Tribology International 84 (2015) 100–109

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

Effect of surface morphology of diamond-like carbon coating

on friction, wear behavior and tribo-chemical reactions
under engine-oil lubricated condition
Kentaro Komori a,n, Noritsugu Umehara b
a
Honda R&D Co., Ltd. Automobile R&D Center, 4630 Shimotakanezawa, Haga-machi, Haga-gun, Tochigi, 321–3393 Japan
b
Department of Mechanical Science and Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi,
464–8603 Japan

art ic l e i nf o a b s t r a c t

Article history: The tribological behaviors of diamond-like carbon (DLC) coatings sliding against steel lubricated with the
Received 14 May 2014 low viscosity engine-oil containing MoDTC and ZnDTP additives are investigated. The “pre-structured
Received in revised form DLC” coatings, which are deposited on the micro-shot peened rough surface substrates, show low
6 November 2014
friction coefficients and no significant wear, in comparison with the DLCs coated on the usual polished
Accepted 13 November 2014
substrates. The surface structuring can have positive effects on the lubricated contact regime to promote
Available online 28 November 2014
MoS2 formation energetically in the additive-derived tribofilm, and inhibit an increasing DLC wear
Keywords: attributed to MoO3 reduction involving hydrogen evolution and transformation of DLC. We discuss that
DLC coatings different tribo-chemical reactions occur, either positive or negative, depending on the surface
Surface morphology
morphology, hydrogen content and mechanical properties of DLC coatings.
Tribochemistry
& 2014 Elsevier Ltd. All rights reserved.
Lubricant additives

1. Introduction During continuous DLC/steel sliding contact, cohesive failure and

In these years, development of materials and mechanical com-
ponents for internal combustion engine has received increasing
demands for improving fuel economy and addressing environmen-
tal issue, such as to be light-weight, compact and loss-reduction.
Lubricant and surface treatment technology will play more impor-
tant roles, in terms of their direct and immediate effects for imp-
roving performance [1].
Zinc dialkyldithiophosphate (ZDDP, ZnDTP) has been used for
many years in the lubricant industry, in particular, as a multi-
functional agent for engine oils. Molybdenum dithiocarbamate
(MoDTC) is applied to automotive lubricants and greases as a
friction-modifier to improve the fuel efficiency and the durability,
later. Today, they are widely spread to automotive lubrication
blends [2–4]. In addition, recent automotive lubrication trends
shift toward the application of low-viscosity oils to improve fuel
efficiency [5,6].
Another approach to respond to these demands is the applica-
tion of low friction and wear resistant coatings in terms of
boundary lubrication in mechanical components. Diamond-like
carbon (DLC) coatings are well-known for their outstanding sliding
performance as well as high hardness and wear resistance [7].
n
Corresponding author. Tel.: þ 81 28 677 3311; fax: þ 81 28 677 7386.
E-mail address: Kentaro_Komori@n.t.rd.honda.co.jp (K. Komori).
transferring of DLC wear particulates to the opposing surface can
lead to DLC/DLC contact, resulting in a remarkable friction coeffi-
cient reduction [8]. Steady state low friction is related to the
transformation of diamond-like to graphite-like carbon under
thermal and strain effects from the repeated friction involving
hydrogen evolution and sp3 structure destabilization [9].
Recent tribological investigations on DLC coatings are progres-
sing toward understanding the effect of lubricants and the inter-
action between DLC coatings and additives, in particular with
antiwear agents and friction-modifier additives. DLC coatings do
not show any friction reduction under boundary lubrication
conditions. It is attributed to the lack of formation of any transfer
film on the counterface material [10]. In motored valve train tests,
lubricant-derived surface films are not present on the DLC-coated
surface under boundary lubrication conditions. However, under
mixed lubrication conditions, patchy additive-derived antiwear
films can be observed on DLC-coated buckets. The antiwear film
appears to be primarily composed of calcium phosphate, which is
different from the composition observed on uncoated steel sur-
faces [11].
On the other hand, Mo-based friction-modifiers interact with DLC
coating to form MoS2 and MoO3, while the tribofilms derived from
ZDDP are not found on the DLC coating surface. It is observed that
the higher the ratio of MoS2/MoO3, the lower the coefficient of
friction [12]. It is also reported that hydrogenated DLC coatings can
exhibit the low friction performance under lubricated condition in

http://dx.doi.org/10.1016/j.triboint.2014.11.010
0301-679X/& 2014 Elsevier Ltd. All rights reserved.
 K. Komori, N. Umehara / Tribology International 84 (2015) 100–109 101

