Wear, 168 (1993) 143-153 143

Review of the tribology of diamond-like carbon

A. Grill
IBM Research llivirion, T..T. Watson Research Center, ~o~t~wn ~e~~ht~, AT 10598 (USA)

(Received July 20, 1992; accepted January 4, 1993)

Abstract

Diamond-like carbon (DE) films are characterized by very low friction coefficients, high wear resistance and
high corrosion resistance. Depending upon the testing environment, the coefficient of friction can be as low as
0.01. As-deposited films are wear resistant in vacuum as well as in atmospheric ambient. However, the tribological
properties of DLC are strongly affected by the deposition method. This paper reviews the friction and wear
properties of DLC, and of similar materials derived from DLC, as a function of the preparation method and
testing environment. Mechanisms proposed to explain the tribological properties are presented and discussed.

Therefore, special attention has been given to the

Diamond-like carbon (DLC) is a term used to describe
hard carbon films which are mostly metastable amor-
phous materials but can include a microcrystalline phase.
DLC films have been prepared by a variety of methods
and precursors, ~n~~udin~ r.f. or d.c. plasma-assisted
chemical vapor deposition (CVD), sputtering, vacuum
arc, and ion beam deposition, from a variety of carbon-
bearing solid or gaseous source materials [l]. DLC
films are characterized by an extreme hardness, which
is ‘measured to be in the range 2000-5000 kg mm-’
[2], a generally low friction coefficient and usually very
high internal stresses 13-51. As a function of the de-
position conditions, the films may contain varying
amounts of hydrogen. The films deposited by plasma-
assisted CVD (PACVD) usually incorporate up to 60%
hydrogen f6], while those deposited by sputtering or
a vacuum are may contain only small amounts of
hydrogen or no hydrogen at all.
The high hardness and chemical resistance of the
DLC films makes them good candidates as wear-resistant
protective coatings for metals, optical, or electronic
components. The use of DLC is especially attractive
in applications where it is required that the thickness
of the protective film be less than 50 nm, as for example
in the case of magnetic recording media. One such
application is in hard magnetic disks, where the trend
towards higher density data storage has led to the
requirement of very low flying heights between a disk
and a recording head 171. The protective coating must
be resistant to wear and corrosion but also thin enough
not to impede the achievement of high recording density.
tribological study of the head-disk interfaces in magnetic
recording drives using thin film media, in order to
develop reliable, high capacity disk files. During normal
operation, the read/write head flies above the disk
surface; however, when the disk starts or stops, the
slider rubs on the surface of the disk. The friction and
wear which can develop between the siider and disk
during contact can result in the failure of the recording
media. In addition, very little debris can be allowed
to form during the start and stop cycles, because the
debris can disrupt the flight of the head and lead to
the failure of the disk surface.
At the operating conditions of magnetic-recording
media and micromechanics in general, microtribology
becomes a key technology for interfaces [$I. Microtri-
bology addresses the changes taking place at the atomic
level in the very superficial layers in contact. Therefore,
the characterization of microtribological properties has
to be performed at ultralow loads. Microtribological
testing tools, such as a contact profilometer [9] or point
contact microscope flO] have been developed for this
purpose by modi~ing a scanning tunnelling microscope.
Measurements have been performed with this tool at
loads as small as 1 pg [9].
In microtribology, the required surface material is
not a self-sacrifice-type solid lubricant but has to be
both wear resistant and lubricating. According to Miyake
and Kaneko [8], to reduce atomic-scale wear, the struc-
ture of the tribological material has to satisfy the
following requirements.

~43-1#8/93/$6.~ 0 1993 - EIsevier Sequoia. All rights reserved

 (1) top layer - shear should always occur at the
sliding interface but not within which requires a material
of low surface energy as the topmost layer;
(2) bulk of tribological film - fracture formation
and defect growth by sliding should be negligible, which
requires a high strength material;
(3) interface to substrate - this should have a large
adhesive strength, which should prevent delamination
of the tribological structure from the substrate.
The third requirement can be fulfilled by a suitable
bonding layer, such as a-Si:H, for deposition of DLC
on silicide-forming metals [ll], or by grading the in-
terfacial layer with a mixture composition of film and
substrate, such as Si-C for deposition of DLC on silicon
[S]. The other two requirements will be discussed later,
showing that DLC, especially the type prepared by
PACVD, and materials derived from it can satisfy these
requirements.
The properties of DLC films make them useful for
a variety of protective applications [12]. Nevertheless,
improvement of their tribological properties and ex-
panding the use of DLC films for tribological protection
in new applications requires a better understanding of
their friction and wear properties, and the dependence
of those on the deposition parameters and on the
operating environment. This is important taking into
consideration that the properties of DLC films can be
significantly affected by the deposition system (i.e.
method, precursor, parameters) [6]. In an effort to
improve the tribological properties of DLC films, a
variety of related materials have been developed and
investigated.
This paper presents a review of tribological studies
of hard carbon films and related materials, and discusses
the mechanisms proposed to explain these tribological
properties.
2. Review of DIE trhology
The structure of hydrogenated DLC can be described
as a randbm network of covalently bonded carbon in
hybridized tetragonal, (sp’) and trigonal (sp’) local
coordination, with some of the bonds terminated by
hydrogen [13]. Robertson [14,15] claimed that, in ad-
dition to the short-range order defined by carbon hy-
bridization and hydrogen content, a substantial degree
of medium-range order on about the 10 8, scale also
exists in the films. According to Robertson, the DLC
can be described as a network of graphitic clusters,
linked into islands by sp3 bonds. Sputtered hard carbon
films are often mostly graphite-like, while, for certain
deposition methods, the hard carbon films are consti-
tuted of a mixture of graphite and diamond micro-
crystallites. Because of this spectrum of microstructures,
the tribological properties of diftcrent carbon films caii
be related to the tribological behavior of graphite 01
diamond. These properties will be first discussed to
serve as a reference to the properties of DLC
The friction coefficient of diamond sliding on diamond
is relatively low and adhesion plays an important role
in determining the friction of diamond on diamond in
air. The diamond surface is normally terminated with
a layer of chemisorbed hydrogen and oxygen. This layer
renders the surface relatively unreactive and prevents
strong C-C bonding across the sliding interface. When
diamond-diamond sliding experiments are performed
in a high vacuum, the sliding action wears off the
chemisorbed hydrogen and oxygen from the surface.
