Diamond and Related Materials 12 (2003) 1003–1007

An improved diamond-like carbon coating with exceptional wear

properties
M. Jarratt*, J. Stallard, N.M. Renevier, D.G. Teer
Teer Coatings Ltd, 290 Hartlebury Trading Estate, Hartlebury, Worcs. DY10 4JB, UK

Abstract

Parameters for the deposition of diamond-like carbon thin films using a hybrid magnetron sputteryplasma-enhanced chemical
vapour deposition (PECVD) system have been optimised in order to improve the properties for high load-bearing applications.
An extensive tribological testing program has been carried out. The main results from this testing program are described. A
typical unlubricated pin-on-disc test in air using a 5-mm-diameter WC–Co pin under a load of 100 N gave a specific wear rate
of 9=10y18 m3 N y1 my1 and a coefficient of friction of 0.02. Extremely low counter-surface wear was also observed. Dry cold
forming simulation tests, carried out using coated WC–Co balls against tin, indicate much lower friction than for uncoated carbide
tools under the same conditions. Due to these properties, the coatings are considered to be suitable for a wide range of industrial
applications. Some current applications are described.
䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Diamond-like carbon; Tribology; Wear; Friction

1. Introduction graphite-like by Raman scattering. They argued that the

As environmental restrictions on the use of lubricants
are enforced, the demand for coatings that allow con-
tacting surfaces to rub against one another with reduced
tangential resistance and low wear is increasing. One of
the most promising candidate coatings is hydrogenated
diamond-like carbon, a-C:H, usually deposited from a
hydrocarbon gas by plasma-enhanced chemical vapour
deposition (PECVD). These coatings are metastable and
contain a mixture of sp2 graphite-like clusters within an
amorphous sp3 diamond-like matrix. The coatings were
designated ‘diamond like’, as some of the properties are
similar to those of diamond, such as high hardness and
a low friction coefficient w1x. It had been thought that
the low friction coefficient of a-C:H coatings is caused
by the occupation of the dangling bonds on the surface
by hydrogen w2x. However, evidence has been presented
w3,4x showing that an interfacial lubricious transfer layer
formed during sliding contact may also be responsible.
Liu et al. w5x have shown the transfer layer to be sp2
*Corresponding author. Tel.:q44-1299-251399; fax: q44-1299-
250171.
E-mail address: mark.jarratt@teercoatings.co.uk (M. Jarratt).
transfer layer formation is due to hydrogen desorption
from the surface, caused by friction-induced localised
annealing at contact asperities, destabilising the sp3
bonding. Under an applied load, shear deformation may
then occur, transforming the sp3 diamond-like bonded
carbon into a sp2 graphite-like bonded carbon layer of
low shear strength.
The attractive properties of a-C:H coatings have
generated a large amount of research on their deposition
and characterisation, and subsequently the development
of the material for industrial applications w6x. Unfortu-
nately, the current range of applications is limited, as
most commercially available a-C:H coatings suffer from
poor levels of adhesion, high intrinsic stresses and low
load-bearing capacities, i.e. the capability of supporting
normal and tangential loads, particularly when deposited
on alloy steels.
Typically, the specific wear rate of a-C:H coatings is
in the range ;10y16 –10y15 m3 Ny1 my1 w7x and the
coatings fail rapidly at contact pressures greater than 1
GPa w8x. To reduce the intrinsic stress of a-C:H coatings,
various metals have been added, but these a-C:HyMe
coatings have higher specific wear rates, ;10y15 m3
Ny1 my1 w9x. The specific wear rate of hydrogen-free
carbon coatings, (a-C) has been shown to be lower,