the presence of the MoDTC additive through the formation of MoS2
during the tribo-chemical reaction in presence of ZnDTP [13].
However, a hydrogen-free DLC coating presents insufficient lubrica-
tion with MoDTC-containing oil. It suggests that appropriate additive
is necessary for lubricating DLC coating, and an ashless friction-
modifier was developed for effective lubrication [14]. Ultralow
friction coefficient is obtained by sliding hydrogen-free tetrahedral
amorphous carbon (ta-C) against ta-C lubricated with poly-alpha-
olefin base-oil containing glycerol mono-oleate (GMO) additive [15].
It is reported that the wear of DLC coatings increase in the
presence of MoDTC in the oil. The decomposition of MoDTC
produces MoO3, which interacts with the DLC coating, resulting
in increased wear [16]. The Mo-oxides destroy the DLC coating
because of its sharp edge crystalline solid structure. After destroy-
ing the DLC coating, the MoDTC react with metals and form MoS2
tribofilm, and decrease coefficient of friction of rubbing pairs [17].
These works suggest that tribological contact mechanics and
chemical reactions will play important roles. At the moment, it is
reasonable to assume that the approach to surface structuring to
promote the further tribofilm formation of MoS2 would respond to
the both low friction and wear resistance requirements, even in
the DLC with highly hydrogen content. It is useful to expand the
availability of DLC materials and the advantage to manufacturing,
because the hydrogenated DLC coatings with the 20–40 at.%
hydrogen content are usually obtained by the general deposition
process. However, the interaction between DLC coatings and
lubricant additives is complicated, because DLC is a non-ferrous
amorphous material. The DLC coating properties can be varied
widely and the tribological performance of DLC coatings with
lubricant additives developed for ferrous-based materials has been
not clear. Some of these give the contradiction which may result
from the different DLC coatings, particularly in related to tribofilm
formation. Therefore, it is essential to understand the effect of
surface morphology and DLC material properties on tribo-
chemical reaction under lubrication condition to obtain improved
performance and advanced application.
In this study, we investigate the tribological effects of surface
morphology of DLC coatings lubricated with the low viscosity
engine-oil containing MoDTC and ZnDTP additives. The “pre-
structured DLC” coatings, which are coated on the steel substrates
made rough surface by micro-shot peening treatment, are pre-
pared. XPS surface analyses are employed to gain an understand-
ing of the tribofilm formation derived from lubricant additives.
conditions varying in 0.03 and 0.05 MPa, respectively, to provide
the different initial surface roughness unlike polished surface. The
hydrogenated DLC coatings were deposited on the pre-structured
substrates (pre-structured DLC) by means of plasma assisted
chemical vapor deposition (PACVD) method using toluene-vapor
(C7H8) as a carbon source. The deposition condition was varied
with the combination of the gas pressure (0.5–4.9 Pa), substrate
bias (400–500 V), plasma power (150–200 W) and coating time
(20–260 min).
By way of comparison, the DLC coatings deposited on the
polished steel substrates were also prepared through the same or
near coating process as mentioned above. Additionally, to obtain
the samples with lower hydrogen content, a DLC coating sample
was deposited by means of another PACVD device with the higher
substrate bias (2000 V) and the lower gas pressure conditions
using acetylene (C2H2) as a carbon source. Moreover, a hydrogen-
free DLC coating was also obtained by means of physical vapor
deposition (PVD) method using arc ion plating (AIP) process.
Thickness of the DLC coatings was regulated to approximately
3–5 mm basically. But, in order to obtain rough surface morphol-
ogies, the thick coatings of approximately 10–25 mm in thickness
were partly applied to DLCs coated on polished substrates. In
contrast, the DLCs deposited by an extra-high bias CVD and an arc-
PVD processes were rather thin coatings of 1.0 mm in thickness.
The different coatings were obtained in terms of hydrogen con-
tent, mechanical properties and microscopic surface morphology,
by varying the deposition conditions. The coated surface did not
have any surface finishing treatment; the so-called as deposited.
2.2. Characterization of DLC coatings
Table 1 shows the characteristics of DLC coating samples. The
hydrogen content of the DLC coatings were characterized by
hydrogen forward scattering spectrometry (HFS) and Rutherford
backscattering spectrometry (RBS) to determine the composition.
The hardness and elastic modulus of the DLC coatings were
measured using nano-indentation method. The pre-structured
DLC coatings tend to show approximately 10% higher hardness
than the DLCs coated on polished substrates in the comparison of
Table 1
Coating process and characteristics of the DLC coatings.

Different tribo-chemical reactions occur during lubricated DLC/

Shot Deposition Thickness H RMS Hardness E-
steel contact depending on the combination of surface morphol- press. condition cont. (Rq) Mod.
ogy and material properties of DLC coatings. We discuss that the [MPa] (Gas pressure / [mm] [at.%] [nm] [GPa] [GPa]
effectiveness of pre-structuring for DLC surfaces in friction and Bias)
wear behavior is shown to depend on the tribo-chemical reactions
Pre-structured DLC: CVD-DLC(hydrogenated) coated on pre-structured substrates
and the tribofilm compositions, compared with the DLC coated on A 0.05 0.5 Pa/high 4.4 26 235 29.9 258
polished substrates. B 0.05 2.3 Pa/high 2.2 32 219 19.9 160
C 0.05 2.3 Pa/low 2.8 36 241 15.4 117
D 0.03 3.3 Pa/low 4.6 37 153 15.8 118
E 0.05 3.3 Pa/low 4.6 37 196 15.8 118
2. Experimental
F 0.05 4.9 Pa/low 3.6 43 193 9.1 65

