Transient Processes in Tribology

G. Dalmaz et al. (Editors)

9 2004 Elsevier B.V. All fights reserved

45

Mechanism of metal doping effect on lubricity of DLC films

T. Numata and S. Sasaki
Research Institute of Mechanical Systems Engineering, AIST
Namiki 1-2-1, Tsukuba, Ibaraki, 305-8564, Japan

DLC films show the excellent tribological properties under th e lubrication with humid air or water. However,
lubricity of industrial oils for DLC films is not so good compared with conventional tribo-materials. It is
considered that the lubricant additives do not act on the DLC surface, because of chemical stabilities of carbon.
Recently, metal elements doped DLC films were developed in order to improve the adhesion property and the
lubricity. In this paper, lubrication mechanism of Ti doped DLC films were discussed with the results of friction
test and surface analysis. The sliding surfaces were analyzed by using the TOF-SIMS.

1. INTRODUCTION
Diamond-like-carbon (DLC) coatings exhibit
excellent properties required for a protective coating
material: chemical inertness, low coefficient of
friction and wear resistance. Therefore, DLC is
expected for application of sliding parts in engine.
DLC films show the excellent tribological
properties under the lubrication with humid air or
water. However, lubricity of industrial oils for DLC
films is not so good compared with conventional
tribo-materials. It is considered that the lubricant
additives do not act on the DLC surface, because of
chemical stabilities of carbon. Recently, metal doped
DLC films were developed in order to improve the
adhesion property and interaction of lubricant
additives [1-3].
On the other hand, owing to the excellent
antiwear,
anti-oxidation
and
anti-corrosion
properties, zinc dialkylthiophosphates (ZnDDP) and
molybdenum dialkyldithiocarbamate (MoDTC) have
been used as lubricant additives. So far, many
studies on the frictional characteristics of these
additives have been reported to the mechanism of
reduction in friction [4-9]. Martin et al was reported
that anti-wear mechanism of ZnDTP have been
explained Hard and Soft Acids and Bases (HSAB)
principle [7]. Muraki et al indicated that preferential

formation of products through the decomposition of

ZnDTP has a role in enhancing wear resistance and
promoting the formation of MoS2 [9]. On the other
hand, it has been reported that the combinations of
additives like ZnDDP can modify the friction and
wear
performance
of
organo-molybdenum
compounds (OMC) [10-11]. It is suggested that a
competitive
reaction
between
phosphorus
compounds and OMC occur at the rubbing surface.
However, frictional property of ZnDTP and MoDTC
on metal doped DLC surface is still not fully
understood.
In this paper, lubrication mechanism of titanium
doped DLC films (Ti-DLC) were discussed with the
results of friction test and Time of Flight Secondary
Ion Mass Spectroscopy (TOF-SIMS) analysis.

2. EXPERIMENTAL
2.1. Materials
Two types of DLC samples were used in this
study. One is a deposited by CVD on stainless steel
plate (DLC). Another is a Ti doped DLC deposited
by PVD on stainless steel plate (Ti-DLC). The
hardness of both DLC was 20 GPa.

46

Fig. 2 Effect of lubricant additives on Lubricity of DLC

Three different lubricant blends were prepared
by mixing MoDTC and ZnDTP in PAO base oil.
One is PAO base oil. Second is mixing 500ppm of
ZnDTP in base oil. Third is mixing 500ppm of
ZnDTP and 200ppm of MoDTC.

were as follows: 50Hz of oscillation frequency,

lmm of distance, 20N of load, 50~ of temperature,
and 60min of test duration.
After the sliding experiment, TOF-SIMS was
used for chemical analysis of wear tracks. Positive
and negative secondary ions were detected in this
study. The analytical conditions were as follows:
Ga primary ion gun and 60. m square of analysis
area.