0925-9635/03/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0925-9635(02)00296-0
1004 M. Jarratt et al. / Diamond and Related Materials 12 (2003) 1003–1007
;10y18 m3 Ny1 my1, but the coatings are only capable
of supporting contact pressures of -1.4 GPa w10x.
Multilayer nanocomposite Tiya-C, TiCya-C and CNya-
C coatings have been deposited that are capable of
supporting contact pressures above 2 GPa, but their
specific wear rates are ;10y16 m3 Ny1 my1 w8x.
A method has been developed for the deposition of
an a-C:H coating, to be referred to as coating A in this
study, that is capable of supporting high contact pres-
sures with a low friction coefficient and low wear rate.
The deposition equipment utilises unbalanced magnetron
sputtering in a closed-field magnetic arrangement w11x
to deposit an adherent interlayer, followed by a pure a-
C:H film by PECVD (without metal addition). The
substrates are biased using pulsed direct current (DC)
rather than conventional radio frequency (RF). Some of
the advantages offered are improved reliability, a reduc-
tion in cost and elimination of load volume limitations
associated with RF-biased systems, enabling the coating
of industrially relevant dimensions and geometries. The
equipment also uses a low-power ancillary RF electrode
to assist the dissociation of the precursor, therefore
allowing independent control of the substrate bias volt-
age and substrate ion current. It is possible to control
and optimise the properties of the coatings with this
system.
In this study the adhesion, plastic hardness and tri-
bological behaviour of the best commercially available
coating, referred to as coating B, is compared to coating
A. This coating also has an (unknown) interlayer for
increased adhesion. The influence of the testing para-
meters (normal load, sliding speed) on the friction
coefficient and the specific wear rate was examined.
Following tribological testing, the suitability of coating
A for the particular high load-bearing application of
cold forming tin was assessed in unidirectional, unlubri-
cated, cold forming simulation tests using coated WC–
Co balls.
2. Experimental procedures
2.1. Coating deposition
Coatings were deposited using a Teer hybrid unbal-
anced magnetron sputter ion-platingyPECVD deposition
system. Substrates were plasma-ion-cleaned prior to
deposition. A chromium layer was first deposited by
DC magnetron sputtering using argon as the working
gas, followed by a chromium carbide base layer by the
addition of butane, controlled via a closed-loop optical
emission monitoring (OEM) system. Finally, an a-C:H
layer was deposited using a pulsed DC bias and an
electrode with a 13.56-MHz RF generator. The maxi-
mum substrate temperature was estimated from experi-
ence to be below 250 8C. The substrates for coatings A
and B were both M42-grade high-speed steel coupons
polished to a 1200-grit SiC finish. The overall thickness
of coating A was 1.7 mm (chromium plus chromium
carbide thickness 0.7 mm, a-C:H thickness 1 mm) in
comparison to an overall coating thickness of 2.2 mm
for coating B, both calculated from taper cross-sections
produced by ball craters.
2.2. Adhesion tests
The adhesion of the coatings was assessed using a
Teer ST3001 scratchywear tester with a Rockwell dia-
mond tip, a load rate of 100 N miny1 and a constant
sliding speed of 10.0 mm miny1, and a standard Rock-
well-C indentation tester (WilsonyRockwell B503-R)
using a load of 150 kgf. Two scratches and two indents
were made on each coated sample to avoid testing
anomalies.
2.3. Plastic hardness and Young’s modulus measurement
The plastic hardness and Young’s modulus of the
coatings were determined using a Fischerscope H100
tester with a Vickers indentor from the load–penetration
curves, assuming a Poisson coefficient of 0.3. Five
indents were made on each sample and the data were
averaged. The loading–unloading rate was 10 mN sy1,
with a maximum applied load of 50 mN.
2.4. Tribological tests
2.4.1. Pin-on-disc tests
The dependence on the load and sliding speed of the
friction coefficient and specific wear rate was assessed
using a Teer POD-2 pin-on-disc tester with a 5-mm-
diameter WC–6% Co ball. The tests were performed
unlubricated and at room temperature (20"4 8C) and
relative humidity (35"3%). The surface roughness of
the balls was not measured. Coating A was tested using
applied loads of 20, 40, 60, 80 and 100 N and a linear
sliding speed of 0.2 m sy1 for a sliding distance of 720
m. Complete spallation of coating B occurred almost
immediately for an applied load of 40 N, and therefore
only the results for 20 and 40 N are shown. Coating A
was also tested using an 80-N load and linear sliding
speeds of 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6 m sy1 for a
distance of 720 m. The coefficient of friction was
monitored using a strain-gauge load cell and continually
recorded. Contact pressures were calculated from the
contact area on the ball, measured using optical micro-
scopic analysis after the test, and the normal applied
load. The wear volumes of the coatings were calculated
from taper cross-sections produced by ball craters on