2.1. DLC coatings CVD-DLC(hydrogenated) coated on polished substrates

a – extra high-bias 1.0 18 20 25.9 253
b – equiv. A 2.6 26 5 27.3 225
The pre-structuring treatment on the polished steel substrates
c – middle of A & B 2.7 29 7 22.1 181
(JIS G 4805/SUJ 2) was applied by the micro-shot peening before d – equiv. B 25 32 15 16.7 137
coating. The shot process was conducted using an air injection e – near B 3.2 33 8 18.1 143
type gun. During this process, the working distance kept 180 mm, f – middle of B & C 18 34 11 12.6 94
and the required peening coverage was over 200%. The shots g – near C 5.0 35 5 14.9 115
h – equiv. C 11 36 11 15.0 116
material was sintered WC/Co (grade 88/12; TRIBO Hartstoff GmbH)
i – equiv. D, E 25 37 20 11.7 87
made by means of a spray granulation method. Shape of shots was j – equiv. F 2.8 43 5 7.7 54
near spherical grits. The grain size range was 45–90 mm and the
PVD-DLC(hydrogen-free) coated on polished substrates
50% cumulative value was 66.2 mm in diameter. The two types of x – AIP 1.0 0.5 28 61 582
substrates were prepared with the different shot peening pressure
102 K. Komori, N. Umehara / Tribology International 84 (2015) 100–109
10μm 5μm
10μm 10μm
Fig. 1. AFM images of micro-surface morphology for the representative DLC samples. DLCs coated on polished substrates as (a) uncoated polished steel substrate; (b) sample-
d; (c) sample-i; (d) sample-j. Pre-structured DLC samples as (e) uncoated pre-structured substrate by 0.05 MPa shot; (f) sample-B; (g) sample-E; (h) sample-F. The pairs of
(b)-(f), (c)-(g) and (d)-(h) are “on polished substrate” and “pre-structured” DLC surfaces deposited by the same conditions, respectively.
the samples deposited by the same process (in Table 1). It seems to
be attributed to the different surface asperities. The microscopic
surface morphology and root mean squared surface roughness
(Rq) of the DLC coatings were estimated by means of atomic force
microscopy (AFM). Fig. 1 shows the AFM images of the represen-
tative DLC coating surfaces. The DLCs coated on polished sub-
strates displayed the surface morphology covered with the small
mound structures. The size and shape of mound structures seemed
to depend on DLC growth process and material. On the other hand,
the pre-structured DLC coatings displayed the unique combined
asperity geometry as the mound structures grown on the rough
undulating surfaces.
2.3. Tribological tests
The tribological behaviors of DLC-coated disks sliding against
steel balls (JIS G 4805/SUJ 2) were examined under lubrication
condition with the full-formulated low viscosity engine-oil
(SAE 0W-20) containing MoDTC and ZnDTP additives. Kinematic
viscosities of the engine-oil were 35.0 mm2/s at 40 1C and
8.29 mm2/s at 100 1C. Viscosity index was 225. Concentration of
the elements corresponding to the additives was 700 ppm of
molybdenum (Mo), 900 ppm of zinc (Zn), 1900 ppm of calcium
(Ca), 800 ppm of phosphorous (P) and 0.24% of sulfur (S), respec-
tively. The diameter of the steel ball was 6 mm. The size of the
DLC-coated disk was 20 mm in diameter and 3.0 mm in thickness,
respectively. The ball was pressed against the rotating disk at a
position that was 10 mm in diameter from the center of the disk,
under lubricated condition. The ball-on-disk tests (Tribometer-
CSEM, CSM Instruments) were performed at 40 1C at a sliding
speed of 100 mm/s under a load of 5 N (initial contact pressure
1.1 GPa) for 50 min.
Many works reported that MoDTC and ZnDDP additives acted
on steel surface to form tribofilm at the higher temperature more
than 80 1C. This is well-known and has been utilized to the actual
engine systems. It was also reported that MoDTC decomposes,
even in low-lubricant bulk temperature tests (30 1C), formed the
same species as in high-lubricant bulk temperature tests (100 and
150 1C), but the tribofilms gave different tribological performance
[18]. In this study, in order to investigate how the difference in DLC
material and surface morphology influenced essentially the ther-
mal and strain effects by sliding contact to generate chemical
height [nm]
5μm 5μm
height [nm]
10μm 10μm
reaction and tribofilm formation, we intentionally performed the
tests at the lower temperature.
After the tribological tests, the worn surfaces of the steel balls
were observed using optical microscopy to estimate the size of
wear scars. The wear amount of the DLC-coated disks was
estimated from the width and depth of the wear tracks measured
using the contact probe profilometer as indexes, respectively.
2.4. XPS analyses
The worn surfaces of the both disks and balls were analyzed by
X-ray photoelectron spectroscopy (XPS). The both disks and balls
were degreased by the organic solvents to eliminate the contami-
nants and residual lubricant, prior to XPS analysis. Then, XPS was
performed with monochromatized Al Ka X-ray source using
Quantera SXM (ULVAC-PHI, Inc.). The X-ray spot size was set at
50 mm in diameter.
Additional attention was paid to the peak fitting of S2p and
Mo3d photopeaks. The photopeak decomposition data were
obtained after the treatment of the XPS spectra. The S2p lines
were fitted with the doublet pairs of S2p3/2 and S2p1/2 peaks. The
S2p3/2 peak to assign as sulfide (S2  ) showed the contribution at
about 162 eV in binding energy. The other contributions were also
shown in the S2p photopeaks. The S2p3/2 peak for C-S chemical
bond showed the contribution at about 164.5 eV, and the S2p3/2
peak for sulfate, sulfonate and sulfone (SO24  , –SO2O  and –SO2–)
showed the contribution at about 168–169 eV in biding energy.
The Mo3d lines were fitted with the doublet pairs of Mo3d5/2 and
Mo3d3/2 peaks. Mo3d5/2 peak contributions attributed to Mo4 þ
(229 eV), Mo5 þ (231 eV), Mo6 þ (232 eV) and Mo(0) (228 eV). We
note that the treatment of Mo3d photopeak decomposition took
account of S2s peaks (at about 226 and 232 eV), because the S2s
peaks overlapped with the Mo3d peaks.
3. Results and discussion
3.1. Friction and wear behavior
Fig. 2 shows that the friction behaviors with the engine-oil
containing MoDTC and ZnDTP additives vary depending on the
pre-structured DLC samples. In contrast, the friction behaviors
 K. Komori, N. Umehara / Tribology International 84 (2015) 100–109 103

with the base-oil containing neither antiwear nor friction-modifier
additives exhibit the higher coefficient of friction around 0.11
steadily, regardless of the different DLC coatings. During tribolo-
gical tests with the engine-oil containing MoDTC and ZnDTP
additives, the coefficient of friction vary within the range of
approximately 0.04–0.10. The sample-B, C, and E run into the
low friction states. In particular, the sample-E reaches the low
friction coefficients, 0.04, earlier than the other samples.
On the other hand, the friction level of sample-D and sample-F
stays higher after the running-in. Then, the coefficients of friction
gradually increase, reaching into the 0.07–0.08 range eventually.
wear scars on the counter steel balls after the tribotests. The
sample-A exhibits a much higher wear on the steel counterface
than the others. It seems that the larger roughness and the higher
hardness of the sample-A can cause the excessive wear of the
opposing steel surface.
Fig. 4 shows the friction coefficients of the pre-structured
DLC coatings in the last state of the tribological tests with the
0.10
0.09

Coefficient of friction
The sample-A exhibits the highest friction during running-in
period. The coefficient of friction is gradually reduced to around 0.08
0.06, but not reaching the lower friction level. Fig. 3 shows the 0.07
0.06
0.14 0.05
Running-in 0.04
with base-oil
period
0.12 0.03
0.02
0.1 A B C D E F
Coefficient of friction

A
D
0.08 0.15
F 0.09

Coefficient of friction
0.06
B 0.08
C 0.07
0.04
E 0.06
0.02 0.05
with engine-oil (MoDTC+ZnDTP) 0.04
0 0.03
0 0.1 0.2 0.3 0.02
Sliding distance/ km a b c d e f g h i j x

Fig. 2. Friction behaviour of the pre-structured DLC coatings against steel lubri- Fig. 4. Coefficient of friction on the average over the last state of the tribotest
cated with the engine-oil containing MoDTC and ZnDTP, in comparison with the lubricated with the engine-oil containing MoDTC and ZnDTP additives for (a) pre-
base-oil lubrication. structured DLC coatings and (b) DLCs coated on polished substrates.