Strong bonding then occurs across the interface, causing
a large increase in the friction coefficient. The friction
can be decreased again by bleeding in hydrogen in the
chamber containing the sample 1161. During sliding in
air, the adsorbates are also removed by sliding but are
replenished through adsorption from the environment,
and the friction coefficient remains low. It was found
that the friction coefficient of diamond on diamond in
air can be changed by heating the samples to 100 “C
or by exposing it to water [17]. The heating causes the
desorption of materials adsorbed on the surface of’
diamond, leading to better interfacial contact and an
increased friction coefficient. In contrast, water has the
opposite effect, reducing the friction coefficient. Lu-
bricating oils do not change the friction coefficient of
diamond on diamond [17].
Wear of diamond occurs through chipping of small
fragments from the surface, while wear through a surface
graphitization mechanism, as a cause for diamond wear,
is generally rejected [16]. Even a soft material, such
as gold, can cause wear of diamond. This is explained
through a fatigue mechanism which causes the formation
and growth of small cracks, leading finally to fracture
of the diamond particles. There is also evidence that
the debris formed during sliding contributes to the low
friction in diamond [18].
It has been shown that water acts as a lubricant for
graphite and improves its wear and lubricating behavior
[19-211. The lubricating action of the water has been
explained as a result of a three-body interaction with
the adsorbed water, which causes reduced adhesion
between the surfaces in contact. Hydrogen has been
found to have a similar lubricating effect on graphite.
Zaidi et al. [22] investigated the sliding wear of graphite
against graphite in an atomic hydrogen atmosphere
produced by passing hydrogen over a tungsten ribbon
at 2000 K. The authors found that atomic hydrogen is
an effective lubricant for graphite and that there is a
close analogy between the lubrication of the graphite
by water vapor and by atomic hydrogen. It appears
that hydrogen passivates dangling bonds at the edges
 A. Grill I Tribology of diamond-like
of the graphite crystallites, leaving only the possibility
of weak interactions with the r bonds, thus resulting
in reduced friction.
2.1. Friction coefficients
Despite the high chemical inertness of DLC films,
their tribological behavior is controlled to a large extent,
as we shall see in the following, by the surface chemistry
of the films. The surface chemistry can be affected by
the environment. However, it is also dependent on the
method used for the preparation of the films, which
determines their structure.
In 1980, Enke et al. [3] reported a very low friction
coefficient of DLC films deposited by PACVD from
acetylene. In nitrogen at a relative humidity (RH) of
less than l%, the friction coefficient between a steel
ball and a DLC-coated silicon wafer was p = 0.01-0.02.
It increased with increasing RH, attaining values of
0.05 at RH= 10% and up to 0.19 at RH= 100%. A
similar behavior was reported for films deposited by
PACVD from ethylene [23]. The films showed a con-
tinuous increase in the friction coefficient with increasing
RH and the friction exhibited a hysteresis effect between
RH =50% and 100%. Values as low as p= 0.005 were
measured in a vacuum [23]. Enke et al. explained the
low friction coefficients by assuming that graphitization
of the surface layer of the DLC films takes place during
testing.
Low friction coefficients were also reported by Weiss-
mantel et al. [4] for carbon films deposited by ion beam
methods. The films had a friction coefficient of 0.19
against steel, decreasing to 0.04 after 10 000 passes in
a pin-on-disk apparatus.
Memming et al. [18] studied the tribological behavior
of amorphous hydrogenated carbon (a-C:H) deposited
by r.f. PACVD from acetylene, toluene or benzene.
Stationary (as referred to by the authors) friction coef-
ficients of DLC against steel were found to decrease
to very low values, i.e. p cO.02, at RH < 1% and this
low value was maintained in ultrahigh vacuum (UHV).
The very low friction coefficient was attained after 25
rotations from an initial value of ~~0.2. The friction
coefficient remained low in dry nitrogen (p= 0.02);
however, it increased drastically to about 0.6 when
nitrogen was substituted by dry oxygen. In humid ni-
trogen or humid oxygen, the friction coefficient was
0.25. The authors found by Auger electron spectroscopy
that, in the conditions of very low friction, carbonaceous
material was transferred from the DLC film to the
steel rider, while, in the conditions of high friction (in
dry oxygen), iron transferred to the DLC surface. The
material transfer changed the chemistry of the interface
layer and, according to the authors, this ‘tribochemical’
behavior explained the different values obtained for
the friction coefficients under various conditions [18].
carbon 145
Memming et al. also found that the loss of hydrogen
after annealing the DLC films above 550 “C caused
large changes in the friction coefficient, which reached
values of ~=0.68 in UHV or dry nitrogen, indicating
that the presence of hydrogen in these films was essential
for obtaining a low friction in dry nitrogen or IX-IV.
However, in a humid atmosphere, the friction coefficient
did not change significantly after annealing 1181.Weiss-
mantel et al. also found previously [24] an increase of
the friction coefficient of DLC upon heating above 400
“C and attributed this increase to a loss of hydrogen
rather than to graphitization of the DLC.
Miyoshi and co-workers studied the tribological be-
havior of hydrogenated DLC films deposited on silicon
nitride by r.f. PACVD of methane or butane in sliding
wear against spherical silicon nitride riders [25,26]. The
friction coefficient was found to be 0.1 in dry nitrogen
and 0.18 in laboratory air. For films deposited at a
power density of 0.08 W cme2, the coefficient of friction
was found to increase with increasing number of sliding
passes in both air and dry nitrogen. In air, however,
the film broke through and was removed from the
sliding zone after only 1000 passes, probably as a result
of poor adhesion. The coefficient of friction of a film
deposited at a higher power density of 0.40 W cm-’
decreased, between 10 and 10 000 passes, reaching a
value of 0.01 in dry nitrogen. The authors explained
the decrease of the friction coefficient above 1000 passes
by assuming the formation of a hydrocarbon rich layer
at the sliding interface. The differences in the behavior
of the films deposited at different power levels were
attributed to differences in film densities; however,
density measurements were not reported.