the wear tracks after testing, and normalised with respect
to the load and sliding speed to give specific wear rates.
 M. Jarratt et al. / Diamond and Related Materials 12 (2003) 1003–1007
Fig. 1. Coefficient of friction as a function of sliding distance for
coating A using applied load of 20, 40, 60, 80 and 100 N.
2.4.2. Dry cold forming simulation test
Many industrial applications require tools to withstand
high contact pressures; one particular application is the
dry cold forming of tin. A Teer ST-3001 scratchywear
tester was used to provide an initial assessment of
coating A for this application using coated WC–Co
balls against tin sheets. The test is unidirectional under
constant load and new material is brought into the
contact zone at the start of each sliding pass. The
coefficient of friction was monitored using a strain-
gauge load cell and compared to uncoated WC–6% Co
balls against tin. A load of 30 N was used to simulate
the contact pressure of the application, ;2 GPa, and
the sliding speed was 0.5 m miny1.
3. Results
3.1. Adhesion tests
Optical analysis of the scratch channel on coating A
showed the critical load Lc)60 N, although isolated
chipping of the coating was observed in the channel at
a load of ;50 N. The test was stopped at 60 N to
prevent damage to the diamond indentor. Total failure
of coating B was observed for a critical load of 50 N,
with initial chipping occurring at 37 N. Optical analysis
showed slight cracking around the Rockwell indents on
coating A; the adhesion level was classed as HFf2.
The adhesion level of coating B was classed as HFf6
due to extensive spallation around the indents. The
failure appeared to be between the substrate and the
interlayer.
3.2. Plastic hardness and Young’s modulus measurement
The plastic hardness and Young’s modulus of coating
A were 18"0.7 and 146"10 GPa, respectively, and the
indentation depth was 536 nm. The plastic hardness and
Young’s modulus of coating B were 36"0.9 and
194"18 GPa, respectively, and the indentation depth
was 465 nm. The indentation depths are greater than
15% of the total thickness, so significant influence from
the interlayer and substrate is expected.
1005
3.3. Tribological testing
3.3.1. Influence of the applied load on the friction
coefficient and specific wear rate
Fig. 1 shows plots of the coefficient of friction as a
function of sliding distance for coating A using applied
load of 20, 40, 60, 80 and 100 N.
The initial value of the coefficient of friction for all
applied loads tested was approximately 0.1. The rate of
decrease, the steady-state coefficient of friction value
and the specific wear rate were found to be dependent
on the load: the greater the load, the faster the decrease,
the lower the steady-state friction coefficient and the
lower the specific wear rate. The steady-state friction
coefficient and specific wear rate ranged from 0.07 and
2.5=10y17 m3 Ny1 my1, respectively, for 20 N (contact
pressure ;1 GPa) to 0.01 and 9.8=10y18 m3 Ny1
my1, respectively, for 100 N (contact pressure ;3.5
GPa). Optical microscopic analysis of the countersurface
pin after testing showed a transfer layer in the contact
area and build-up in front of the contact area in the
direction of sliding that increased in quantity with
applied load. Attempts to detach the transfer layer
showed that the majority was easily removed, but a
small amount remained in the contact area. A slight
smoothing of the outermost peaks of the surface rough-
ness was also observed on the pin for all applied loads.
Fig. 2 shows typical plots of the friction coefficient
vs. sliding distance for coating B using applied load of
20 and 40 N.
Using a load of 20 N the friction coefficient of
coating B started at 0.13, but within the first few seconds
had reduced to 0.08. A gradual reduction was then
observed until a steady state of 0.04 was reached near
the end of the test. The level of wear was too small to
measure using optical microscopic analysis, and the
specific wear rate was therefore calculated to be less
than 1.4=10y17 m3 Ny1 my1. Optical microscopic
analysis of the countersurface pin after testing showed
a transfer layer in and ahead of the contact region that
was easily removed, and a slight smoothing of the
outermost peaks of the surface of the pin. When a load
Fig. 2. Coefficient of friction vs. sliding distance for coating B using
applied load of 20 and 40 N.
1006 M. Jarratt et al. / Diamond and Related Materials 12 (2003) 1003–1007
of 40 N was used the coating failed immediately,
indicated by a sudden increase in the coefficient of
friction (Fig. 2). Optical microscopic analysis of the
wear track showed complete coating delamination.
3.3.2. Influence of the sliding speed on the friction
coefficient and specific wear rate
The rate of decrease of the coefficient of friction of
coating A was similar for all sliding speeds tested. The
steady-state coefficient of friction was reached within
the first 100 m and showed a slight trend towards lower
values with the sliding speed, ranging from 0.04 for a
sliding speed of 0.1 m sy1 and 0.03 for 0.6 m sy1. The
specific wear rate showed no obvious correlation and
