Available online at www.sciencedirect.

com

Wear 264 (2008) 505–517

Potential of wear resistant coatings on Ti–6Al–4V

for artificial hip joint bearing surfaces
W. Österle a,∗ , D. Klaffke a , M. Griepentrog a , U. Gross b , I. Kranz b , Ch. Knabe b
aBAM, Berlin, Germany
b Charité Universitätsmedizin, Berlin, Germany
Received 2 May 2006; received in revised form 5 March 2007; accepted 2 April 2007
Available online 16 May 2007

Abstract
Tribological screening tests (simple, reciprocating ball-on-flat tests) were performed with the objective to identify an appropriate coating for
the articulating surfaces of artificial hip joints whose acetabular cups and femoral stems are made from Ti–6Al–4V alloy, which is appreciated
for its light weight, good biocompatibility and elastic properties similar to those of natural bone. Standard coatings like TiN or CrN performed
better than more complicated multi-layer systems, though not as good as different types of amorphous carbon coatings, generally referred to as
diamond-like carbon or DLC coatings. Among the latter, hydrogenated amorphous carbon (a-C:H) displayed the best properties, especially if the
hydrogen content was increased by reducing the bias voltage during PA-CVD-deposition.
The optimised a-C:H coating revealed the most promising wear behaviour under the applied testing conditions, i.e. the increase of linear wear
with the number of cycles was close to zero. Regarding the materials examined in this study, correlation of wear with mechanical properties
obtained by nano-indentation revealed that high hardness was not an adequate criterion for selecting appropriate coatings. A high ratio of hardness
and elastic modulus (H/E) proved to be more important. Microstructural and micro-analytical investigations revealed transformation of TiN and
CrN to TiO2 and Cr2 O3 , respectively, and amorphous carbon was, at least partly, transformed to graphite. Furthermore, incorporation of Al2 O3
from the ball was observed at a very fine scale. The wear debris of favourable coatings always formed agglomerates of nano-scale particles. It was
shown that commercial nano-particles of Al2 O3 , Cr2 O3 and carbon black are comparable to particles generated by the tribological tests. However,
it is uncertain whether they are comparable to those formed during simulator studies or in vivo. Furthermore, the performance of the favourable
coating has to be tested in a hip joint simulator before its potential for application in prostheses can be assessed.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Coating; Implant; Titanium alloy; DLC; Wear debris; Nano-particles

1. Introduction Ceramic-on-ceramic joints, on the other hand, show very low

Many different material combinations as metal-on-metal
bearings, metal-on-UHMWPE (ultra high molecular weight
polyethylene), ceramics-on-UHMWPE and finally ceramic-on-
ceramic solutions are used for artificial hip joints. Although
metallic or ceramic femoral heads articulating against an
UHMWPE acetabular cup function well in most cases and there-
fore are most commonly used for total hip replacements, they
suffer from high wear of the soft cup which may cause asep-
tic loosening of the implant after various years of function.
∗ Corresponding author at: Federal Institute for Materials Research and Test-
ing (BAM), 12200 Berlin, Germany. Tel.: +49 30 8104 1511;
fax: +49 30 8104 1517.
E-mail address: Werner.oesterle@bam.de (W. Österle).
wear rates of the order of 1 ␮m per year, compared to 100 ␮m per
year for a standard ceramic-on-UHMWPE bearing [1]. Shafts
and inlays for fixation of the joint are preferentially made from
titanium alloys or pure titanium, respectively. In spite of the
excellent biocompatibility, the tribological properties of bearing
surfaces made from titanium alloy are inferior to those of other
materials. Several attempts have been undertaken to improve
the surface properties of titanium alloys or cobalt–chromium
alloys either by plasma treatment [2] or by applying appropriate
coatings [2–7]. In a recent review article Dearnaley and Arps
have stated an optimistic view with respect to biomedical appli-
cations of diamond-like carbon (DLC) coatings [8]. Very low
wear rates can be expected, if both sides of the joint are coated
with DLC layers, but this was only verified for a metal-on-
metal joint [9]. Although good tribological behaviour has been