According to Miyoshi and co-workers, annealing in
vucuo above 500 “C causes hydrogen loss from the
surface of the DLC and the formation of a graphite-
like layer through a two-step process [25,26], i.e. a
carbonization stage in which the film loses hydrogen,
followed by a polymerization stage, forming graphitic
crystallites or sheets. During heating in z)acuo, the
friction coefficient remained low up to 500 “C (~<0.2)
but increased strongly at 600 “C (~=0.7), presumably
as a result of the assumed graphitization process. The
initial friction coefficient in humid air of the films
annealed at 700 “C was lower than that in dry nitrogen,
the film thus behaving similarly to graphite, which
requires water to produce a low friction value [19,20].
It appears from the results presented above that, in
hydrogenated DLC films, hydrogen has a similar effect
to that in diamond [16] or in graphite [22]. Hydrogen
passivates the dangling bonds in the hydrogenated DLC
films and permits only weak interactions between DLC
and the sliding partner. When hydrogen is lost from
hydrogenated DLC by annealing, the dangling bonds
created cause strong interactions between the contacting
surfaces, resulting in increased friction in UHV or dry
nitrogen, similar to the cases reported for diamond or
graphite [16,22]. Humidity reduces the friction coef-
ficient to an intermediate value, as it would do for
graphite, but also for diamond, although the values are
closer to that of graphite.
The tribological properties of DLC films deposited
on silicon by r.f. PACVD from a methane and hydrogen
mixture have been reported by Kim et al. 1271. The
friction was measured against a silicon nitride ball in
argon and air at different humidities. The friction
coefficient varied from p= 0.2 in 50% humid argon and
100% humid air to ~=0.06 in dry argon. This variation
of the friction coefficient was attributed to material
transferred between DLC and the ball in the contact
area. In dry argon, material was transferred from the
DLC to the silicon nitride ball and this reduced the
friction coefficient. In dry or humid air, an interfacial
layer - identified by microprobe Fourier transform IR
as a carbonyl compound (oxidized hydrocarbon) ---
formed by a tribochemical reaction covered both the
DLC and silicon nitride contact areas and increased
the friction coefficient [27].
The effects of the deposition temperature and sub-
strate bias on the tribological properties of DLC films
deposited by r.f. PACVD from acetylene have been
reported by Grill et al. [28]. The DLC films were
deposited on silicon wafers at temperatures between
100 and 250 “C and substrate biases of - 80 and - 150
V (d.c.). The films were annealed in z)acuo at tem-
peratures up to 590 “C for 3-4 h. The original hydrogen
content in the films decreased from 40% in the as-
deposited film to 22% after annealing at 590 “C. The
friction coefficients were measured in air at
RH=40%-70% against a spherical steel rider. The
friction coefficients of the as-deposited DLC films were
found to decrease from 0.35 f 0.04 for films deposited
at 100 “C to 0.20f 0.04 for films deposited at 250 “C,
with the surface bias having a negligible effect. Within
the experimental error, the friction coefficients of the
annealed films were essentially the same as those of
the as-deposited films. The insensitivity of the friction
coefficients to the annealing temperature was similar
to what was observed by Memming et al. [18] and
Miyoshi [26] in humid air.
The tribological properties of sputtered DLC films
have been reported on by several authors [29-321.
Agarwal et al. [29] measured the sliding friction of
amorphous carbon films 30 nm thick sputtered on
magnetic recording fihns (CoNi and COP) against single-
crystal, hemispherical sapphire. The tests were per-
formed at a linear speed of l-5 m s- ’ up to 20 000
disk revolutions. After an initial decrease, as a result
of surface burnishing, the friction coefficient increased
from an initiar value of 0.3
I .O with increasing number
Marchon nr~d co-worker<
tron-sputtered carbon films
ceramic sliders of Mn-%n .md (.‘a l’if&. ‘I’he tests were
performed under a controlled atmosphere at <Ironstan!
drag speed of’ 0.06 m s ‘. In ;t I-cgular atmosphere,
the friction coefficient of the sputtered films was found
to increase gradually from 0.2 to I.2 during the testing,
while. in dry nitrogen, the value of the friction coeficient
remained constant at 0.2 up to 5f! h of testing. When
oxygen was introduced into the system, the friction
coefficient increased to 1.2 but decreased again when
oxygen was replaced with nitrogen. 0wing to the gradual
increase of the friction coefficient and the drastic effect
produced by oxygen - compared with the effect of an
inert gas .- the changes in the friction coefficient were
attributed to a chemical (corrosive) type of wear,
If the sliding wear is adhesive isear, the frictlonnl
force F between the surfaces of the friction couple is
given by [-lo]
where A, is the area of contact and S the shear stress
at the contact area.
When the surface of the carbon 1s exposed to oxygen,
surface oxides can form. In graphite, chemisorbed ox-
ygen is desorbed as CO at temperatures above 600 “C
[32]. According to Marchon et al. [33], at sliding speeds
of 1 m s---’ -- as typically encountered between head
and disk during start-stop operations - flash tem-
peratures can reach values of several hundreds of
degrees centigrade, which are sufficient to cause thermal
desorption of CO and CO,. However, at low sliding
speeds of 0.06 m SK’ as used in the experimental testing,
such high temperatures are not reached. Nevertheless,
it is possible that the desorption temperature could be
lowered by the catalytic effect of the slider material
in contact with the film (as was shown by a 20-fold
increase in the reactivity of graphite with oxygen when
CaTiO, powder was added to graphite powder). Another
explanation for the desorption of the carbon oxides at
the lower temperatures could be the direct transfer of
energy from mechanical friction to chemical reaction,
as suggested by Fischer [35].
