ball-on-disk test, which could ensure the high
contact pressure and simulate many sliding parts such as valve train
components in internal combustion engines, was conducted in this
study. In this study, ta-CNx was coated onto the ball side to precisely
calculate the wear, and the counterpart disk was uncoated high carbon
steel (S55C), which is widely used in mechanical parts. The geometry of
the steel disk was 22.5 4 mm. The upper ball was xed to prevent
from rotating to ensure the pure sliding condition, and located 5 mm
eccentrically from the disk center. The lower, at disk was mounted on
a steel holder xed to a rotary turntable. The oil temperature was
controlled by a thermocouple tted to just below the holder. All the
experiments were conducted in poly-alpha-olen (PAO) base oil with
19 mm2/s viscosity and 17.08 GPa1 pressure-viscosity coecient at
40 C. To ensure the boundary lubrication regime and avoid the peeling
o eect, sliding speed was set as 0.052 m/s and normal load was set as
0.7 N, equivalent to a maximum initial Hertzian contact pressure of
0.530.66 GPa, varied with dierent nitrogen contents. And each test
was repeated for three times under the same condition for the re-
producibility. Prior to each test, samples were cleaned in an ultrasonic
bath of benzene and acetone for respective 15 min to remove the con-
taminants. Fig. 2 displays the schematic of the tribo-tester and ball-on-
disk conguration.
Firstly, to evaluate the wear behavior of ta-CNx coatings depending
on the sliding distance wear tests were performed repeatedly with ta-
CNx coatings under 80 C for 45, 90, 125, 189, 281 and 374 m. In the
oil temperature eect study, the tribological tests were conducted at 23,
50, 80, 120 C at a sliding distance of 189 m, respectively, for each test.
In addition, the coatings were rubbed against two kinds of alumina
disks (sintered alumina and sapphire disk) in oil for comparison. The
X. Liu et al. Wear 390391 (2017) 312321

where V is the wear volume (mm3), W is the load (N), and L is the
sliding distance (m). Raman spectroscopy measurement (Jasco NRS-
1000 and Renishaw) was performed on the wear scars to identify the
graphitization. The morphology and roughness of the coatings and
counterpart disks after friction were measured by atomic force micro-
scopy (AFM, SEIKO Instruments, Nanopics 1000).

