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 Proceedings of the ASME 2015 International Mechanical Engineering Congress and Exposition
TRIBOLOGICAL BEHAVIOR OF CARBON BASED MATERIALS
Dr. Yılmaz ÖZMEN
Pamukkale University, Biomedical Engineering Department,
Denizli, TURKEY
ABSTRACT
Diamond-like carbon (DLC) films have excellent
tribological properties. These include low friction, high
wear resistance, high corrosion resistance, and a high anti-
seizure resistance. DLC film with and without Si doping
(due to its promising effect on friction coefficient), at
approximately 1-2 µm thickness, was synthesized by a
reactive ion plating method using C6H6 source on WC-Co
substrate. Si addition on tribological properties of DLC was
evaluated. The effects of relative humidity and contact load
are also investigated. When the Si content was increased
above 5.9 at. %, tribological properties of the coating were
deteriorated. These properties are, however, affected by
film deposition parameters and sliding conditions such as
normal load, sliding speed, mating materials, and
atmospheric conditions. The effect of environment is
particularly significant.
INTRODUCTION
Number of factors influence tribological performance of
mechanical systems. These factors include, type of
materials, contact stresses, surface hardness and roughness,
number of cycles, lubricants, coatings, solution particle
count and distribution, oxidation of materials, and surface
abrasions of both materials, etc. The search continues for
novel materials, coatings, and lubricants (both liquid and
1 Copyright © 2015 by ASME
IMECE2015
November 13-19, 2015, Houston, Texas
IMECE2015-50233
solid) that can potentially reduce friction and wear. In micro
and nanotribology, most exciting materials will be advanced
carbon materials, such as DLC, carbon nanotubes (CNT),
graphene and fullerene (C60) to be strong candidates for
possible application in nanotribology. Tribology study on
these materials started in the late 1990s. Reducing friction
and wear-related mechanical failures in moving mechanical
systems has gained increased attention due to friction’s
adverse impacts on efficiency, durability, and
environmental compatibility.
The ability to form versatile structures and networks makes
carbon one of the key elements of life and material sciences.
In combination with other elements it offers endless
structural possibilities. Even with no other elements in the
structure, carbon exhibits its originality and diversity in so-
called allotropes. Generally, they are divided into four
groups: (a) zero dimensional (fullerenes), (b) one
dimensional (carbon nanotubes—CNTs), (c) two
dimensional (graphene) and three dimensional (graphite and
diamond).
The field of carbon-based materials and coatings has
enjoyed strong and growing interest from all kinds of
scientific disciplines and industries during the last three
decades, because it is one of the most remarkable elements