200μm

Fig. 3. Optical micrograph of wear scars on the counter steel balls after the tribotests against pre-structured DLC samples-A – F with the engine-oil. B’, E’ and F’ indicate the
sample-B, E and F tested with the base-oil, respectively.
104 K. Komori, N. Umehara / Tribology International 84 (2015) 100–109
wear track
200μm
Fig. 5. Optical micrograph of wear tracks of the pre-structured DLC samples-A – F after the tribotests.
8000
* undetectable
Wear amount / nm 2
1000
800
600
400
200
0 *
a b c d e f g h i j
Fig. 6. Wear amount of DLC coated on polished substrates after the tribotests
lubricated with the engine-oil containing MoDTC and ZnDTP additives.
engine-oil, in comparison with the DLCs coated on polished
substrates. The friction coefficients shown in Fig. 4 are the average
values over the last 30 s of the each test. The friction coefficients of
the pre-structured DLCs are generally reduced in comparison with
the equivalent DLC materials coated on polished substrates, except
the sample-D. For the DLCs coated on polished substrates, the
“sample-a” also exhibits lower friction level. This coating has both
higher hardness and larger roughness in the hydrogenated DLCs
coated on polished substrates. We note that the tribotest of the
“sample-e” is stopped very earlier at about 0.03 km (5 min). The
friction behavior is deviated after early running-in period and the
coefficient of friction reaches about 0.15 at the maximum value.
In addition, Fig. 5 shows that no significant wear is observed on the
surfaces of the pre-structured DLC coatings regardless of the different
DLC materials. The wear of the pre-structured DLC coatings is clearly
improved to undetectable extent, while the equivalent DLC materials
coated on polished substrates are worn more deeply as shown in Fig. 6.
In particular, the sample-e is worn out remarkably and the deep wear
track seems to reach the steel substrate partially. On the other hand,
the DLCs coated on polished substrates, which have the larger surface
roughness, tend to exhibit relatively low wear (sample-a, d, f, i, and x
in Fig. 6). In particular, the wear of the hydrogenated DLC with the
lowest hydrogen (sample-a) and the hydrogen-free DLC (sample-x) is
undetectable level.
These results suggest that different tribo-chemical reactions occur
during the DLC/steel contact with lubricant additives, depending on
the surface roughness, hydrogen content and mechanical properties of
DLC coatings.
3.2. XPS analyses
The XPS results on the steel balls and the DLC disks are
shown in Tables 2 and 3, respectively. Table 2 shows that the
additive-derived chemical elements are observed particularly on the
steel balls. First of all, it is noticed that Zn and P elements derived
from ZnDTP additive are detected on the steel ball surfaces. ZnDTP is
well-known as an antiwear additive and probably the most widely
used in formulated engine-oils. It also acts as an antioxidant and
corrosion inhibitor. It has been also reported that ZnDTP degradation
products form poly-phosphate tribofilm to prevent metal-to-metal
contact between parts [19,20]. Fig. 3 shows that the wear scars of
steel balls after tribotests with the engine-oil are smaller than those
* with the base-oil, regardless of hydrogen content and hardness of the
x counter DLC coatings. It seems that ZnDTP can act on the steel ball
surfaces and form the antiwear tribofilm efficiently.
The sulfur and molybdenum elements derived from MoDTC
and ZnDTP are also detected on the steel ball surfaces. The
quantitative variation of the sulfur with the different DLC samples
corresponds to that of molybdenum, as shown in Table 2. The S2p
photopeaks on the steel balls mainly show the contribution of
sulfide. But, the sulfate, sulfonate and sulfone are also detected in
the S2p photopeaks on the sample-C, sample-D and sample-j in
low proportion.
The results of Mo3d photopeaks decomposition give the Mo4 þ ,
Mo5 þ , Mo6 þ and Mo(0) species in elemental composition respec-
tively, as shown in Table 2. Mo4 þ indicates the presence of MoS2 or
MoO2. In this study, Mo4 þ seems to show mainly sulfide, because the
quantitative variation of Mo4 þ depending on the each sample
corresponds to that of S2 from S2p photopeak analysis. Mo6 þ
indicates the presence of the MoO3, and Mo5 þ is present in original
MoDTC molecule or in oxysulfide (MoSxOy). Mo(0) suggests the
presence of metallic-Mo or Mo-carbide (mainly Mo2C) effectively,
although weak peaks. The MoS2 come from degradation of MoDTC
by the tribo-chemical reaction during contact. MoDTC decomposes
into the core unit of MoDTC molecule and the chain ends through the
electron transfer on the Mo-S chemical bonding in MoDTC molecule
[4,13]. The core unit of MoDTC molecule forms the oxysulfide,
whereas the chain ends recombine to form thiuram disulfide
including C-S chemical bonding. The oxysulfide decomposes into
MoS2 and MoO2. These can be oxidized into MoO3 in the presence of
O2 [13]. Moreover, Mo-oxides can be reduced into metallic-Mo and
Mo-carbide in the presence of hydrogen and carbon.
It is reported that ZnDTP additive increases the tribo-chemical
formation of MoS2 on the steel surfaces in presence of MoDTC and
ZnDTP binary lubricant mixture [2–4,13,18–22]. It is important
that ZnDTP principally have the role to provide the sulfur atoms to
promote the sulfuration of the oxysulphide. The effect of ZnDTP
concentration has been also investigated [13,19]. The sufficient
concentration of ZnDTP can lead to form a lot of MoS2 units and
diffuse in the phosphate matrix. These units can form a grown
 K. Komori, N. Umehara / Tribology International 84 (2015) 100–109 105

Table 2
Elemental composition and photopeak decomposition results from XPS analyses on the steel ball surfaces after tribotests.

ball Detected elements /at.% S2p, Mo3d/ % Ratio

C O P S Ca Fe Zn Mo SO24  , –SO3 ,  SO2  CS S2  Mo4 þ Mo5 þ Mo6 þ Mo(0) S2  /Mo4 þ Mo4 þ /Mo6 þ

Pre-structured DLC
A 48 26 2.6 9.7 1.9 3.3 1.3 7.0 0 0 100 69 15 16 0 2.01 4.31
B 56 23 0.5 8.9 0.8 3.8 0.8 6.5 0 0 100 75 8 12 5 1.83 6.25
C 46 27 1.1 12 1.0 4.2 1.2 8.1 2 0 98 75 9 15 9 1.87 5.00
D 90 8.3 0.1 0.2 0.5 0 0.2 0.1 18 0 82 64 15 22 0 2.56 2.91
E 52 23 1.8 9.5 2.2 2.8 1.0 7.7 0 0 100 71 11 13 6 1.74 5.46
F 54 25 2.8 7.2 2.9 1.9 2.1 4.6 0 0 100 72 7 17 5 2.17 4.24

DLC coated on polished substrates

a 45 26 2.8 11 2.0 1.4 2.8 8.5 0 0 100 79 9 13 0 1.56 6.08
b 35 39 4.1 4.7 5.9 4.3 3.7 2.1 0 0 100 64 14 15 7 3.50 4.27
c 36 38 2.3 3.8 2.7 12 2.4 2.1 0 0 100 62 14 14 10 2.92 4.43
d 36 31 3.5 10 2.4 5.5 2.5 7.8 0 0 100 61 9 12 17 2.14 5.08
a
e 41 40 1.0 15 0.5 0.4 0.3 1.6 0 0 100 33 11 35 20 16.2 0.94
f 30 41 4.5 5.4 5.4 6.7 3.9 3.2 0 0 100 71 2 19 9 2.38 3.74
g 33 41 3.2 4.3 5.4 7.4 3.2 2.5 0 0 100 56 14 17 13 3.07 3.29
h 32 39 3.3 5.3 5.2 5.6 3.7 5.0 0 0 100 58 4 21 17 1.83 2.76
i 36 36 3.4 6.8 5.4 4.4 1.9 5.2 0 0 100 62 14 15 10 2.11 4.13
j 33 41 2.6 5.0 8.0 3.1 2.9 2.3 9 0 91 50 10 31 8 3.96 1.61
x 34 37 4.9 6.5 2.5 4.7 4.3 3.3 0 0 100 67 15 18 0 2.94 3.72

a
worn out at early running-in period.