3. Results and discussion

3.1. Coating characterization

Table 2 summarizes the important characteristic parameters of

Fig. 2. Schematic of ball-on-disk tribo-tester. various N content ta-CNx coatings. With the nitrogen mass ow rate
increasing, ta-CNx coatings with N/C atomic ratio of 0.4%, 2.2% and
11.0% were fabricated, and referred as ta-C, ta-CNx1 and ta-CNx2 in
Table 1
Properties of counterpart disks. the following text. It is clear that with the nitrogen content increasing,
hardness and Young's modulus both decrease by more than half. The
Counterpart disk Hardness, GPa Young's modulus, GPa Roughness Ra, nm coating thickness presents a slight reduction with the N/C ratio, prob-
ably dues to the low energy species enhancing the etching of carbon
S55C steel 4.9 0.1 200.2 10.1 10.4 0.5
sapphire 32.4 1.2 406.5 13.8 6.3 0.8
matrix by nitrogen [32]. Meanwhile, the roughness measurement of the
sintered alumina 33.1 1.1 407.3 10.3 25.2 3.9 ta-CNx on disks from the surface proler demonstrates that ta-CNx
coating shows smoother surface than ta-C. Raman results suggest the
increasing ID/IG with N content indicating the clustering of sp2 phase,
properties of steel disk and alumina disks were listed in Table 1. Both and the decreasing G peak position implying the replacement of olenic
the alumina disks were quite hard compared to steel disk, and sintered groups with aromatic groups and a great loss of local disordering.
alumina was much rougher than the smooth sapphire disk. Each test Furthermore, the much decreased sp3/sp2 ratio calculated from XPS
was conducted in 23 C with test duration of 1 h corresponding to also conrm this eect of nitrogen doping. Raman and XPS results are
sliding distance of 189 m, and the normal load was set as 0.5 N and 1 N, consistent with the decreasing hardness and Young's modulus, illus-
equivalent to a maximum initial Hertzian contact pressure of trating nitrogen doping could promote the conversion of sp3 bonding
0.600.81 GPa and 0.761.06 GPa. into sp2, leading to the lower hardness.
Furthermore, tribological tests of the oil temperature eect study
were repeated with sapphire disk at 23, 50, 80 and 120 C under 0.5 N 3.2. Eect of sliding distance
for with sliding distance of 189 m for the clarication of wear me-
chanism of ta-CNx coatings in oil. Firstly, to investigate the wear behavior of ta-CNx coatings under
The theoretical minimum lm thickness (hmin) and the dimension- dierent friction periods, the sliding distance eect was studied with
less lambda () ratio were calculated to conrm the lubrication regime wear volume measurement conducted after dierent sliding distances.
[31], where U, G, W are the dimensionless speed, material, load para- New steel disks was used for specication of the excellent wear re-
meters respectively, and Rq,a, Rq,b present the root mean square sistance and wear slope depending on the sliding distance.
roughness of coating and counterpart. The wear volume loss of three kinds of ta-CNx coatings as a function
hmin = 3.63RU 0.68G 0.49W 0.073 (1e0.68k ) (1) of the sliding distance is shown in Fig. 3. The wear volume left-to-right
corresponds to the sequence of increasing nitrogen content of ta-CNx
hmin coatings, with the decreasing wear slope demonstrating the better wear
=
Rq2, a + Rq2, b resistance of ta-CNx2. For both ta-CNx1 and ta-CNx2 the wear volume
(2)
increasing linearly with the sliding distance, and ta-CNx coatings are
The calculated lambda ratios from the as-deposited coatings and not worn out even for sliding distance of 374 m. However, ta-C presents
as-received disk were all less than unity meaning the initial friction was dierent wear behavior, the wear volume loss raises up step by step
boundary lubrication. drastically with much higher slope. The optical microscopy images of
wear scars under dierent sliding distances (Fig. 4) further reveal the
distinct wear behaviors of ta-CNx and ta-C coatings. ta-CNx1 and ta-
2.3. Surface analysis
CNx2 coatings are worn progressively with mainly polishing wear oc-
curred on the sliding surface, while ta-CNx2 appears to reach a quite
Wear scars of the coatings were studied using optical microscopy to
steady wear state under long sliding distance, implying the much lower
quantify the specic wear rates, calculated by using the wear equation
wear rate. While for ta-C, the clear wear scar occurs at the initial 45 m
V sliding process, expands to be larger at 90 m, and starts to peel o
specific wear rate = ,
WL (3) around 125 m, resulting in the partial exposure of bright steel substrate,

Table 2
Characteristics properties of various nitrogen content ta-CNx coatings.

Sample name Nitrogen mass ow rate, N/C ratio Hardness, GPa Young's modulus, Surface proler analysis Raman Analysis XPS Analysis
sccm GPa
Thickness, nm Roughness Ra, nm ID/IG G peak Position, sp3/sp2 ratio
cm1

ta-C 0 0.40% 62.72 986.02 298.3 9.67 0.15 1584.25 2.02

ta-CNx1 5 2.20% 45.01 610.37 290.2 7.17 0.27 1572.55 1.59
ta-CNx2 20 10.80% 26.85 300.25 276.5 6.17 0.38 1553.45 1.10

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Fig. 3. Wear volume of ta-C and ta-CNx coatings against steel disk as a function of sliding Fig. 5. Specic wear rate of ta-C and ta-CNx coatings against steel disk as a function of oil
distance. temperature.