The formation and desorption of the carbon oxides
is a tribochemical wear which leads to surface smoothing
of the sputtered film (in the specific case, from an
initial surface roughness of 20 A to about 6 A), a
gradual increase in the true contact area A, and an
increase in the friction coefficient in air. Tribochemical
wear of the carbon surface is thus the cause of the
frictional build-up (as observed from 0.2 to 1.2) in an
oxygen-containing atmosphere [30]. In contrast, in a
clean environment, when the existing surface oxides
are removed from the carbon surface through desorption
by the action of the rubbing slider, the clean carbon
surface locally reconstructs to saturate dangling bonds
and the friction coefficient remains low. The drop in
the friction coefficient when oxygen is replaced by
nitrogen was explained by Marchon et al. as resulting
from a change in the shear strength with the change
of atmosphere [33]. The magnitude of the friction drop
when oxygen is replaced by nitrogen is not always
predictable. A lubricant could reduce the wear of the
carbon film by reducing the contact temperature, thus
reducing the removal and regeneration rate of oxides,
and by serving as a shield, preventing oxygen chemi-
sorbtion on the surface.
The tribology of sputtered carbon films can be im-
proved when deposited by sputtering in hydrogen-con-
taining argon [36], or by exposing the carbon films to
an atmosphere of fluorine, which oxidizes the graphite
to graphite-fluoride, even at room temperature 1331.
In these cases, the hydrogen or fluoride probably block
the active sites at the surface which could interact with
oxygen.
Similar results were reported by Strom et al. [32] for
tests performed on commercial, circumferentially tex-
tured unlubricated disks coated with sputtered carbon
films 30 nm thick on top of a Co-Pt-Ni magnetic layer.
The tests were performed with sliders composed of
Al,O,:TiC= 70:30, in contact with the disk, at a slider
load of 15 g. The measurements were performed in
oxygen, nitrogen, argon and helium. Similar to that
reported by Marchon et al. [30], it was found that the
friction increased continuously in dry oxygen, while, in
the other gases (nitrogen, argon and helium), the friction
increased slightly only during the initial three revolutions
and remained constant afterwards. At RH = 4%, little
differences were observed in the friction in the different
gases. The behavior was explained by the tribochemical
mechanism described before. Adhesive friction was
assumed to be the dominant friction mechanism and,
since the frictional force is proportional to the real
contact area, the smoothing of the surface by the
tribochemical wear resulted in higher friction. During
rubbing in the presence of water, the carbon appears
to be removed in the same way as occurs during rubbing
in oxygen, with the oxidation of the carbon being
preceded by the dissociation of water molecules [32].
At low humidity (RH=O%-OS%), the increase in
friction with sliding cycles was smaller than that at
higher humidities. In contrast to the case with conditions
of higher humidity, at the lower humidity debris was
observed to form at the sliding interface as a result
of mechanical wear. The debris maintained a small
contact area, resulting in corresponding lower friction
[32]. After a larger number of cycles, an equilibrium
was reached between mechanical wear (which caused
debris fo~ation) and chemical wear (which removed
the debris and smoothed the surface), and the friction
coefficient reached a constant value [32].
Marchon and Khan [34] used scanning tunnelling
microscopy (STM) to obtain topographic and spectro-
scopic images of 30 nm thick magnetron-sputtered
carbon films 30 nm thick. The spectroscopic images,
showing the derivative dZ/ds of the tunnelling current
I with respect to the tip-to-surface distance s, provided
info~ation on the chemical nature of the film in terms
of the local value of the work function. Areas of large
d&is fluctuation were observed and were attributed to
local changes in the structure of the sputtered carbon
from graphitic to diamond-like microdomains, according
to the model described by Robertson [ 141. No correlation
was observed between the topographic and spectroscopic
images of the films. Atomic structures have been resolved
locally, showing short-range graphitic order, especially
in films of poor durability, while harder DLC films
showed a totally disordered structure. Sputtered carbon
films with better mechanical properties produced spec-
troscopic images of greater homogenei~, indicating a
more uniform film microstructure [34].
The effect of the surface topography and chemistry
on the tribological behavior of sputtered carbon was
addressed by Hilden et al. [31]. Carbon films were
sputtered in argon on two types of disk: disks make
of particulate media (y - Fe,O, or cobalt-doped
y - Fe,O,) in organic binders and thin film disks pre-
pared by sputtering a cobalt-based magnetic alloy plus
a carbon overcoat on polished NiP substrates. Ruth-
erford back scattering (RBS) analysis showed that the
carbon films contained small amounts of oxygen and
argon and 2%-3% hydrogen, although the source of
the hydrogen was unclear. The films were characterized
by continuous sliding tests and start-stop tests against
sliders of A120,--TiC at a load of 35 sf.
It was found that the behavior of the carbon-over-
coated particulate disks did not change significantly
with humidity. The friction coefficient changed slightly,
remaining between 0.2 and 0.4, with a maximum ob-
tained at 45% humidity. However, the dynamic friction
coeflicient of the carbon sputtered on the thin film
disks showed a high sensitivi~ to the presence of water
and decreased from p= 1.3 at RH -5% to ~=0.9 at
RH =40%, then decreased drastically to ~=0.3 at
RN = 60%. The decrease in the friction coefficient with
increasing humidity may indicate that these films were
more graphite like than diamond like. The authors
explained the differences in the behavior of the two
types of disk by the differences in their surface to-
pography. During sliding of the head against the carbon
surface, the roughness owing to processing corrugations
can be ironed out, increasing greatly the contact area
in the case of thin film disks. The surface roughness
of the particulate disks with a wealth of pores and
148 A. Grill I Tribology of diamond-like
crevices was not significantly affected by the wear tests
and the contact area remained constant.