Table 3
Elemental composition and photopeak decomposition results from XPS analyses on the DLC disk surfaces after tribotests.

disk Detected elements /at.% S2p, Mo3d/% Ratiob

C O P S Ca Fe Zn Mo SO24  ,  SO3 ,  SO2- CS S2  Mo4 þ Mo5 þ Mo6 þ Mo(0) S2  /Mo4 þ Mo4 þ /Mo6 þ

Pre-structured DLC
A 86 11 0.1 0.2 0.8 0.8 0.2 o0.1 44 0 56 27 22 51 0 4.2 0.53
B 87 11 0.1 0.1 0.8 0 0.1 o0.1 46 0 54 17 14 69 0 3.2 0.25
C 87 11 0.1 0.2 0.9 0 0.1 o0.1 46 0 54 13 14 74 0 8.3 0.18
D 85 12 0.1 0.2 1.0 0 0.1 0.1 27 0 73 23 15 61 0 6.4 0.38
E 90 8.0 0 0 0.6 0 0.1 o0.1 0 0 0 0 53 47 0 – –
F 84 13 0 0.2 1.5 0 0.1 0.1 60 0 40 18 22 60 0 4.4 0.30

DLC coated on polished substrates

a 80 14 1.0 0.4 1.9 0 0.5 0.3 13 0 87 40 28 32 0 2.9 1.3
b 86 11 0.4 0.6 1.1 0 0.4 0.1 24 0 76 62 11 27 0 7.4 2.3
c 84 12 0.2 0.5 1.9 0 0.2 0.1 33 0 67 34 37 28 0 9.9 1.2
d 81 15 0.3 0.5 1.9 0 0.4 0.2 24 13 62 43 16 39 3 3.6 1.1
ea 53 28 0 0 1.9 8.7 0 0 – – – – – – – – –
f 85 12 0.1 0.3 1.5 0 0.2 o0.1 13 0 87 35 42 24 0 7.5 1.5
g 84 12 0.1 0.3 2.1 0 0.1 o0.1 26 0 74 57 35 8.0 0 3.9 7.1
h 81 15 0.1 0.2 2.8 0 0.1 0.1 29 0 71 47 26 27 0 3.0 1.7
i 82 15 0.1 0.3 2.0 0 0.2 0.1 20 0 80 14 37 49 0 17 0.29
j 84 13 0.2 0.6 0.6 0 0.2 0.1 30 0 70 62 16 22 0 6.8 2.8
x 86 8.7 0.4 0.5 1.9 0.3 0 0.1 33 22 45 20 33 47 0 11 0.43

a
worn out at early running-in period.
b
calculated by Mo: 0.1 at.% in case of Mo o 0.1.