and is totally worn out at 189 m, causing the high wear volume. compared to ta-C at 80 C before coatings worn out. Hence, nitrogen
doping into ta-C coatings could improve the wear resistance and en-
hance the durability greatly under oil lubrication, especially under
3.3. Eect of oil temperature
higher temperature.
The steady-state friction coecients, calculated with the average
Comparing the wear rates above at 80 C with the earlier results at
value of the last 10 min each friction tests, are shown in Fig. 7 as a
room temperature [27], the specic wear rates of ta-CNx are almost an
function of the N/C atomic ratio. Broadly, ta-CNx coatings present
order of magnitude higher. Accordingly, the oil temperature eect on
lower friction than ta-C when rubbed against steel in oil. Under low
the tribological properties of ta-CNx coatings is investigated.
temperature, although there is no clear dierence between 23 C and
Fig. 5 shows the specic wear rates of three kinds of ta-CNx coatings
50 C, and the slight decreased friction with nitrogen content could be
as a function of oil temperature. Generally, increased oil temperature
explained by the softer ta-CNx coating more likely to experience the
leads to higher wear rate for all the studied coatings in PAO oil. When
lubrication regime transition to mixed lubrication [27]. While for high
tested at low temperature of 23 C and 50 C, the wear rates of the
temperature, the poor durability of the coatings at 80 C and 120 C
coatings are as low as 108 mm3/Nm, with not so obvious dierences
results in the total wear, and the direct contact of steel leads to the
between each other. But as the temperature increases to 80 C, ta-C
gradually increasing friction coecient with quite high friction at last,
begins to be worn out (as can be seen in the ta-C wear scar of 189 m in
although it decreases to the a low level of 0.040.06 in the initial
Fig. 4), and further increasing to 120 C results in the totally wear of all
period. As for ta-CNx coatings, and the lowest friction coecient is
the coatings, as shown in Fig. 6, exposing the bright substrate material.
observed at 80 C, with an ultra-low friction coecient around 0.028,
From the friction coecient curve of each test under 120 C, the worn
which could be attributed to higher contents of sp2 bonds induced by
out sliding distances of ta-C, ta-CNx1 and ta-CNx2 are approximately to
the increasing temperature, consistent with a graphitic-like behavior
be 72 m, 102 m, 137 m, with the sequentially smaller wear scars to-
[33].
gether indicating longer life-time of higher nitrogen content ta-CNx
under high temperature. Meanwhile, it is noted that the wear rate
dierence between the coatings also increases signicantly with the
temperature, and the wear rate of ta-CNx2 decreases almost 70%

Fig. 4. Representative wear scars of ta-C and ta-CNx coatings on balls against steel disk at dierent sliding distances (The arrows indicate the sliding direction of disk).

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X. Liu et al.
Fig. 6. Representative wear scars of ta-C and ta-CNx coatings on balls against steel disk at (1) 50 C (2) 120 C.
Fig. 7. Friction coecients of ta-C and ta-CNx coatings against steel disk as a function of
N/C ratio under dierent temperatures.
3.4. Eect of counterpart material
As it is suggested that the high wear of ta-C coatings against steel
might due to the high solubility of carbon in steel [34,35], therefore, to
remove the eect of carbon and iron anity, two kinds of alumina disks
(sintered alumina and sapphire disk) were used to rub against the
coatings.
Fig. 8 displays the specic wear rates of ta-C and ta-CNx coatings
rubbed against three kinds of counterpart materials under room tem-
perature. Sliding against sapphire, ta-C presents markedly the lowest
wear rate, especially under 0.5 N, while ta-CNx1 and ta-CNx2 give
much higher wear rates compared to ta-C coating, approximately in-
creased one order of magnitude under 0.5 N and more than twice under
1 N, respectively. The results shows that ta-CNx coatings exhibits in-
creasing wear rates with the N/C ratio under both applied loads, and
meanwhile, the wear rates against sintered alumina disk under 0.5 N
also follow the same increasing tendency, although the wear rate is
higher than against sapphire, especially for ta-C coating. Interestingly,
this shows contrary tendency with the results from sliding against steel
disk, which presents decreasing wear rate with the N/C ratio. It in-
dicates that ta-CNx coating will lose its better wear resistance
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Wear 390391 (2017) 312321
Fig. 8. Specic wear rate of ta-C and ta-CNx coatings against dierent material disks
under room temperature.
advantage when the counterpart disk is changed from steel to alumina
disks after removing the eect of carbon and iron anity. Fig. 9 shows
the optical microscopy images of wear scars on ta-C and ta-CNx coated
balls after sliding against sapphire and sintered alumina disk under
0.5 N of applied load. ta-CNx presents much larger and smoother wear
scars, implying the high wear rate is resulted from the softer ta-CNx
under severe polishing wear. Meanwhile along with the polishing ef-
fect, local abrasive grooves could also be clearly observed on the worn
surface of ta-CNx coatings, and the grooves are much deeper in the
wear scars of ta-C, which could not be found in those rubbed against
steel. Furthermore, it is noted in the Fig. 8 that in the case of sliding
against sintered alumina under 1 N, which is regarded as the severest
friction condition, providing the highest wear rate of the level of
107 mm3/Nm, ta-CNx coatings conversely shows lower wear rate than
ta-C.
Fig. 10 shows the steady-state friction coecients sliding against
the three dierent counterpart materials as a function the N/C atomic
ratio. Sliding against sapphire and steel disk present similar decreasing
tendency of friction coecient as a function of the N/C ratio, probably
caused by ta-CNx2 has smoother surface after polished, which also
supported by the fact that sliding against sapphire under 1 N, corre-
sponding to more polishing wear of ta-CNx, leads to lower friction than
X. Liu et al. Wear 390391 (2017) 312321