2.2. Sliding test

Sliding experiment was carried out using pin on
plate type Oscillating tribotester. Fig. 1 shows a
summary of the tribotester. In this, a steel ball
oscillated under load on flat DLC surface. The
friction force between the two specimens was
measured with load cell. Experimental conditions

-~
~

0.5
0
0.5
1.0

O-

0.5
0
0.5
1.0
1.5

S-

P~)2

PO3-1

DLC

Pi3-

Ti-DLC
SO 4-

H
C2HCH-

1.5

.,.i

3. RESULTS AND DISUCCUSION

Component in
wear ~

S-

po 2PO1

Component in
original surface

CH-

H20

40

60
Mass, amu

Fig. 3 TOF-SIMS spectra observed from DLC surfaces

(PAO + ZnDTP + MoDTC)

80

100

47

1.2x10-~.

1.4x10 4
1.2x10 4

P-

1.0xl0 s

1.0xl0 4.

t~
"~
8.0xl 0 4

8.0X103"
>2
9~ 6.0X103,

6.0xl 04
wear track

4.0x103.

~f

2.0X103.

~I~ 4.0xl 0 4

~_.____~ Ti-DLCoriginal
DLC wear track

31'.0
Mass, amu

"

Ti-DLC original

2.0x104'

DLC original

0.0.
30.9

k ..._ Ti-DLCweartrack

0.0 i
31.8

31'.1

S~,~231'.9

(a) Around mass 31amu

DLC wear track

DLC original

32.0
"
Mass, amu

32.1

32.2

(b) Around mass 32 ainu

Fig. 4 Narrow spectra around mass 31 and 32 amu

Lubricant: PAO + ZnDTP + M o D T C
T i - D L C was decreased in case of P A O + Z n D T P +
MoDTC.

3.1. T r i b o l o g i c a l test
Fig. 2 gives the friction coefficient of the steel
b a l l / D L C plate pair lubricated with P A O oil
containing the Z n D T P and M o D T C . T h e s e values
are friction coefficient at steady state. It can be seen
that the friction coefficient of D L C was did not
c h a n g e d each lubricant. Therefore, these lubricant
additives d o n ' t affect friction coefficient of D L C . In
case of T i - D L C lubricated with P A O and P A O +
Z n D T P , the coefficient of friction was same value to
D L C . On the other hand, the friction coefficient of
4.5x104

3.2. Surface analysis

Fig. 3 s h o w s subtract spectra of the inside and
outside of wear track. T h e f r a g m e n t ions originated
from lubricant additives such as S , PO2-, PO3, S O 4
were detected mainly inside wear track. Furthermore,
the fragment ions of Fe +, Ti +' Zn +, M o + were
detected in positive spectra (not s h o w n ) . This result
indicates that these lubricant additives absorbed on
wear tracks. Martin and c o w o r k e r s have reported
6.0x103

Zn +.

Mo +

4.0x10 a
3.5x10 ~
= 3.0xl 04
O
2.5xl fit
.-_ 2.0xl fft~

~ 4.0xl 03

Ti-DLC
wear track
_

1 5x10
-- 1.0xl0-t~

Ti-DLC original
DLC wear track
DLC original

./"x.__

5.0x10 ~
0-0 i
63.8

Ti-DLC wear track

63.9

" 6,~.0 "