Figure 1: Schematic representation of hardness and
coefficients of friction (COF) of carbon-based and other
coatings [1].
among all others in the periodic table. Since carbon-carbon
covalent bonds are among the strongest in nature, its
allotropes would ideally produce an exceedingly strong
material. It exists in more than 90% of all known chemical
substances and has the largest number of allotropes. Carbon
has been the driving force behind several technological
revolutions: in the 19th century, energy production by
burning carbon was integral to the industrial revolution; in
the 20th century, carbon-based plastics revolutionized the
manufacturing industry; in the 21st century. Other than
graphitic carbon, CNT and graphene might be a key
component in a third technological revolution, due to their
exceptional properties such as super-high hardness and
thermal conductivity, like in diamond (Fig. 1). Overall, the
exceptional tribological behavior of carbon-based films or
solid lubricants appears to be due to a unique combination
of surface chemical, physical, and mechanical interactions
at their sliding interfaces. These films have attracted even
more interest, and they are still the subject of numerous
scientific studies [1-5].
Mechanical efficiency and material damages in moving
mechanical systems due to friction and wear still remains
one of the greatest challenges of our time [6, 7]. At present,
using various forms of carbon-based nanomaterials to
reduce the wear in general is gaining high momentum. DLC
is the wide known material or coating that can provide both
high hardness and low friction under dry sliding conditions.
Figure 1 illustrates this point better by categorizing various
classes of tribological coatings with respect to their typical
hardness and friction values [1].
The understanding of tribological phenomena in amorphous
carbon-based lubricant/coating materials appears rather
complicate due to their complex structure and the great
dispersion in tribological results depending on the synthesis
procedure and testing conditions. Carbon is an unusual
material in that it exhibits both metallic and nonmetallic
characteristics. Carbon exists in both crystalline and
amorphous forms [8, 9]. The layers (basal planes)
themselves are relatively far apart and the forces that bond
them are weak van der Waals forces. These layers can align
2 Copyright © 2015 by ASME
themselves parallel to the direction of the relative motion
and slide over one another with relative ease, thus providing
low friction. Strong interatomic bonding and packing in
each layer is thought to help reduce wear. Operating
environment has a significant influence on lubrication, i.e.
low friction and low wear, properties of graphite. It
lubricates better in a humid environment than a dry one [10].
Also, the development of the lubricant high-toughness
nanocomposites made of small crystals of a hard phase
embedded in a soft matrix (usually carbonaceous) needs
further characterization [11, 12].
Specifically, it has been postulated that active chemical
species (such as hydrogen, oxygen, and water molecules) in
the test environment can easily attach to and passivate the
dangling σ bonds of carbon atoms on the surface of diamond
and DLC films. Apparently, when such bonds are
completely passivated, the adhesion component of friction
is drastically reduced [13-15]. Conversely, if these bonds
are reactivated by ion-beam etching or thermal desorption
of chemical species from the surface, their friction
coefficients increase dramatically, presumably because
reactivated σ bonds are free to participate in strong adhesive
interactions across the sliding contact interfaces and hence
cause very high friction [16-18].
Si doped DLC have been investigated by researchers
because of its promising results under different humidity.
The friction coefficient is said to be less dependent on
humidity [19]. In this paper, we discuss C allotropes, i.e.,
DLC coating applications in friction and wear related fields,
such as engines components, bearings and cutting tools for
metal working operations. Wide scattering data show
improved response of these materials under sliding contact
[20]. This enhanced tribological performance of the C
allotropes containing DLC was attributed to the special role
played by C structures, acting as solid lubricant and
modifying. The purpose of this paper to evaluate the effect
of Si addition on tribological properties of DLC. The effects
of relative humidity and contact load are also investigated.
EXPERIMENTAL PROCEDURE
DLC films were synthesized by reactive ion plating onto
WC-Co alloy chips 20x20x5 mm to perform the tribological
tests and also onto silicon wafer for film thickness
measurement as detailed in [21]. Parameters in the DLC
coating are seen in Table 1. Deposition rate was
approximately 0.3-0.5 m/h. Hardness was measured by a
nano hardness tester and surface roughness was measured
by a non-contact surface profilometer. Si and O contents
were measured by Auger electron spectroscopy (AES).
 Figure 2: Schematic drawing of DLC coating process by
reactive ion plating (a), and Graphene coating process by
CVD (b).

Table 1: The deposition parameters of DLC films.

DLC film Si-DLC film

Substrate WC-Co WC-Co
Gas C6H6 C6H6+(CH3)6Si2O
Pressure 0.3 Pa 9.33x10-2 Pa
Bias voltage -2300 V -1000 V
Hardness 28 GPa 21 GPa
Si content ~20 atom %
O content ~1.5 atom % Figure 3: Ball-on-plate tribo-testing system with humidity
Film thickness 1,5 m 1,2 m control.
Surface roughness Ra: ~1 nm Ra: ~1.3 nm