Fig. 9. Representative wear scars of ta-C and ta-CNx coatings on balls against (1) sapphire and (2) sintered alumina disks under applied load of 0.5 N.

0.5 N. It is interesting that the friction coecients sliding against sap-
phire disk are higher than steel disk, although the sapphire disk is even
smoother. Generally sintered alumina gives the highest friction among
the three counterparts, and for ta-CNx coatings sliding against sintered
alumina disk, the dierence of friction coecients between 0.5 N and
1 N of applied load is not signicant.
3.5. Surface analysis
To further clarify the wear mechanism of ta-CNx coatings, the worn
surfaces were analyzed. For the oil temperature eect study Raman
measurement was conducted on the wear scars of coatings to identify
graphitization, and for the counterpart disk eect study AFM mea-
surements was taken on both of the worn surfaces of coating and disk to
calculate the lambda ratio .
3.5.1. Raman spectroscopy results
As DLC is a metastable structure of amorphous carbon containing a
mixture of sp3 and sp2 bonds, tribo-induced graphitization could occur
on the wear surface of DLC coatings as a structural transformation
during the friction [36], which is greatly inuenced by the temperature
[37]. Therefore, Raman measurement is taken on coatings before and
after rubbed against steel disk under dierent oil temperatures. Gra-
phitization can be interpreted from an obvious increase in intensity
ratio (ID/IG) of the Raman spectra [38]. Fig. 11 compares the Raman
spectra of the wear scar after 80 C test and as-deposited coatings of ta-
C, ta-CNx1 and ta-CNx2 with ultra-violet (UV) Raman (Renishaw). As
observed in the spectra, no signicant change between before and after

Fig. 10. Friction coecients of ta-C and ta-CNx coatings against dierent material disks as a function of N/C ratio.