The tribological properties of a different type of DLC
film, deposited by condensing carbon from the plasma
flux generated by vacuum arc discharges, have also
been investigated [37-40]. Films 3-4 pm thick with a
Vickers hardness in the range 40-180 GPa were de-
posited by Aksenov and Strel’nitskij [37] on both surfaces
of a friction couple (hardened steel-45 disk and spherical
ball-bearing steel, Cr-15 rider). In air at a sliding speed
of 0.8 m s-‘, a friction coefficient in the range 0.04-0.13
was found to be independent of the load up to a critical
load of 70 N. In a vacuum of lo-’ Pa and below a
critical load of 18-20 N, the friction coefficient was
0.01-0.14. Above the critical load, the friction coefficient
in mcuo increased gradually to 0.6 at 60 N.
During friction testing in air, a fine powdered debris
identified as turbostratic graphite was formed on the
friction couple and the authors assumed that, in this
situation, the frictional force was determined by the
sliding of graphite against graphite. The wear debris
formed in vucuo was claimed to contain polycrystalline
diamond and carbine in addition to graphite (no in-
dication was given how this composition was deter-
mined). The graphite particles were presumably carried
away from the contact zone during the friction testing
and the surfaces interacted directly with the hard
diamond and carbine particles. The normal load was
thus applied mainly to the hard components of the
DLC and the true contact area was smaller than that
in air. This could explain why the friction in mcuo was
less than that in air. The authors tested different
combinations of DLC coating with various hardnesses
(40-180 GPa) and found the lowest friction coefficient
(0.04 in air and 0.01 in vacm) for the combination of
DLC coatings with highest hardness [37].
Tochitsky et al. [38] deposited films 0.5-3 pm thick
by accelerated flows of plasma from pulsed vacuum
arc discharges at substrate temperatures below 373 K
and obtained carbon films with fine-grained structures.
The films were tested for up to 100 h by reciprocal
sliding at RH = 50%-60% at a rate of 3000-5000 min- ’
without lubrication. The films had a hardness of 70-100
GPa and the friction coefficients against steel were 0.1
(static) and 0.07 (dynamic).
Hirvonen et al. [40] have deposited DLC films on
steel using a vacuum arc discharge [40]. In dry sliding
wear against a hardened steel pin in air at RH = 45%,
a friction coefficient of 0.18 was measured in a pin-
on-disk tribotester at a sliding speed of 10.8 cm s- ’
and a hertzian stress of 860 MPa. After 100 000 cycles,
the friction coefficient decreased to 0.12. Scanning
electron microscopy (SEM) analysis showed that a
transfer layer was formed on the pin during sliding.
This layer, which appeared to be softer than the initial
carho!!
DLC film, probably had the donrrnant effect on tht’
tribological behavior of the friction couple, determining
the value of the friction coefficient and producing iin
extremely low wear coefficient for- the DLC film.
To improve the mechanical and triboiogical properties
of DLC, different derivatives of hydrogenated DLO
films have been investigated. Such derivatives arc
silicon-. metal- or nitrogen-containing DLC. as well as
fluorinated variations of some of these materials [&-IO,
41-461. The modifications of the DLC films were gen-
erally made (even if not always stated explicitly) to
improve their qualities according to requirements
(l)-(3) described in the Introduction.
Miyake and co-workers [9,10] performed microtri-
bological studies of silicon-containing carbon films and
fluorinated silicon-containing carbon films. Point contact
microscopy (PCM) (a tool developed from STM) was
used to investigate the microscopic wear and frictional
properties of different carbon films. ‘The measurements
were performed at room temperature in ambient air
at RH -450/o-50%. Silicon was incorporated into the
film to improve the adhesion of the DLC to the silicon
substrates, and fluorination was carried out to reduce
the surface energy of the DLC film. Electron cyclotron
resonance (ECR) was employed to deposit films 1 ,um
thick from silane and ethylene, and the films were
subsequently fluorinated by exposure to CF, plasma.
The fluorination resulted in the incorporation of up
to 28% surface fluorine and reduced the friction coef-
ficient of the silicon-containing carbon film to less than
0.3. The hardness of the films increased with increasing
silicon content, reaching a maximum at 40% Si, and
was not changed by fluorination. The surface energy,
evaluated by the contact angle with water, decreased
as a result of fluorination and the adhesion of the
carbon film to the silicon substrate increased with the
addition of small quantities of silicon. The life of the
coating was measured in the microtribological tester
as the time to reach a friction coefficient of 0.3. The
lifetime thus defined was maximal for films containing
lo%-20% Si. Films containing more than 20% Si had
a higher initial friction coefficient. The silicon-containing
carbon films had less wear than did the pure DLC
films, while the fluorinated films showed even less weal
WI.
The tribological properties of silicon-containing car-
bon films (Si-DLC) were also reported by Oguri and
Arai [41]. The films were deposited by a d.c. plasma
of CH4, Sic&, H, and argon and were found to contain
about 40% H. The wear and friction coefficients were
measured by a pin-on-disk apparatus, using a ball-
bearing steel ball (AISI 52100) as a rider. According
to the authors, the films with compositions of 70% CC/
(C + Si) < 85% had a DLC character. These films were
found to have the lowest friction coefficients of about
 A. Gtill / T~boio# of diamond-i~ke carbon
0.04 against steel in an ambient atmosphere at
RH= 50%-70%. The low friction coefficient was ex-
plained by the formation of SiO, debris and its inter-
action with ambient gases and the DLC. The authors
also suggested that the low friction coefficient could
be explained by temporary melting of the SiO, at the
interface between the two parts of the friction couple
1411.
A material similar to amo~hous carbon was studied
by Hioki and co-workers [44,45]. The films of i-siiicone,
prepared by ion-beam-assisted deposition (IBAD), were
deposited by combining evaporation of a silicone oil
(pentaphenyl-trimethyl-trisiloxilane; (Si,O,C,,H,,),)
with simultaneous irradiation of the surface of the
growing film with energetic ions (1.5 MeV Ar+, 400
KeV N’ or 200 KeV Ti+). RBS analysis showed that
the composition of the IBAD carbonaceous film, with
the exception of hydrogen, is C:Si:O = 0.8:0.1:0.1, which
is similar to that of the original oil, i.e.