lamellar sheet progressively and reduce the friction efficiently. The
low concentration of ZnDTP reduces the sulfuration, and the
presence of Mo-oxide is predominant. In this latter case, the
MoS2 sheets form isolated bundles in a carbon and oxygen rich
matrix. Then, these do not reduce the friction [13].
From the study of Mo3d photopeaks, the proportion of Mo4 þ on
the steel balls varies with the DLC samples, but typically more than
that of Mo5 þ and Mo6 þ . This Mo3d photopeak clearly indicates the
strong presence of Mo-sulfide in comparison with Mo-oxide. More-
over, the proportion of Mo4 þ on the pre-structured DLC surfaces is
stably more than that on the DLCs coated on polished substrates.
These results suggest that the surface roughness, hydrogen content
and mechanical properties of DLC coating affect the sulfuration on
the steel balls to vary the composition of tribofilm derived from
ZnDTP and MoDTC additives.
On the other hand, the peaks obtained on the DLC disks are
typically very weak, but it appears to be present effectively also on
the DLC surfaces, as shown in Table 3. Most of the lubricant
additives for current engine system are designed to interact with
ferrous-based materials. Many researchers have reported the inter-
action between DLC coatings and lubricant additives [23]. The
results are contradictory on whether some additive-derived tribo-
film formed or not. In this study, Table 3 shows that Zn and/or P
elements derived from ZnDTP additive are detected also on the DLC
surfaces in low proportion, typically a few atomic percent. No iron is
detected on the DLC surfaces, except the sample-A, sample-e and
sample-x. The iron on the sample-A and sample-x seems to be
transferred from the steel balls. The sample-e is the “worn-out”
sample as above mentioned. It appears that the ZnDTP-derived
tribofilm typically can be form even on the non-ferrous DLC
106
surfaces. However, no phosphorus is found on the DLC surfaces of
the sample-E and sample-F. It suggests that some of discrepancies
in the tribofilm formation on the DLC surfaces may result from
different DLCs being studied, and it can be varied depending on the
combination of DLC materials and micro-surface roughness of DLCs.
Calcium is typically detected on the DLC surfaces. Calcium
seems to be derived from Ca-sulfonate as a detergent-dispersant
additive in the engine-oil. Calcium is detected also on the steel
balls. It should be noted that the proportion of calcium on the DLC
surfaces is comparable to that on the steel surfaces, unlike the
other additive-derived elements. The quantitative variation of
calcium on the DLC surfaces tends to correspond to that of the
oxygen.
The S2p photopeaks on the DLC surfaces typically show the
contribution of sulfate, sulfonate and sulfone in addition to the
sulfide, unlike that on the steel ball surfaces. It is difficult to
correctly assign to these chemical components, but the sulfonate
might correspond to the Ca-sulfonate. The contribution of the C-S
chemical bonding is observed only on the sample-d and sample-x.
This is never observed on the steel ball surfaces, might correspond
to the thiuram disulfide. From the study of Mo3d photopeaks, the
proportion of Mo4 þ on the DLC surfaces is typically less than that
on the steel balls. In contrast, the proportion of Mo5 þ and Mo6 þ
on the DLC surfaces is much more than that on the steel balls.
These results generally indicate the additive-derived tribofilm
can be formed on the DLC surfaces, however, the sulfuration is
reduced on the DLC surfaces and the incomplete decomposition of
the MoDTC molecule is increased in comparison with the tribofilm
on the steel balls. In the comparison of the DLC surfaces deposited
by the same process, the sulfur and molybdenum elements
detected on the pre-structured DLC surfaces are typically less than
those detected on the DLCs coated on polished substrates. The
Mo4 þ proportion also shows a similar tendency. It is interesting to
notice that this tendency is converse to that on the steel balls.
From the viewpoint of the relation to friction behavior, the DLC
samples which exhibit the lower friction results (sample-B, C, E,
and a) typically show a lot of additive-derived elements on the
steel ball surfaces (in Tables 2 and 3). It is also noticed that these
samples show approximately 50 at.% carbon on the counter steel
balls. It is interesting that these DLCs, particularly the pre-
structured DLCs, can form the additive-derived tribofilm efficiently
with the relatively higher proportion of carbon on the steel balls.
On the other hand, for the sample-D which exhibits the higher
friction result, the additive-derived elements on the steel ball are
particularly tiny, but 90 at.% carbon that is much more proportion
than the other samples is observed as shown in Table 2. The
carbon on the counter steel seems to be primarily composed of
7.0
Pre-structured DLC
CVD-, ▲PVD-DLC on polished substrates
6.0
5.0
S2-/Mo4+ ratio
j
4.0
b E
c x
3.0 g D
f B
d i
2.0
h E C
a Pre-structured DLC
1.0
0 0.0
1 10
RMS roughness/ nm
2 4þ
Fig. 7. Variation of the S /Mo ratio with the surface roughness of DLC coatings.
K. Komori, N. Umehara / Tribology International 84 (2015) 100–109
transferred carbon from the DLC surfaces. Although the additive-
derived elements on the steel ball of the “worn-out” sample-e are
also tiny, this is due to the different reason from the sample-D. It
can be noticed that the additive-derived composition on the steel
ball of the sample-D is similar to that on the DLC surface, as shown
in Table 3. Therefore, it suggests that transferring of DLC-derived
carbon to the opposing steel surface during DLC/steel sliding
contact can lead to DLC/DLC contact.
The results suggest that the different combinations of the
micro-surface roughness and material of DLC coatings affect the
composition and formation of tribofilm, resulting the different
friction and wear behavior. The tribofilm derived from MoDTC and
ZnDTP additives is formed predominantly on the counter steel
surface involving carbon transferring. We discuss how the effec-
tiveness of the DLC coating properties on friction and wear
behavior is shown to depend on the tribo-chemical reactions
and the tribofilm compositions particularly on the steel balls, in
the following.
3.3. Relation between S2  /Mo4 þ ratio and surface roughness of DLC
Fig. 7 shows that the S2  /Mo4 þ ratio on the steel balls
continuously decreases with increasing the surface roughness of
the DLC, eventually reaching 2.0. The quantitative ratio S2  /Mo4 þ
of about 2.0 corroborates the presence of molybdenum sulfide
(MoS2) [24]. However, the hydrogen-free DLC (sample-x) presents
the higher S2  /Mo4 þ ratio regardless of its larger surface rough-
ness, and it appears to deviate from the tendency of the hydro-
genated DLC samples. We note that the “worn-out” sample-e
exhibits a remarkable high S2  /Mo4 þ ratio of about 16, so that it
is not shown in Fig. 7.
On the other hand, the S2  /Mo4 þ ratio of the pre-structured
DLCs generally indicates the value closer to 2.0, in comparison
with the DLCs coated on polished substrates. It is reasonable to
assume that the pre-structured surfaces of DLC coatings can
promote the tribo-chemical reactions leading to MoS2 formation.
3.4. Relation between coefficient of friction and tribofilm
composition
Fig. 8 shows the relation between the coefficient of friction and
the S2  /Mo4 þ ratio on the steel balls. The coefficient of friction
tends to be generally reduced with the decreasing S2  /Mo4 þ ratio
into 2.0. However, the pre-structured sample-D and sample-F, as
well as the DLCs coated on polished substrates plotted around
them, stays at the higher friction, although the S2  /Mo4 þ ratio for
0.1
0.09
D j
0.08 h i f c
b
Coefficient of friction
0.07 F g
d x
0.06 A
0.05
0.04 a C
F 0.03
B
A 0.02
0.01
CVD-, PVD-DLC on polished substrates
0
2.0 4.0 6.0
100 1000 S2-/Mo4+ratio
Fig. 8. Relation between the coefficient of friction and the S2  /Mo4 þ ratio on the
worn steel ball surfaces.
 K. Komori, N. Umehara / Tribology International 84 (2015) 100–109 107

these samples is relatively close to 2.0. The sample-D is equivalent 7.0

to the sample-E in hydrogen content and mechanical properties of enhanced B
a
DLC material, but the S2  /Mo4 þ ratio of the sample-D indicates 6.0
E
the higher value than that of the sample-E. It seems that the high
MoS 2 d C
friction coefficient of the sample-D is attributed to the lack of 5.0
formation c