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X. Liu et al.
Fig. 11. Raman spectra of ta-C and ta-CNx coatings before and after sliding against steel
disk at 80 C.
friction could be observed and so is the case of 23 and 50 C. Although
the comparison of the ID/IG ratios shows that after the friction there is a
slight increase, it is insucient to be regarded as graphitization.
3.5.2. AFM measurements
The both worn surfaces (ball and disk) of ta-CNx coatings sliding
against steel, sapphire and sintered alumina disks before and after
friction tests were measured by AFM, to get the roughness Ra. The wear
scar roughness of the coatings decreases with the N/C ratio for all the
three disks, and it is noteworthy that sliding against the two kinds of
alumina disks produces much higher roughness of wear scars, respec-
tively to be 5.731.95 nm for sapphire disk and 24.872.04 nm for
sintered alumina disk, than sliding against steel disk, which the wear
scar of coating roughness varies from 2.03 to 1.33 nm, although the
sapphire is the smoothest counterpart. Moreover, the roughness of the
counterpart wear tracks from AFM measurement shows the sapphire
wear track ranks the smoothest, while sintered alumina has the highest
roughness. The representative AFM images of wear tracks (sliding
against ta-CNx1 under 1 N), as shown in Fig. 12, reveal the dierent
surface morphology of wear track for dierent counterpart disk. For
steel disk, rough abrasive scratches parallel to the sliding direction
associated with some obvious plastic deformation generated. It is in-
teresting that the two alumina disks present quite distinguishing wear
tracks that sintered alumina disk is extremely rough, with some big
Fig. 12. AFM images of wear track from dierent material disks after sliding against ta-CNx1 under 1 N.
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Wear 390391 (2017) 312321
spalled holes and irregular scrubbed traces, while sapphire disk is re-
latively clean, only with some shallow parallel grooves.
Furthermore, the theoretical transition lambda () parameter ( =
1 for BL-ML and = 3 for ML-HL), is presented in Fig. 13 to ascertain
the lubrication regime in the nal friction process. Before friction test,
ratio varies from 0.23 to 0.39, implying the critical boundary lu-
brication of the initial period. The slightly decreasing roughness caused
by nitrogen doping results in the a little higher ratio, and there is
unnoticeable dierences of the ratios between the three disks.
However, the ratios after friction dier a lot, implying the tribological
mechanism is much inuenced by the counterpart material. For both
steel disk and sapphire disk, the ratios increase with the N/C ratio,
with ta-CNx2 showing the value of more than 1, indicating the lu-
brication transition to mixed lubrication. Interestingly, in the case of ta-
CNx coatings, as for steel disk the ratios under two applied loads are
similar, while for the sapphire disk 1 N of applied load produces higher
ratio than 0.5 N, might due to more polishing eect of hard sapphire.
The ratios from sintered alumina disk shows distinct results after
friction, remaining to be as low level as before friction, and even lower
than the initial under 1 N, stating the severe boundary lubrication all
the process against sintered alumina.
3.6. Discussion
3.6.1. Wear behavior of ta-CNx coatings under the inuence of dierent
factors
The obtained tribological results reveal that nitrogen doping leads
to great change to the wear mechanism of ta-C coating under oil lu-
brication. Firstly, the wear behavior study of the sliding distance shows
that the softer ta-CNx coating presents much better wear resistance
compared to ta-C. For ta-CNx/steel contact wear takes place mainly as
smooth polishing wear with slowly increasing wear volume, while ta-C
exhibits rapidly rising wear loss and relatively limited life-time.
Moreover, the results from oil temperature eect further conrm the
much lower wear rate of ta-CNx coating against steel disk, especially
under high temperature. However, the counterpart material eect re-
sults of rubbing against two kinds of alumina disks as a comparison
reveal an interesting conclusion that when the counterpart material is
changed from steel to alumina, the wear rate increases with the N/C
ratio, contrary to the results against steel, meaning ta-CNx coating has
lost the advantage of wear resistance. Understandably, as alumina are
much harder than steel (see in Table 1), even than ta-CNx2, sliding
against alumina results in much higher wear rate of ta-CNx. But in the
case of ta-C, the wear rates show no big dierence between steel and
alumina, and even ultra-low wear against sapphire under 0.5 N. Hence,
it is hypothesized that the accelerated wear rate of ta-C against steel
with increased temperature could be attributed to tribo-chemical wear
caused by the high solubility of carbon in steel [35], and nitrogen
doping could improve the wear resistance by partially passivating the
carbon of ta-C. Apparently, by changing to alumina disk this eect is
totally eliminated with only mechanical wear left. To further conrm
X. Liu et al.
Fig. 13. Lambda ratios of ta-C and ta-CNx coatings against dierent material disks as a function of N/C ratio.
Fig. 14. Specic wear rate of ta-C and ta-CNx coatings against sapphire disk as a function