C:Si:O = 0.87:0.08:0.05. The evaluated density of the
film was 2.6 g crrP3, compared with 1.1 g cmP3 for
the original oil. Secondary ion mass spectroscopy (SIMS)
measurements indicated that the films also contained
about 10% H [45]. The authors explained the findings,
assuming that the irradiation caused the emission of
the hydrogen from the oil, resulting in its solidification.
Some i-silicone films 0.1-0.3 pm thick were tested
on a pin-on-disk apparatus against hardened SUJ2 steel
pins. The films had low friction coefficients (~=0.05)
in air or nitrogen at RH= 20%-70%. In dry nitrogen,
i-silicone showed a very low friction coefficient of
~~0.02. For the same steel disk coated with an unir-
radiated oil fihn, the friction coefficient was 0.1. The
authors found that i-silicone material was transferred
to the steel rider during testing and they related the
low friction coefficients to that transfer [44].
Metal-containing hydrogenated carbon films (Me-
DLC) were studied by Dimigen and co-workers [42,43].
Metal was incorporated into the films to reduce stresses
and improve the adhesion of DLC to the metals. The
films, deposited by sputtering a metal or metal carbide
target in an Ar + hydrocarbon plasma, had an H:C ratio
of 0.2-0.5 and a metal mole fraction xMe=cMe/
(chne-i-c=)> 0.02. The films were identified as having a
granular structure consisting of nanocrystalline metal
or carbide particles in a DLC matrix. The friction
coefficients and adhesive wear were measured with a
pin-on-disk apparatus, using uncoated steel or cemented
carbide spheres.
The friction coefficient of the Me-DLC films has
been found to be strongly dependent on the metal
incorporated into the films. In an earlier paper 1421,
Dimigen et al. reported that, in humid air or humid
nitrogen, the coefficient of friction was found to be
~~0.2. At a very low relative humidity, i.e. RH<O.l%,
149
the value of the friction coefficient was found to scatter
and to depend on the metal, its concentration and
sliding speed. Also, the friction coefficient increased
with increasing metal concentration. A very low friction
coefficient of 0.06 was found for an Ru-DLC film with
x Ru= 0.07 at RH=O.l% and a sliding speed of 1.6 cm
S --I. However, at higher sliding speeds, the friction
coefhcient was much higher (~=0.7). In WHV the
friction coefficient became high even at very low speeds.
~though the friction ~e~cient of pure DLC (without
metal) was 0.02 in UHV, a small amount (5%) of metal
led to a considerable increase in the friction coefficient
to 0.15 in UHV. In humid air or humid nitrogen at
RH > l%, the friction coefficient of the metal-containing
films was generally below 0.2 [42]. More recent results
obtained in ambient air at RH= 18%-41% showed a
minimal friction coefficient of 0.04 at 12 at.% metal
in Ta-DLC films 1431. For W-DLC films containing less
than 13 at.% W, the friction coefficient against steel
decreased from 1.5 at RH=40%-80% to about 0.02
in dry nitrogen (RH<O.l%). For a tungsten concen-
tration higher than 30 at.%, the humidity had an opposite
effect on the friction coefficient 1431.
Dimigen and Klages [43] explained the tribological
behavior of the Me-DLC films based on their mechanical
properties and surface energy. According to them,
tribological materials are frequently divided into three
groups: metals, ceramics and polymers. The Me-DLC
films attain a hardness H typical of inorganic ceramics
but have Young’s modulus values E significantly lower
than those of ceramics. The corresponding H/E ratios
are relatively high and their values are typical for
polymers. The surface energy S of the Me-DLC fihns
with low metal contents are also more similar to that
for polymers than to those for metals or ceramics. The
combination of the high H/E with low S/H ratios (S/H
values being smallest among the other type of ma-
terials) could explain the low adhesion to the Me-DLC
films, their low friction coefficient and the low wear
1431.
The above explanation of the tribological behavior
of metal-containing DLC films may to a large extent
be applied to pure hydrogenated DLC or to silicon-
containing and/or fluorinated DLC films. The excellent
tribological performance of DLC films and their de-
rivatives might be attributed to a combination of fa-
vorable properties which are ceramic-like, on the one
hand (high hardness), and polymer-like, on the other
hand (high elasticity, H/E and low surface energy).
2.2. Wear
As shown above, a significant number of studies have
investigated the friction of DLC, starting as early as
1981, and have suggested mechanisms to explain the
friction coefhcients of DLC films and related materials.
However, the wear behavior of DLC has been only
recently addressed in a systematic way. The following
studies will be discussed according to the type of DLC:
(corresponding to the deposition method) and not in
chronological order.
Namura et al. f7] investigated the failure mechanisms
of hard magnetic disks coated with sputtered carbon
by contact start-stop (CSS) tests against Al,O,-TiC
sliders. The carbon films, 20-30 nm thick were sputtered
on top of a sputtered magnetic layer of Co-Cr and
permalloy. The tests were performed at rise times in
the range of 2-24 s and relatively low humidities of
15%-20% to prevent slider stiction. The slider was
pressed on the disk with a load of 5 mN before starting
the tests. The acceleration time of the disk was identical
to the deceleration time. The wear of the carbon layer
was found to be minimal during CSS testing under the
conditions investigated. Disk failure was found to occur
abruptly. Fatigue cracks were observed to develop in
the disk with repeated CSS cycIes. The cracks extended
in-plane and propagated to the surface of the disks.
When the crack reached the surface, flaking occurred
abruptly. The authors concluded that the cyclic load
is dominant over the forces acting at the start, because
of higher static friction coefficient and dynamic load
factor.