sufficient sulfuration on the steel counterface, because the exces-
sive transferred carbon might lead to DLC/transferred DLC contact.
The sample-D has the smallest roughness in the pre-structured
DLC samples. It comes from the shot-peened substrate treated by
the lower shot pressure. The uniqueness of pre-structured DLC is
the combined surface structure which consists of the large
undulation from rough substrate and the mound by DLC growth.
If the undulation is small, it might lead to contact uniformly with
the large area. It might cause the excessive carbon transferring. For
the sample-F, the XPS result on the steel balls shows that the
detected quantity of S and Mo is smaller than the other samples
regardless of the S2  /Mo4 þ ratio close to 2.0, as shown in Table 2.
Then, to add another viewpoint, the XPS analysis of the Mo4 þ /
Mo6 þ ratio which suggests the quantitative ratio of MoS2 against
MoO3 is applied. Fig. 9 shows that the Mo4 þ /Mo6 þ ratio indicates
a good correlation with the coefficient of friction that is reduced
with increasing the ratio of Mo4 þ /Mo6 þ . These results suggest
that not only the S2  /Mo4 þ ratio as chemical states but also the
Mo4 þ /Mo6 þ ratio as quantitative factor of molybdenum sulfide in
tribofilm composition is very important in the relation with the
friction behavior.
It should be noted that the S2  /Mo4 þ ratio on the DLC surfaces
of the DLCs coated on polished substrates shows the similar
relationship with the coefficient of friction as that on the steel
balls. However, these absolute values are not comparable as shown
in Table 2. No significant relation is found clearly from the S2  /
Mo4 þ ratio on the DLC surfaces of the pre-structured DLCs. The
Mo4 þ /Mo6 þ ratio on the pre-structured DLC surfaces are typically
quite smaller than that on the DLCs coated on polished substrates.
Additionally, the Mo4 þ /Mo6 þ ratio on the DLC surfaces, regardless
of the difference in substrates, shows the small dependency on the
different DLC samples. It is difficult to find the remarkable relation
with the coefficient of friction (in Table 3).
3.5. Mo4 þ /Mo6 þ ratio and Hydrogen content of DLC
Fig. 10 shows that the Mo4 þ /Mo6 þ ratio from XPS analyses on
steel balls is decreased with increasing hydrogen content of DLC
coating. The pre-structured DLCs show the higher Mo4 þ /Mo6 þ
ratio than the DLCs coated on polished substrates with the similar
0.1
0.09
D tribofilm on the steel ball, but pare off the tribofilm immediately.
0.08 j f
h
Coefficient of friction
Mo4+/Mo6+ ratio
A i F
4.0 x b f
lack
g
3.0 D
h
2.0
j
Pre-structured DLC e
1.0
CVD-, PVD-DLC (worn out)
on polished substrates
0.0
0 10 20 30 40 50
Hydrogen content of DLC/ at.%
Fig. 10. Variation of the Mo4 þ /Mo6 þ ratio with hydrogen content of the DLC
coatings.
hydrogen content. The pre-structured DLC sample-B, C, and E
show the higher Mo4 þ /Mo6 þ ratio and exhibit the lower coeffi-
cient of friction, approximately 0.04. On the other hand, the Mo4 þ /
Mo6 þ ratio of the DLC sample-F which has rich-hydrogen and low
hardness indicates the lower value than that of the sample-E,
while the sample-E and the sample-F are similar in surface
roughness. These results show that the quantitative ratio MoS2/
MoO3 of the DLC coatings, which have larger roughness and/or
higher hardness, tends to increase generally. It appears that
molybdenum sulfide formation is more favorable to the tribologi-
cal contact energetically than the molybdenum oxide.
It seems that the pre-structured surface of DLC coatings can
promote MoS2 formation effectively to increase the Mo4 þ /Mo6 þ
ratio. The correlation between the Mo4 þ /Mo6 þ ratio and hydrogen
content of DLCs shifts into a “new trend line” for the pre-
structured DLC coatings from that for the DLCs coated on polished
substrates, as shown in Fig. 10.
However, the result shows that the Mo4 þ /Mo6 þ ratio of the
sample-A indicates the lower value than that of the sample-B, C,
and E, although the sample-A which has the high hardness and the
large roughness is expected to promote the MoS2 formation
leading to low friction. According to the results of the friction
behavior and the excessive wear on the steel counterface of the
sample-A, it is reasonable to assume that the aggressive properties
of this DLC coating prevent the stable MoS2 formation on the steel
counterface. We notice that the 0.8 at.% of iron is detected on the
surface of the DLC coatings in evidence from the XPS results (in
Table 3). Therefore, it suggests that this sample-A can form the
ib c
These repeat might show the slow friction reduction as shown by
Fig. 2. Similarly, the sample-D shows the lower value in the Mo4 þ /