of oil temperature.
that, the oil temperature eect experiments (Fig. 5) were repeatedly
conducted with sapphire disk under 0.5 N, as shown in Fig. 14. It shows
that rubbed against sapphire disk the wear rate just presents slightly
increasing tendency with oil temperature, which most likely due to the
decreased viscosity of oil, proved by the higher friction with tempera-
ture. And the wear rate is much lower under high temperature com-
pared to that against steel disk, especially for ta-C and ta-CNx1 reduced
by two orders of magnitude. The little inuence of oil temperature on
the wear rate against sapphire disk could further prove the hypothesis.
3.6.2. Wear mechanism of ta-CNx coatings sliding against alumina disks
In this study the wear mechanism of ta-C and ta-CNx coating sliding
against alumina disk under base oil lubrication is further claried,
which it is thought to be only with mechanical wear as they are che-
mically inert. Generally, sintered alumina disk gives much severer wear
to the coatings than sapphire disk, and the wear rate tends to increase
with N/C ratio. It cannot be ignored that (Fig. 8) the wear rate of sliding
against rough sintered alumina under 1 N of applied load, which is
regarded as a harsh condition, is abnormally high especially for ta-C
and ta-CNx1, with oppositely decreasing wear rate with N/C ratio.
Accordingly, the fracture toughness of various N/C ratio ta-CNx coat-
ings has been measured from the radial cracks after micro-indentation,
as shown in Fig. 15, illustrating an obviously improved fracture
319
Wear 390391 (2017) 312321
Fig. 15. Fracture toughness of ta-CNx coatings as a function of N/C ratio.
toughness with the increase of nitrogen content of the coatings.
Meanwhile, by comparison of the surface morphology of wear track of
the two alumina disks (Fig. 12), the big holes on the sintered alumina
imply the wear particles of alumina are generated during the repeatedly
rubbing. For ta-C sliding against the rough sintered alumina disk under
1 N of applied load, which equals to 1.1 GPa of Hertzian contact pres-
sure, not only the disk asperity is easily to cause the spalling of coatings
and the wear debris in turn accelerate the wear, but also the wear
particles generated from the disk will also work as the third body [39],
together resulting in the extremely severe wear. Through nitrogen
doping, the improved fracture toughness makes ta-CNx could bear
higher applied load, with the lower hardness together causes with less
wear particles from both worn surfaces, leading to much better wear
resistance. However, as the applied load is reduced by half to 0.5 N, the
load is supposed to be not enough to trigger the spalling of coating and
disk, the hardness of coating becomes the deciding factor of wear rate
under this condition since the counterpart is quite hard, resulting in the
contrary tendency with that of 1 N. Given the above, the wear me-
chanism of ta-CNx coating sliding against rough and hard sintered
alumina disk is supposed to be mainly abrasive wear with polishing
wear, also veried by the grooves observed in the wear scars and even
decreased ratio after friction (Fig. 13) after friction. While as sapphire
disk is much smoother with quite clean wear track, indicating less wear
X. Liu et al.
particles generation, the wear mechanism of ta-CNx coating sliding
against sapphire disk is mainly polishing wear with abrasion, more
abrasion for ta-C and more polishing for ta-CNx, which can also get
proof from the increased ratio after friction and higher ratio with
the N/C ratio (Fig. 13).
3.6.3. Wear mechanism of ta-CNx coatings sliding against steel disk
However, unlike sliding against the alumina disks, the wear me-
chanism of ta-C and ta-CNx coating sliding against steel in oil is not
only mechanical wear, but also greatly inuenced by the high solubility
of carbon in steel. Previous studies from the perspectives of experi-
mental and molecular dynamics (MD) indicate that the extremely high
wear rate of diamond when rubbed against steel is caused by the strong
anity for carbon and ferrous materials to form a covalent bond
[4042]. As Fe atom has unlled d-orbital in their electron congura-
tion, it tends to react with carbon by overlapping their d-orbital with
carbon's p-orbital, which makes Fe possess one of the highest diusion
coecients for carbon among transition metals and form the metastable
iron carbide Fe3C [43]. For the DLC/Steel friction process, this reaction
is readily to be triggered by the temperature and pressure. In the earlier
study [27], with the same experimental condition as this paper, the
generation of Fe3C as the reaction product has been conrmed by XPS
analysis. Moreover, in this study as the oil temperature increases to
aggravate the carbon and iron anity, the wear rate rapidly increases.
And when changing to chemical inert alumina disk to remove the af-
nity, the wear rate shows oppositely increasing tendency with N/C
ratio, and almost decreases by two orders of magnitude compared to
steel disk under high temperature. The above results strongly suggest
the high wear rate of ta-C and ta-CNx coatings against smooth and soft
steel disk under high temperature is caused by the removal of the
topmost active carbon atoms from the coating surface through friction