Mass, amu

6,~.1 ....... 6,~.2

"~

~~~'kf7nl

4+

2.0xlO 3

Ti-DLC original
~-DLC wear track

0.0

DLC original

--'=

97.6

(a) Around mass 64amu

9"].8

98.0
"
Mass, amu

(b) Around mass 98 amu

Fig. 5 Narrow spectra around mass 64 and 98 amu

Lubricant: PAO + Z n D T P + M o D T C

98.2

98.4

48

Fig. 6 Chemical image of wear track on Ti-DLC

Lubricant : P A O + ZnDTP + MoDTC
Image size : 60 x 60 lam
that zinc polyphosphate was generated by
tribochemical reaction of ZnDTP [7]. Therefore, it is
considered that POx- fragment ions in wear track
were generated by the tribochemical reactions of
ZnDTP.
Fig. 4 shows narrow spectra around mass 31 and
32amu from DLC and Ti-DLC surfaces. It can be
seen P- and S- originated from these lubricant
additives detected on the wear track of both DLC
surfaces. Additionally, intensity of P - a n d Sfragment ions of Ti-DLC were stronger than at wear
track of DLC. Fig. 5 shows narrow spectra around
mass 64 and 98amu obtained from DLC and Ti-DLC
surfaces. Zn and Mo were clearly observed on the
wear track of each DLC. Furthermore, large amount
of Zn and Mo were detected on wear track of TiDLC.
From these results, it is clearly indicated that
lubricant additives easily adsorbed on the Ti-DLC
surface. Therefore, it is considered that large amount
of Molybdenum compounds was generated on the
wear track of Ti-DLC. Grossiord and coworkers
have been investigating that tribochemical reaction
of MoDTC using XPS and TEM analysis. They were
reported that the formation to MoS2 by
tribochemical reaction of MoDTC under the sliding
condition [8]. It its reasonable explains that the
Molybdenum sulfide play important role on low
coefficient of friction in case of Ti-DLC/PAO +
ZnDTP + MoDTC.
TOF-SIMS image of inside wear track of TiDLC lubricated PAO + ZnDTP + MoDTC was
shown Fig. 6. It can be seen that elemental
distributions of Ti and Zn ion were different on the
wear track. Therefore, we were defined Ti rich
region and Zn rich region.

Fig. 7 Chemical component of wear track on Ti-DLC

Lubricant" PAO + ZnDTP + MoDTC
Fig. 7 shows chemical property of two regions
calculated from TOF-SIMS spectra obtained from
two regions. In this result, the intensity ratio is ratio
of intensity of fragment ion in wear track and out
wear track. It can be seen that large intensity ratio of
Zn and PO3 was detected in Zn rich region. This
result suggested that a large amount of zinc
phosphate was generated in Zn rich region.
Furthermore, TiO2 was detected in Zn rich region.
Schroeder and coworkers have been investigated
chemical properties of Ti containing DLC by XPS
analysis [12]. They were reported that the chemical
state of Ti in DLC film was oxide and carbide.
Therefore, TiO2 was existed on DLC surface
originally. However, since the intensity ratio of TiO2
was larger than 1, TiO2 in wear track was increased
by oxidation of Ti. In Zn rich region, the intensity
ratio of Ti was 0.4. This value means that the
intensity of Ti was smaller than outside wear track.
It can be considered that a thick zinc phosphate layer
was existed on top of Ti-DLC surface. Therefore,
the intensity of Ti at Zn rich region becomes
smaller.
On the other hand, large amount of Mo MoS
and MoO were detected in Ti rich region. Since
amount of Mo compounds in Ti rich region is larger
than Zn rich region, the Ti rich region play more
important role on low friction property of Ti-DLC.
These results suggested that ZnDTP and MoDTC
were competitive absorbed on the wear track of Ti-

49
DLC. Therefore, the Mo intensity of Zn rich region
was decreased by ZnDTP.
The intensity ratio of Ti was more than 1.0 as
shown in Fig. 7. This result means that the chemical
state of Titanium was changed by sliding experiment.
Additionally, sulfur containing species (TiS+~ ZnS
MoS are detected in the Ti-rich region. These
results suggested that formation to titanium sulfide
by the reaction of titanium. Since TiS was detected
on outside of wear track, this reaction is possibly
thermal reaction.

4. SUMMARY

Lubrication mechanism of titanium doped DLC

films were discussed with the results of a friction
test and Time of Flight Secondary Ion Mass
Spectroscopy analysis. The results can be
summarized as follows:
1. Ti doped DLC was indicated low friction
coefficient at ZnDTP and MoDTC was used as
lubricant additives.
2. Tribochemical reactions of ZnDTP and MoDTC
were detected by TOF-SIMS analysis.
3. From TOF-SIMS analysis, it is clearly indicated
that lubricant additives easily absorbed to the TiDLC surface.

ACKNOWLEGEMENTS

The author would like to thank S. Mori and H.

Nanao from lwate University, for performing TOFSIMS analysis. The author also thanks M. Miyanaga

from Sumitomo Electric industries and T.

Nakahigashi from Nippon ITF for providing DLC
samples. The author also thanks T. Sato from
TonenGeneral Sekiyu K.K. for providing oil
samples.

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