was in the range ;1.2–1.6=10y17 m3 Ny1 my1.
Optical microscopic analysis of the countersurface pin
showed a similar amount of transfer on the pin, in and
ahead of the contact area. The majority was easily
removed, but a small amount remained in the contact
area. Slight smoothing of the outermost peaks of the
surface roughness was also observed on the pin for all
sliding speeds.
3.4. Dry forming simulation test
Only coating A was tested due to the high contact
pressure, ;2 GPa, of the application. A low coefficient
of friction of 0.1–0.2 was measured throughout the dry
cold forming simulation process, in comparison to 0.4–
0.7 for uncoated WC–Co tools. Full details of the test
and the results are given elsewhere, including similar
results for aluminium alloy and stainless steel w12x.
4. Discussion
Low wear rates and friction behaviour were observed
for coating A for high loading and high-speed testing
conditions. The coefficient of friction vs. sliding distance
plots in Fig. 1 all showed a ‘running in period’. The
friction started at ;0.12 and was followed by a rapid
decrease, then a gradual reduction until reaching a
steady-state ultra-low friction value (0.02–0.03) near
the end of the test. When tests using higher loads were
carried out, the coefficient of friction reduced at a faster
rate, reached the steady-state friction level sooner and
resulted in a lower specific wear rate. Microscopic
observations of the WC–Co pin material after testing
showed a transfer layer that increased in quantity with
the applied load. Attempts to detach the transfer layer
from the pin showed that the majority was easily
removed, but some remained in the contact area. Optical
microscopic analysis of the countersurface pin after tests
showed slight smoothing of the outermost peaks of the
surface roughness, and consequently pin wear could not
be measured.
Coating B could not withstand loads greater than 20
N, corresponding to a contact pressure of approximately
1 GPa, and failed almost immediately. However, this
coating exhibited a low specific wear rate and steady-
state friction for an applied load of 20 N.
Low friction and wear behaviour were observed for
coating A for all sliding speeds tested using an applied
load of 80 N. The coefficient of friction vs. sliding
distance plots all showed a ‘running in period’ before
reaching a steady-state value. No correlation between
the rate of decrease of the coefficient of friction and the
specific wear rate with the sliding speed was observed.
However, the steady-state coefficient of friction value
reduced slightly with sliding speed. Optical microscopic
analysis of the countersurface showed a similar level of
transfer on the pin for all sliding speeds. It is probable
that the transfer layer is responsible for the low friction
behaviour, and a higher load may increase the contact
asperity temperature and the strain energy more than the
sliding speed, resulting in a higher level of dehydroge-
nation and shear deformation. Further tests using lower
loads will be carried out and presented at a later date.
The suitability of coating A for the application of
cold dry forming tin was assessed in simulation trials.
Lower friction behaviour of coated WC–Co balls was
measured in comparison to uncoated balls. Following
the simulation trials, the coating is now in use by a
manufacturer for the dry cold forming of tin. The
manufacturer has observed an improvement of over 10-
fold in tool lifetime compared to uncoated WC–Co
tools. Many other highly loaded tribological applications
are also under investigation, including the coating of
automotive engine cam followers, plastic injection
moulds and CD dies.
5. Conclusions
An industrial-scale hybrid unbalanced magnetron
sputter ion platingyPECVD deposition system has been
used to deposit a-C:H coatings. Unlubricated pin-on-
disc experiments on these coatings have shown low
friction behaviour and coating wear rates under high
loading conditions corresponding to contact pressures in
the range 1–3.5 GPa. When higher loads are used the
coefficient of friction reduces at a faster rate, reaches a
lower steady-state value and a lower specific wear rate
is also observed. When tested using different sliding
speeds and an 80-N applied load, the steady-state friction
value is slightly lower for higher speeds, but no similar
correlation was observed for the rate of decrease of the
coefficient of friction or the specific wear rate. A transfer
layer is observed on the WC–Co ball countersurface
after all tests that appears to increase in quantity with
applied load. This is probably the cause of the low
friction behaviour of the coatings and may also be
responsible for the protection of the countersurface.
 M. Jarratt et al. / Diamond and Related Materials 12 (2003) 1003–1007
Coated WC–Co balls showed lower friction behaviour
in comparison to uncoated balls in unlubricated cold
forming tin simulation tests. Following these tests,
industrial field trials of coated WC–Co tools by a cold
forming manufacturer have shown over a 10-fold life-
time improvement in comparison to uncoated tools.
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