induced thermo-chemical interaction of iron with carbon, which can be
regarded as tribo-chemical wear. Furthermore, the smoother wear scars
against steel and the rough wear scars against sapphire and sintered
alumina could also support the above mechanism, as it has been found
that low friction condition is associated with formation of smooth
contact surfaces through tribo-chemical wear, at the opposite of me-
chanical wear forming rough surface [44]. As for the excellent wear
resistance of ta-CNx coatings against steel, it is hypothesized that ni-
trogen doping could reduce this carbon and iron interaction by partially
passivating the active carbon atoms in the surface. But it is noted that
ta-CNx still shows the essential character of ta-C, as the wear rate also
increases with temperature in Fig. 5, implying that nitrogen doping
cannot fully eliminate the eect. Sliding against steel disk (hardness =
4.9 GPa), which is much softer compared to both ta-C and ta-CNx
coatings, the tribo-chemical wear has more inuence than the me-
chanical wear, leading to the interesting phenomenon that softer ta-
CNx possess better wear resistance that ta-C. However, as the coun-
terpart is changed to alumina disk with hardness 32.433.1 GPa, the
hardness of the coatings on the ball becomes the deciding factor, and
thus ta-CNx lost it advantage over ta-C. It is also worth mentioning that
the similar increasing ratios with N/C ratio sliding against steel and
sapphire disk (Fig. 13) imply the insuciency of using transition to
mixed lubrication to explain the excellent wear resistance of ta-CNx,
although it might indeed have a slight favor for reducing wear [27]. In
summary, the wear mechanism of ta-CNx coatings sliding against steel
disk in PAO oil is mainly polishing mechanical wear associated tribo-
chemical wear, and nitrogen doping could eectively improve the wear
resistance by reducing the tribo-chemical wear.
Based on above, several mechanisms might simultaneously exist in
the wear process of ta-CNx coatings in base oil. Normally higher
hardness of the coating could lead to better wear resistance, and the
mechanical wear, such as abrasive wear and polishing wear, is the main
wear mechanism, as the results of sliding against alumina disks shown
above. Meanwhile, it should not be ignored that other mechanisms
might also exist, and even exceed to be the dominant factor, just like the
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Wear 390391 (2017) 312321
tribo-chemical wear in the study against steel under high temperature,
and thus the softer ta-CNx coatings present better wear resistance than
ta-C. Furthermore, for all the counterpart disks under base-oil lubrica-
tion, it shows quite low wear, supposed to be from abrasion and addi-
tional tribo-chemical wear for steel. Finally in a tribo-system as the
wear properties of DLC coatings are strongly aected by the working
temperature, counterpart materials, contact pressure, test environment,
selection of a specic coating for better synergism is of great concern
[2,18]. According to the present study, through reasonably doping ni-
trogen into ta-C coating, we could not only eectively reduce the high
wear of rubbing against steel or other metal with high carbon solubility,
especially under high temperature condition, but also remain the re-
latively high hardness of the coating, while ta-C is strongly suggested if
the disk is hard and without anity with carbon. Finally, it also should
be noticed that for those extremely heavily loaded mechanical com-
ponents, ta-CNx might possess its clear superiority due to the improved
fracture toughness compared to ta-C, leading to dierent applied load
eect on the wear of various nitrogen contents ta-CNx coatings, which
subjects to further study.
4. Conclusions
In this study, ta-CNx coatings have been deposited on steel using ion
beam assisted ltered arc deposition (IBA-FAD) system, and the eects
of sliding distance, oil temperature, and counterpart material on the
tribological properties in base-oil have been investigated. It has been
found that:
The hardness, Young's modulus, the ratio of sp 3
bonding structure
and roughness of ta-CNx coatings decrease with the increase of ni-
trogen content.
ta-CNx shows obviously lower wear rate and distinct wear behavior
compared to ta-C when rubbed against steel, more slowly increasing
wear with sliding distance and much longer lifetime.
The wear rates of ta-C and ta-CNx coatings against steel disk greatly
increase with the oil temperature. But high temperature leads to
severe wear of ta-C, while ta-CNx can eectively reduce the high
wear by more than half especially under high temperature, due to
nitrogen doping could reduce the thermally activated tribo-chemical
wear.
Sliding against sapphire and sintered alumina disks, the wear rate
presents oppositely increasing tendency with the nitrogen content,
as hardness becomes the dominating factor for this pure mechanical
wear.
Nitrogen doping into ta-C could increase the fracture toughness of
coating, in favor of bearing greater applied load and less spalling
eects.
Acknowledgments
This research was supported by Grant-in-Aid for Scientic Research
(25220902), we appreciate this support. Also, I would like to thank
China Scholarship Council for the nancial support.
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