0.07 F
g x d Mo6 þ ratio. But, it seems to come from the excessive carbon
0.06
A transferring on the steel ball as mentioned above.
0.05 Although the different reason, the both of these sample-A and
E a
0.04 sample-D preventing the stable tribofilm formation stays around
C B the trend line of the DLCs coated on polished substrates. Also, for
0.03 the DLCs coated on polished substrates, a hydrogen-free DLC
0.02 coating (sample-x) appears to affect similarly as the former
Pre-structured DLC
sample-A, because of the remarkable high hardness and the larger
0.01
CVD-, PVD-DLC on polished substrates roughness come from the sp3-rich carbon bond structure and the
0 PVD process. The sample-e, which worn remarkably, does not
0.0 2.0 4.0 6.0 8.0
show the stable MoS2 formation, too. Conversely, the sample-d
Mo4+/Mo6+ ratio and the sample-i, which have the larger surface roughness, are
Fig. 9. Relation between the coefficient of friction and the Mo4 þ /Mo6 þ ratio on the plotted rather close to the trend line of the pre-structured DLC
worn steel ball surfaces. samples.
108
25
Pre-structured DLC
CVD-, PVD-DLC on polished substrates
20
Proportion of Mo(0)/ %
15
c i
10
b substrates exhibit the highly wear within the 25–40 at.% range of
5
x a A D
0
0 10 20
Hydrogen content of DLC/ at.%
Fig. 11. Variation of the Mo(0) proportion with hydrogen content of the DLC
coatings.
We note that a “trend line”, strictly speaking, should be defined
with a uniform contact regime and a surface asperity quantified by
contact model, but the tendency is clearly visible in this case by
comparing the DLCs on pre-structured substrates and polished
substrates. The results imply that the tribofilm composition would
be mainly dominated by a certain thermal energy or a certain
contact pressure generated depending on the hydrogen content,
hardness, and/or surface roughness of DLC material, through the
chemical reactions during tribological contact, essentially.
3.6. Mo(0) and Hydrogen content of DLC
The XPS analysis of Mo(0) suggests the presence of the metallic-Mo
or Mo-carbide, as above-mentioned. Fig. 11 shows that the Mo
(0) proportion of the DLCs coated on polished substrates increases
remarkably within the 25–40 at.% range of hydrogen content of DLCs,
while the Mo(0) is not observed particularly on the hydrogen-free DLC
(sample-x) surface. As reported in Fig. 10, the result implies that the
proportion of MoO3 would be increased with an increasing hydrogen
content of DLC coatings. Then, it seems that the metallic-Mo and/or
Mo-carbide are generated as the result of reduction from molybdenum
oxides (MoO3 and MoO2) in the presence of plenty hydrogen and
carbon [16,25]. Moreover, the higher the hydrogen content of DLC
coatings, the lower the hardness of that. It is related to the transforma-
tion of carbon bond structure and transferring during tribological
contact. Such transformation of diamond-like to graphite-like carbon
will occur under thermal and strain effects from repeated sliding, even
without chemical reaction with additives [9]. Simultaneously, these
chemical reactions would lead to promote transformation of DLC
material to further weak graphitic structure involving hydrogen evolu-
tion and destabilization of carbon bond structure. Thus, it suggests that
the wear of DLC coatings can be increased significantly. It is interesting
to notice that the “worn-out” sample-e presents the highest value at
the peak in the Mo(0) proportion, as shown in Fig. 11. It should be
noted that Mo(0) can be an indication of reduction of Mo-oxides, but
all the detected amount of Mo(0) should not necessarily correspond to
the wear amount of DLC coatings, one-to-one, because it might include
the chemical reactions with the transferred carbon, the other carbo-
naceous or the hydrocarbon. Moreover, the Mo(0) are almost not found
on the DLC surfaces (in Table 3), so that such chemical reactions might
be caused on the steel ball side involving the carbon transferring from
DLC. It implies that the wear in the presence of MoDTC might be
caused not only due to chemical reaction with DLC but also due to
carbon transformation and transferring, moreover, forming the Mo-
carbides of high hardness compounds might be concerned.
K. Komori, N. Umehara / Tribology International 84 (2015) 100–109
On the other hand, the proportion of Mo(0) is decreased with the
more than 37 at.% range of hydrogen content. It seems that the DLC
coatings with highly hydrogen content cannot give the sufficient
e (worn out)
energy to generate chemical reaction, because of their low hardness
and elastic modulus. In particular, the wear of the DLC with more than
h
d 40 at.% hydrogen content occurs mainly due to its low hardness. The
chemical reaction at the nearly 37 at.% hydrogen content appears to be
g
critical in terms of which the chemical properties or the mechanical
properties strongly concern, depending on the DLC material and
f surface roughness. Actually, the hydrogenated DLCs coated on polished
j
E
B hydrogen content, in the engine-oil containing MoDTC and ZnDTP
F additives. The DLC coatings which have smaller roughness (sample-b,
C c, e, and g) show remarkable wear (in Fig. 6). Moreover, it is reported
that such significant wear has not been observed in the case of
30 40 50 lubricating with the base-oil not containing any friction-modifier
additives and antiwear agents [26].
In contrast, the Mo(0) proportion of the pre-structured DLCs
exhibits generally lower value than that of the DLCs coated on polished
substrates, as shown by Fig. 11. As reported in this study, the wear
behaviors of the pre-structured DLCs are clearly improved to unde-
tectable extent, even for the sample-E and sample-F with highly
hydrogen content. It appears that the surface structuring can have
positive effects on the tribological behavior of DLC coating in terms of
contact mechanics. One important factor of the positive effects seems
to be the concentrated contact to build up the tribofilm energetically.
Another factor seems to be the appropriate separation of the surfaces
in asperity geometry and height distributions. If the surfaces are too
smooth and not well-separated, it might cause increasing of the local
contact areas involving the DLC transformation, suggesting an increas-
ing wear of hydrogenated DLC. In either case, the proportion of Mo
(0) is stably reduced by surface structuring, although the interaction
between DLC material and MoDTC might be sensitive.
These results show the controlling micro-surface morphology has
the possibility of inhibiting the wear of hydrogenated DLC coating from
increasing, as well as it can enhance the MoS2 formation effectively, in
the presence of MoDTC. It suggests that the tribo-chemical react-
ions are also related to the wear of DLC coatings, in terms of the
molybdenum sulfides formation and the reduction of molybdenum
oxides, involving carbon transformation and transferring.
As prospects for the future, more study is needed to understand
the interaction between micro-surface morphology of DLC coating and
tribofilm formation. At the moment, only assumption can be con-
sidered based on the surface roughness of DLC coatings. Not only
surface roughness but also shape of mound in asperity geometry
should be considered. Moreover, the dependency of lubricant tem-
perature and sliding velocity on the chemical reactions is also need to
investigate. It will be essential to understand the effects of contact
regime on how to cause the tribo-chemical reaction and form the
tribofilm by thermal and strain effects.
4. Conclusions
In this study, we investigate the tribological effects of surface
morphology of hydrogenated DLC coatings during the DLC/steel sliding
contact with the lubricated engine-oil containing MoDTC and ZnDTP
additives. To obtain the different surface roughness of DLC in asperity
geometry, the “pre-structured DLC” coatings, which are deposited on
the micro-shot peened rough surface substrates, are prepared.
Different tribo-chemical reactions occur depending on the
combination of surface morphology and material properties of
DLC coatings, resulting the different friction and wear behavior.
XPS results show that the additive-derived tribofilm on the DLC
surfaces is typically tiny and the compositions are different from
that on the steel surfaces. The tribofilm derived from MoDTC and
 K. Komori, N. Umehara / Tribology International 84 (2015) 100–109
ZnDTP additives is formed predominantly on the counter steel
surface involving carbon transferring.
The effectiveness in friction and wear behavior is shown to
depend on the tribo-chemical reactions and the tribofilm compo-
sitions. The DLC coatings, which have the larger surface roughness
and/or the higher hardness, show the higher ratio of MoS2/MoO3
in tribofilm, leading to the lower friction coefficients. The results
imply that the tribo-chemical reactions are related not only to the
Mo-sulfides formation, but also reduction of Mo-oxides and Mo-
carbides formation in the presence of plenty hydrogen and carbon.
Hydrogen evolution and transformation of DLC to weak graphitic
structure suggests an increasing wear of DLC.
The pre-structured DLC coatings show the positive effects to
improve the friction and wear behavior effectively in comparison
with the equivalent DLC materials coated on polished substrates.
An important factor of the positive effects seems to be the
concentrated contact to promote the MoS2 formation energeti-
cally. However, excessive attack against the counterface, or insuffi-
cient tribo-chemical reaction seems to be an obstacle to generate
low friction, depending on the combination with DLC materials.
Surface structuring for DLC coating has a great possibility of
responding to the both low friction and wear resistance requirements
under lubricated condition. The lubrication trends shift toward appli-
cation of low-viscosity lubricants to improve fuel economy. The
tribological interaction among DLC coatings, lubricants and additives
will play an important role in making the best use of boundary and
mixed lubrication potential.
Acknowledgments
The authors would like to thank Mr. M. König, Mr. C. Hormann,
Mr. B. Blug, and Dr. S. Meier, from Fraunhofer-Institut für Werkstoff-
mechanik IWM, Freiburg, Germany, for co-operating with fabrication,
characterization of DLC coatings, and valuable discussions.
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