DLC coated plate specimens sliding against a stationary SiC

ball 4.8 mm in diameter were examined under two different
relative humidity conditions 20% (LH) and 80% (HH)
(±5%) using an air-tight reciprocating friction and wear test
system at 100 cycle/min and 5 mm stroke for total duration
of 2 hours (Fig. 3). Specimens were cleaned in benzin and
acetone solution ultrasonically, and dried in vacuum. In
every step, optical photographs were recorded immediately
after the stopping of each test. For every case, scanning
electron microscope SEM. images were also taken. Friction
force was recorded automatically by a PC and processed
after the test was finished. The wear rate was calculated by
measuring the volume of the wear track. Testing time and
load were selected for the purpose of understanding the
failure mechanism of the DLC film. The loads (1 N and 2
N) have been decided by a rough experiment and our
previous experience.
RESULTS and DISCUSSIONS
Hardness of the films (Fig. 4) was measured by nano-
indentation. In addition, scratch resistances were measured
to clarify the adhesion (critical load) of the films to the
substrate (Fig. 5). Although the hardest (23.8 GPa) film is a
pure DLC, its adhesion is the poorest about (320 mN).
When the small amount of Si (1.6%) is added, the adhesion
is increased considerably about 580 mN without losing
much the film hardness value (22.4 GPa). Continuing to
increase the Si content decreases the adhesion and hardness
steadily.

3 Copyright © 2015 by ASME


0 5 10 15
Si (at. %)
Figure 4: Nano-indentation harness of the Si-DLC films vs
Si concentration.
1,61 5,91
Si (%):
1,61 5,91
800
Critical Load (mN) (Bars)
600
400
200
0 0
1 2
Number of Exp.
Figure 5: Scratch resistance of Si-DLC films and friction
coefficients at failure point.
The friction forces were recorded throughout the
experiments and converted to friction coefficient (Fig. 6).
During experiments sometimes severe pikes are seen in the
friction coefficients and then it reaches steady state
situation. Thus, we take average friction coefficients to
compare the results at the end of experiments, are seen in
figure 7. Each value corresponds to a new ball contact point
and sliding track on the specimens. It is seen in figure 7, that
increasing Si amount up to certain level (5.9 %) decreases
friction coefficient to around 0.1. Then, it increases above
0.2 and the film becomes more prone to fail. It could be
because, the most of the Si in these films is expected to be
bonded to carbon. Therefore, when the Si amount increases,
this is more likely to happen and SiC-like structures takes
place. Considering the ball materials as SiC, it may increase
adhesion of two similar mating materials, and so that
bearing higher friction coefficient. While the friction
coefficient trends are almost same versus Si concentration
in all experimental conditions, DLC film containing Si 5.9
% (HH) and 8.9 % (LH, HH) failed in an early stage under
the 2 N normal load, with the exception of the film having
15.5 % Si. Generally speaking Si amount after certain level
30 (5.9 %) did not render the friction property of our DLC film
Hardness (GPa)
25 under HH. Apparently, friction and wear mechanism
20
phenomena have been changing and it needs more study to
15
10 reveal these results. There appears no clear advantages in
5 terms of friction coefficient between Si-DLC/SiC pair.
0 However, Si might be used up to this extend to tailor friction
20 coefficient under relatively low humid environment.
The wear rates of these experiments versus Si content is
given in figure 8. Total wear volumes were assessed by
taking profile of a wear track at three different points along
the track by optic profilometer at the end of each test.
Increasing Si concentration after certain level (5.9 %)
adversely affects wear rates in all cases. Wear and friction
8,91 15,54 coefficient correlation is difficult to establish. Like friction
8,91 15,54 coefficient, wear is also affected badly from increasing
amount of Si. Furthermore, our films also includes O
0,4 coming from sources gas that expected to act either as
Friction Coefficient at Failure (Points)
lubricant or and agent for tribochemical wear depending on
0,3 the relative humidity.
The properties of the film strongly depend on the conditions
0,2 at which it is prepared and environmental conditions. Wear
rates and friction coefficients at the end of each test have
been given from our studies. At the same time, for the case
0,1 of DLC film without Si interface, there is a good correlation
between wear rate and friction coefficient. However, this
harmony disappears for the DLC/Si coating. This may be
3 due to the Si interface, although the reason remains to be
clarified.
From characterizations of our DLC films, one can depict the
frictional behavior of carbon-based materials in general,
DLC films in particular is controlled by a number of
extrinsic (test condition specific) and intrinsic (film
specific) factors. When the humidity condition is varied, the
failure mode of films seems to change: under one humidity
condition films may be worn off, but they may allegedly
peel off by fatigue under another humidity condition as
further explained below and [19].
It is important to remember that most of these hypotheses
are based on observations made on a specific DLC film
tested under very specific conditions. The family of DLC
coating is rather large and, depending on the deposition
method and/or condition, graphite like phases and large
amount of hydrogen may be present in their structures.
Therefore, the proposed friction mechanism should not be
regarded as universal and applicable to all carbon films
designed as DLC.
4 Copyright © 2015 by ASME
 HH-100 CPM-1 N
HH-100 CPM-2 N
2 LH-100 CPM-1 N
Friction Coefficient