Agarwal et al. [29] described the wear of the sputtered
carbon films by a wear coefficient K, defined as the
ratio of the vertical cross-section of the wear track
produced in the pin-on-disk tester to the horizontal
contact area of the slider. The values of K obtained
were 5 X 10M6for CoNi and 9 x 10e6 for COP with hard
carbon over-coating, U.Y.50x lo-’ for uncoated COP,
indicating an increase in wear resistance by a factor
of 6 as a result of coating the magnetic metallic film
with the carbon layer, despite the high friction coef-
ficient. The wear was found to increase with normal
load and the number of revolutions but was independent
of the linear speed. According to the authors, the
principal contribution to the friction coefficient of DLC
is inelastic in nature; the mechanical energy is dissipated
primarily in the form of heat through inelastic processes
rather than the generation of lattice defects or other
mechanisms of plastic defo~ation~ Nevertheless the
small fraction of the total energy consumed to form
lattice defects causes plastic deformation and this,
coupled with fragmentation of surface material, results
in macroscopic wear.
Wear tests performed by Strom el al. [32] on thin
film magnetic disks with sputtered carbon overcoats,
using commercial read/write ceramic heads as sliders,
indicated that the carbon overcoats wear through a
tribochemical mechanism in the presence of oxygen
and through a mechanical mechanism in the absence
of oxygen. In dry gas without oxygen, debris is produced
almost mnnedrately through mecnatncal wear irr,o trr;
debris precludes the development of high friction itn<i
reduces the wear. In the prcserloc ,)1‘ cirq oxygen OI
small amounts of water, tribochcmical wear takes place.
without the formation of debris, and high friction cir:.-
velops between the slider and dii;Ei
In systems which are sensitrvc itt the f~~rrn~~t~~)n of
particles. eg. magnetic storage hytcms, tribochemical
wear without debris formation may be preferred tc)
mechanical wearwhich causes the generation ofparticles
[32]. A dry inert environment, which allows rapid me-
chanical wear, is undesirable in ~;uch devices using
sputtered carbon films.
Hilden d (zl. [31] found that the RH value had a
significant effect on the lifetime of carbon-overcoated
thin film disks. Values of the lifetime to failure from
2 min at RH = 2% to greater than 1300 min at RH = 70%
were observed, corresponding to the decrease of the
friction coefficient with increasing humidity. More than
20 000 start-stop cycles have been achieved for carbon-
coated disks, though the authors did not indicate for
which type of disks or condition,
Miyoshi 1201 found that DLC deposited at a low
power density failed in air and was removed from the
sliding zone after 1000 passes, while films deposited
at higher power density did not wear off the substrate,
even after 10 OO(I passes. Even with the superficial
graphite-like layer assumed to be formed on the surface
of annealed DLC. the wear life of the high density
fihn was reduced in humid air %3y a factor of two
compared with that in dry nitrogen. The differences
in the behaviors of the films deposited at different
power levels were attributed to thu differences in the
densities of the films.
G-ii1 and co-workers measured lhe wear of the DLC
films deposited by PACVD from acetylene in a pin-
on-disk tribometer against a ball-bearing steel rider at
a hertzian stress of 21.5 MPa in nitrogen at RH=5%
and in air at RH=40%-70% [47.483. The wear tests
were performed by running the apparatus for a preset
number of rotations (260 000) and measuring the re-
sulting wear tracks with a profilometer. The wear of
the DLC films, expressed as the track depth (A) per
lo4 rotations in the tribotester, is presented in Fig. I
as a function of the annealing temperature. The values
over 3000 indicate that the respective DLC films were
completely worn through after only a few thousand
rotations.
The as-deposited films showed very little wear, in-
dependent of the deposition temperature, with the films
deposited at a bias of -150 V (de.) having only a
negligible amount of wear. After annealing at 390 “C,
the films deposited at -80 V (d.c.) at 100 and 180 “C
had very low wear resistances and were completely
worn through after a few thousand rotations both in
 A. Grill 1 Tribology of diamond-lip carbon 151

Em et al. 1271 measured the wear rates of the r.f.

PACVD DLC films against a silicon nitride ball in a
pin-on-disk tribometer. The wear tests were performed
in argon and air at different humidities. The wear rates
(a) of the silicon nitride ball and the DLC at RH =50%
were lop8 and 10e7 mm3 N-’ m-’ respectively. In dry
argon, dry air and 100% humid air, the wear rates of
DLC were two orders of magnitude lower and that of
L
the ball was undetectable. An interfacial oxidized layer
AsDee. 390 440 490 590
formed from mechanically scissored particles, which
3.000
02 In Air combined to produce macrowear soft debris, was ob-

1
‘;’ 1.000
300
E
100
30
10
As Dep. 390 440 490 590
Temperature ( “C )
DeposTemp
BeIs
Fig. 1. Wear of DLC films vs. annealing temperature:
nitrogen; (h) in air.
nitrogen and humid air 1491. The film deposited at
-80 V (dc.) at 250 “C and annealed to 440 “C did
wear at a higher rate than the as-deposited film and
was worn through in nitrogen after annealing at 490
“C, while in air it lost its wear resistance after annealing
at 400 “C. DLC films deposited at 180 or 250 “C at a
bias of - 150 V showed negligible wear in nitrogen
after annealing at 390 “C, wore more rapidly after
annealing at higher temperatures but remained wear
resistant in nitrogen, even after annealing at 590 “C
(see Fig. 1). In humid air, the wear resistance decreased
and the film deposited at 180 “C at - 150 V lost its
wear resistance after annealing at 490 “C. However,
the film deposited at 250 “C at - 150 V remained wear
resistant in humid air, even after annealing at 590 “C
[491.