0043-1648/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.wear.2007.04.001
506 W. Österle et al. / Wear 264 (2008) 505–517
obtained with surface-treated titanium alloy [2], it is difficult to
obtain good adherence of coatings to the UHMWPE. Bruinink
et al. [10] reported a high tendency for hydrogenated DLC (a-
C:H) coatings on UHMWPE to form delaminated fragments.
However, these fragments did not show any adverse effects on
cellular behaviour during in vitro studies in which bone mar-
row cells [10] or macrophages [11] were utilized. Moreover
numerous studies, which were outlined in a recent review by
Dearnaley and Arps [8] corroborate the good biocompatibility
of DLC coatings. Thus amorphous carbon coatings, commonly
referred to as DLC, seem to be suitable for implant applica-
tion, provided that long-term chemical stability [9] and good
adherence to the substrate can be achieved [3,12]. Since the
latter is not the case for coated UHMWPE, different types of
joint designs have been considered for which coated titanium
alloy might be advantageous. Consulting implant manufacturers
led to the conclusion that the substitution of the thick ceramic
layer on the acetabular component of the ceramic-on-ceramic
joint by surface engineered titanium alloy or stainless steel sheet
might be a promising alternative, especially with regard to pro-
cedures which involve minimal invasive surgery. Apart from
DLC and graphite-like carbon TiN [2,4–7] and CrN [4–6] have
been proposed for wear protection of metallic implants. Fur-
thermore, nano-structured or multi-layered coatings offer the
opportunity to improve mechanical properties [13–18]. Based
on these findings, the objective of this study was to identify
the most appropriate combination with respect to the tribolog-
ical couple ceramic ball on coated titanium alloy Ti–6Al–4V.
In addition to favourable tribological performance the char-
acterization of the wear debris is of paramount importance
with respect to biocompatibility considerations. A good bear-
ing results in an extremely low wear rate. However, in these
cases the formation of nanometer-sized wear particles will be
expected [19]. Particles, smaller than 40 nm in size can pene-
trate cellular membranes easily and thus have the potential to
cause genetic damage [20]. Another concern is that the release
of metal ions either directly from the bearing surfaces or from
particles after phagocytosis may cause cancer. The current study
determines the size, chemical composition and microstructure
of wear particles generated by the coatings, which appeared to
be most promising from the tribological point of view. Stud-
ies which examine the effect of micron- and nanometer-sized
wear particles on cell functions will be presented in a separate
publication [21].
2. Experimental procedure
2.1. Materials
Substrate specimens were cut from the same batch of heat
treated (730 ◦ C, 1 h, air cooling) medical grade Ti–6Al–4V
which had been supplied by Jäckel + Co., Frankfurt, Germany
(rod of 30 mm diameter and 3000 mm length). The chemical
composition corresponded to ISO 5832/3. According to the
inspection certificate the mechanical properties were: 890 MPa
yield strength, 955 MPa tensile strength, 15.7% elongation and
48.7% area reduction.
Coatings on polished samples (diameter 30 mm, height
10 mm) were obtained from six different sources.
TiN, CrN and TiN/CN- as well as TiC/C-multi-layered coat-
ings were prepared in our institute with a PVD apparatus of
type HTC 625 Multilab ABS (HAUZER Techno Coating Europe
BV). The nominal coating thickness was 2 ␮m, but with respect
to TiN and CrN, also thicker coatings were produced. Adher-
ence to the substrate was improved by applying a 50 nm thick
titanium interlayer. When producing multi-layered structures,
the thickness of the single layers was adjusted by variation of
the rotation speed while sputtering simultaneously from tita-
nium and graphite targets. Cross-sectional TEM investigation
revealed a single layer thickness of approximately 2 nm for 420
rotations during a deposition time of 5 h (Fig. 8b).
When 1800 rotations per 5 h were applied, single layers were
no longer identified by conventional TEM. This is also true for
the TiN/CN-multi-layer when nitrogen was injected as reactive
gas.
A hydrogen-free tetrahedral carbon coating (ta-C) was pro-
vided by Fraunhofer institute IWS, Dresden, Germany. Pulsed
vacuum arc deposition was applied, as described elsewhere
[22,23]. However, when using this technique, it was not possi-
ble to fully avoid coating defects in the form of carbon particles,
which are depicted in the cross-sectional TEM micrograph in
Fig. 8c. Therefore roughness of the coated surface was reduced
by mechanical polishing.
Hydrogenated amorphous carbon coatings (a-C:H) were pro-
duced by the Fraunhofer Institute IST, Braunschweig, Germany
using a high frequency PA-CVD device (Balzers 13.56 MHz)
operated at 200 ◦ C. A 0.5 ␮m thick titanium interlayer was
produced by magnetron sputtering in the same device prior
to the deposition of the main coating. With standard condi-
tions (bias voltage 800 V) the hydrogen content of the coating
is approximately 15%. With decreasing bias voltage the coat-
ings become softer and the hydrogen concentration can increase
up to 30%.
In addition to the coatings described above, we examined
three additional coatings which were obtained from various
manufacturers. These were amorphous carbon (a-C) or graphite-
like coatings. The latter were denominated as a-C1, a-C2 and
a-C3. Coatings a-C2 and a-C3 were provided by Teer company,
UK and FZ Karlsruhe, Germany, respectively. The manufacturer
who supplied the a-C1 coating requested that his name would
not be disclosed.
2.2. Tribological characterization
The tribological investigations were performed using a tri-
bometer for reciprocating sliding motion, described in more
detail in [24]. We used this rather simple methodology as a
screening test in order to select the most suitable material com-
bination for the desired application. In selecting this approach
it was taken into due consideration that results of simple tests
as these may not be consistent with findings regarding wear