1,5

1
(a) (b)
0,5
Figure 9: SEM images of DLC without Si interface
0
0 5000 10000 15000
CYLE

Fig. 6: Sample friction coefficient throughout test of DLC

versus 15.5 % Si content. Figure 10: Optical images of DLC without Si interface
(total sliding distance 5 mm).

Example of the SEM (Fig. 9) and optical (Fig. 10) images

have been shown. From figure 9, in general, one may judge
HH-100 CPM-1 N LH-100 CPM-1 N
HH-100 CPM-2 N LH-100 CPM-2 N
the failure of DLC films existed and debris (third body)
0,45
Average Friction Coefficient

formation. However, examination of the topographies

0,4
0,35
together of the wear tracks convey some more
0,3 understanding on wear mechanisms. In figure 10, taken just
0,25 after the complete failure of the film, reveals that it is a
0,2 brittle failure mode. It is seen that, after reaching the critical
0,15
shear strength, at first a micro crack starts to open and
0,1
0,05
continue to surround the wear fragment. After fragment
0 (hole) existed, which can be called as pitting, is exposed to
0 1,6 5,9 8,9 15,5 repeated loading by reciprocating ball specimen. Then, this
Si %
region becomes more critical to be fully raptured of the film
Fig. 7: Average friction coefficient of DLC versus Si %. completely. Besides, fragments (third bodies) taken place
from the pitting hole are crashed (fig. 9b) and may behave
also abrasive grounder, and start another critical region.
Therefore, fatigue can be speculated as a dominant failure
0 1,6 5,9 8,9 15,5 mode of DLC films. The chaotic nature of mechanical
20
Wear Rate (mm3/N.m)x10-7

18 scratches and the irregular features of these substrates

16 resulted in inhomogeneous DLC films. This often caused
14
12 chipping and fragmentation during sliding, and more wear
10 of the DLC film or the counter surface resulting from third
8 body effect.
6
4
2
0
HH-100 CPM- HH-100 CPM- LH-100 CPM- LH-100 CPM-
1N 2N 1N 2N
CONCLUSIONS