These results also showed that the wear of the DLC
films was not directly related to the values of their
friction coefficients. In addition, while other physical
properties showed only small differences in behavior
between the films deposited at various temperatures
and substrate biases [48], the wear resistance of the
films and their thermal stability were strongly affected
by the deposition conditions. A higher wear resistance
after annealing was obtained for DLC deposited at
higher temperatures and films deposited at the higher
biases remained wear resistant, even after annealing
at 590 “C.
served between the sliding parts. Kim el al. claimed
that, in 100% humid air, water molecules produce
strong adhesion of the wear debris and that a dense
layer covered the track on the DLC and reduced the
oxidation rate in the wear track. This oxidized debris
layer was thick enough to separate the DLC from the
silicon nitride and so reduce the wear. In 50% humid
air, the debris was found to be a mixture of oxidized
hydrocarbon and hydrated SiO, from the ball. However,
the debris appeared to be loose and not covering the
wear track. According to the authors, the wear of DLC
against silicon nitride is determined by the transfer
(a) in layer of wear debris. The wear is determined by an
adhesive (mechanical) wear mechanism in dry argon
but by tribochemistry in air and humid environments
[27]. The authors found no correlation between wear
and the friction coefficients in the various testing con-
ditions.
Microt~bological studies performed by Miyake et al.
[9] for Si-DLC films and fluorinated Si-DLC films
showed an increase in the lifetime of the films with
increasing silicon content, with a maximal lifetime being
obtained for films containing lo%-20% Si. Under the
conditions of microtribological testing, wear tracks 3
nm in size were obtained at a load of 7 FN on
un~uorinated film, while wear of the ~uorinated film
was undetectable. The wear increased with load and
was lower for the fluorinated films at all loads. The
wear of Si-DLC films was also reported on by Oguri
and Arai [41]. The wear of a steel rider against Si-
DLC was found to be the same as that against DLC
coatings; however, the wear of the Si-DLC coating was
found to be higher than that of DLC.
In the study of the wear of Me-DLC films, for W-
DLC films with 12 at.% W, the authors observed a
two-order reduction in the sliding wear of the coated
disk against steel compared with that for the bare
substrate and a drastic reduction in the wear of the
sliding counterparts 1431. When the test was carried
out against TiN or T&N films, significant wear of the
steel balls was observed, with the transfer of steel to
the nitride films. For the Me-DLC films, such a transfer
of steel onto the W-DLC was not observed. Dimigen
and Klages [43] also measured the abrasive wear rates
152 A. Grill I Triboloa
of the Me-DLC using a glycerine suspension of Al,O,
particles 5 pm in size. The abrasive wear rates showed
a minimum at about 13 at.% W in W-DLC films (a
composition at which the lowest friction coefficient was
obtained). The minimal abrasive wear rates were two
and eight times lower than the abrasive wear rates of
TiAlN and TiN respectively. However, the abrasive
wear rate of Me-DLC was two times larger than that
of pure DLC films. The combination of a low energy
surface (low S/H ratio) with a relatively strong, cross-
linked microstructure, resulting in high hardness and
high H/E values, could explain the low adhesion to the
Me-DLC films and their low friction coefficient and
low wear [43].
The DLC films deposited by vacuum arc discharge,
as reported by Aksenov et al. [37], were found to have
a high wear resistance both in air and vacuum. The
best wear resistance was obtained for the combination
of DLC coatings with highest hardness. DLC coatings
improved the lifetime of drills made of tool steel by
a factor of 1.5-3 during drilling of abrasive glass-
reinforced polymers and increased by a factor of four
the lifetime of carbide tools for turning titanium. The
application of DLC on burnishers made of hardened
tool steel made it possible to reduce the surface rough-
ness of non-ferrous metals by two or three classes [37].
Tochitsky et al. [38] found that the service life of the
steel parts coated with arc-discharge-deposited DLC
increased by 3-40 times.
3. Summarizing remarks
The excellent tribological performance of DLC films
and their derivatives might be attributed to a combi-
nation of favorable properties which are ceramic-like,
on the one hand, i.e. high hardness, and polymer-like,
on the other hand, i.e. high elasticity and H/E and low
surface energy. The results reviewed show that, although
the tribological properties of DLC or derived materials
deposited by different methods span a wide range, the
materials appear to have several common characteristics:
the value of the friction coefficient of hydrogenated
DLC deposited by PACVD is low in humid nitrogen
or oxygen, extremely low in dry nitrogen or UHV, and
very high in dry oxygen;
the loss of hydrogen through annealing at high tem-
peratures causes a marked increase in the friction
coefficient in UHV but affects only slightly its value
in a humid atmosphere.
In UHV or an inert atmosphere, these films display a
frictional behavior similar to that of diamond. However,
in a humid atmosphere, their behavior seems to be
closer to that of graphite. The mixed type of frictional
of diamond-l& c‘crrix)I!
behavior reflects the mixture ot sp and sp-’ carboti
hybridization in the hydrogenated carbon films.
The behavior of DLC deposited by other method:,
is less systematic, though very h t‘riction coefftcicnts
in UHV were found for vacuum-arc-deposited films
and a behavior similar to that <tf ihe PACVD films
was observed in dly oxygen anti nitrogen for- some
sputtered films. The behavior of the friction coefhcients
of the sputtered carbon films indicates that this type
of film is more graphite like than diamond like.
The high friction values found in the tests run in
dry oxygen and the low friction in dry nitrogen appear
to be common features of amorphous carbon with
diamond-like properties.
Lowering of the surface energy ot the DLC films,
e.g. by fluorination, can reduce their friction coefficients.
The friction of all DLC films, especially after a large
number of sliding passes, appears to be controlled in
many cases by the formation of an interfacial transfer
layer, the properties of which depend on the cnviron-
ment and on the sliding partner.
The wear resistance of DLC appears to be strongly
dependent upon the deposition conditions of individual
films. The data reported do not permit us to establish
a correlation between the wear resistance and the
friction coefficient. However, it seems that the interfacial
transfer layer, which affects the friction, also determines
the wear behavior of the DLC films. The testing en-
vironment can determine whether the wear mechanism
is mechanical (adhesive) or tribochemical and can de-
termine the degree of wear.
In addition to its friction coefficient, a factor which
most probably affects the wear behavior of DLC, is
the adhesion of films to the substrates investigated.
This factor, which can be controlled by the preparation
of the substrate and by the deposition parameters, is
not addressed directly in most cases.
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