Fig. 8: Total Wear Rate of DLC in terms of Si % content.
5 Copyright © 2015 by ASME
A more complete understanding of mechano-chemical
interactions of two sliding bodies with their environment
should be one of the challenges and major issues in modern
tribology concepts. It is also valid in Carbon based
coatings/additives/composites, etc. It can be concluded
from the characterization of DLC films on different metal
substrates that, even though there is not much difference in
the structural, mechanical hardness, and frictional
characteristics, the adhesion of the coating to the substrate
is the main parameter that determines the long-term
tribological application of the coating. The adhesion of the
DLC coating depends on the substrate on which it is
deposited. In particular, the combination of high chemical
inertness with excellent wear resistance and super-low
friction makes these materials ideal for a wide range of
demanding tribological applications. The frictional
behavior of carbon-based materials in general, DLC films
in particular is controlled by a number of extrinsic (test
condition specific) and intrinsic (film specific) factors.
Wear and friction coefficient correlation is difficult to
establish. Like friction coefficient, wear is also affected
badly from increasing amount of Si. Furthermore, our films
also includes O coming from sources gas that expected to
act either as lubricant or and agent for tribochemical wear
depending on the relative humidity.
REFERENCES
1. Donnet, C. and A. Erdemir, Tribology of
diamond-like carbon films: Fundamentals and
applications. Tribology of Diamond-Like Carbon
Films: Fundamentals and Applications. 2008. 1-
664.
2. Fontaine, J., C. Donnet, and A. Erdemir,
Fundamentals of the tribology of DLC coatings,
in Tribology of Diamond-Like Carbon Films:
Fundamentals and Applications. 2008. p. 139-
154.
3. Ferrari, A.C., et al., Science and technology
roadmap for graphene, related two-dimensional
crystals, and hybrid systems. Nanoscale, 2015.
4. Ohmae, N., Humidity effects on tribology of
advanced carbon materials. Tribology
International, 2006. 39(12): p. 1497-1502.
5. Jahanmir, S., A.Z. Hunsberger, and H. Heshmat,
Load capacity and durability of H-DLC coated
hydrodynamic thrust bearings. Journal of
Tribology, 2011. 133(3).
6. Donnet, C. and A. Erdemir, Solid lubricant
coatings: Recent developments and future trends.
Tribology Letters, 2004. 17(3): p. 389-397.
7. Maboudian, R., W.R. Ashurst, and C. Carraro,
Tribological challenges in micromechanical
systems. Tribology Letters, 2002. 12(2): p. 95-
100.
8. Bhushan B, G., B K Handbook of Tribology:
Materials, Coatings and Surface Treatments.
1997, Malabar, FL: Krieger
9. Bhushan, B., Principles and Applications of
Tribology, Second Edition. Principles and
Applications of Tribology, Second Edition. 2013.
10. Bhushan, B., Chemical, mechanical and
tribological characterization of ultra-thin and
hard amorphous carbon coatings as thin as 3.5
6 Copyright © 2015 by ASME
View publication stats
nm: Recent developments. Diamond and Related
Materials, 1999. 8(11): p. 1985-2015.
11. Voevodin, A.A. and J.S. Zabinski, Supertough
wear-resistant coatings with 'chameleon' surface
adaptation. Thin Solid Films, 2000. 370(1): p.
223-231.
12. Savan, A., et al., Use of nanoscaled multilayer
and compound films to realize a soft lubrication
phase within a hard, wear-resistant matrix.
Surface and Coatings Technology, 2000. 126(2-
3): p. 159-165.
13. Erdemir, A., O.L. Eryilmaz, and G. Fenske,
Synthesis of diamondlike carbon films with
superlow friction and wear properties. Journal of
Vacuum Science and Technology A: Vacuum,
Surfaces and Films, 2000. 18(4 II): p. 1987-1992.
14. Erdemir, A., The role of hydrogen in tribological
properties of diamond-like carbon films. Surface
and Coatings Technology, 2001. 146-147: p. 292-
297.
15. Jahanmir, S., H. Heshmat, and C. Heshmat,
Evaluation of DLC coatings for high-temperature
foil bearing applications. Journal of Tribology,
2009. 131(1): p. 1-11.
16. Andersson, J., R.A. Erck, and A. Erdemir,
Friction of diamond-like carbon films in different
atmospheres. Wear, 2003. 254(11): p. 1070-1075.
17. Gardos, M.N. and B.L. Soriano, Effect of
environment on the tribological properties of
polycrystalline diamond films. Journal of
Materials Research, 1990. 5(11): p. 2599-2609.
18. Eryilmaz, O.L., et al., Deposition,
characterization, and tribological applications of
near-frictionless carbon films on glass and
ceramic substrates. Journal of Physics Condensed
Matter, 2006. 18(32): p. S1751-S1762.
19. Ozmen, Y., A. Tanaka, and T. Sumiya,
Tribological studies of DLC films contaning
different amount of silicon coated by reactive ion
plating. Fundamentals of Tribology and Bridging
the Gap between the Macro-and
Micro/Nanoscales, ed. B. Bhushan. Vol. 10. 2001,
Dordrecht: Springer. 565-570.
20. Gonzalez-Julian, J., et al., Enhanced Tribological
Performance of Silicon Nitride-Based Materials
by Adding Carbon Nanotubes. Journal of the
American Ceramic Society, 2011. 94(8): p. 2542-
2548.
21. Özmen, Y., A. Tanaka, and T. Sumiya, Effect of
humidity on the tribological behavior of diamond-
like carbon (DLC) film coated on WC-Co by
physical vapor deposition method. Surface and
Coatings Technology, 2000. 133-134: p. 455-459.