performance when the same materials are evaluated using mul-
tidirectional pin-on-plate tests or hip joint simulators [25], and
may even result in a different kind of wear particles.
 W. Österle et al. / Wear 264 (2008) 505–517
The coated disks were tested articulating against an alumina
ball (10 mm diameter, polished surface Ra = 0.013 ␮m) on top of
the disk. Except for two preliminary tests with lapped surfaces
prior to coating (Fig. 3b and c), polished surfaces were used pro-
viding Ra values of the order of 0.01 ␮m (see also Table 2). A
droplet of distilled water was applied to the articulating surfaces
prior to testing and after time intervals of 12 h to maintain ade-
quate lubrication throughout the testing period. After completion
of the test period, the residual water droplet containing the wear
debris was allowed to evaporate leaving debris particles at the
surface in the vicinity of the wear track. These particles were
characterized as described in Section 2.5. Since pure water was
essential for this type of investigation, we were not able to apply
the usual lubricants which are physiological aqueous saline solu-
tions containing bovine serum. Again this may also have had
an effect on the wear debris, which needs to be taken into due
consideration. All tests were performed with the same set of test
parameters: stroke x = 2 mm; frequency ν = 2 Hz, normal force
Fn = 10 N; temperature T = 23 ◦ C. The initial Hertzian pressure
was approximately 900 MPa (maximum) or 600 MPa (mean),
neglecting the mechanical properties of the thin coatings. For a
first screening the number of reciprocating cycles was fixed at
n = 30 000. These were short-term tests lasting 4.1 h each. Only
one test was performed for each material combination.
The friction force is measured in each test with 500 data, for
comparison the average value of the second half of the testing
period is used. The coefficient of friction is defined as the ratio
of friction force and normal force.
The wear is determined after the test by measuring the dimen-
sions of the wear track and an additional profile of the track
across the centre of the track perpendicular to the sliding direc-
tion. Fig. 1 shows a schematic diagram of the experimental set-up
and the principle applied for profilometry. Preliminary tests with
four equidistant profiles across the track within the stroke length
revealed a scattering range of less than ±10%. Since this degree
of accuracy was sufficient for the screening tests only one pro-
file across the centre of the track was measured. Actually, the
area below the surface is the planimetric wear Wq . The con-
tour of the native ball is plotted in the profile (dotted line), the
distance between the profile and the ball contour represents the
ball wear in a qualitative manner. From the dimensions of the
wear track and the planimetric wear of the cross-section the vol-
umetric wear of both bodies (ball and disk) can be estimated
separately applying the set of equations given in [26]. The total
Fig. 1. Schematic diagram of test procedure and evaluation.
507
coefficient of wear, k, is determined from the sum of volumetric
wear at both bodies (Wv,ball + Wv,disk ) divided by the load Fn and
the total sliding distance, s. In the end, the depth of the wear
track in relation to the coating thickness determined the residual
life time of the coating for the given test conditions. End of life
was reached when the wear track depth approached the coating
thickness.
Since none of the coatings was worn through after 10 000
cycles, but some of them were perforated in the central part of the
track already after 30 000 cycles, tests with 30 000 cycles were
considered sufficient for ruling out inferior coatings from further
testing. With coatings that were not worn through after 30 000
cycles additional tests were performed with 100 000 cycles (test
duration: 13.9 h) and finally 300 000 cycles. These tests with
increased number of cycles allowed the determination of the
evolution of wear and to separate steady-state behaviour from
running-in effects. Furthermore, an extrapolation of wear evo-
lution is possible based on these tests and an estimation of “life
time” of a coating with given thickness can be derived. Since, in
our experiments the contact area was small, the running-in phase
lead to a polishing of only a small area which was completed
after several thousand cycles. When a real artificial hip joint is
tested, usually more extensive wear is required before optimal
geometrical alignment is achieved. In this case the running-in
effects of metal-on-metal joints have been shown to last one
million cycles on the average [4].
2.3. Mechanical characterization
Nano-indentation was applied to reveal mechanical prop-
erties i.e. hardness and elastic modulus of the coatings, the
substrate and the alumina ball which was used as counterpart
for tribological testing.
Dynamic indentation measurements were performed using a
Nano Indenter XP (MTS Systems Corporation, Nano Instru-
ments Innovation Centre) with MTS’ continuous stiffness
measurement (CSM) technique. In this technique a small sinu-
soidal oscillation is superimposed on the primary indentation
loading signal and the response is analysed. By measuring the
amplitude ratio and phase shift between the force and displace-
ment oscillations a continuous measure of the stiffness and
damping of the contact is obtained. Using dynamic indentation
the determination of elastic modulus and hardness as continuous
function of indentation depth will be possible.
508 W. Österle et al. / Wear 264 (2008) 505–517

In the reported indentation experiments primary loading was
controlled such that the strain rate (loading rate divided by
load) was held constant at 0.05 s−1 . The maximum indentation
depth for all experiments was 2 ␮m. Frequency and ampli-
tude of the sinusoidal oscillation were held constant at 45 Hz
and 2 nm, respectively. The Berkovich indenter used was a
so-called AccuTipTM (MTS Systems Corporation, Nano Instru-
ments Innovation Centre). These are very sharp tips with a
nominal tip radius of about 50 nm while conventional Berkovich
tips have a radius of 200 nm or more.
2.4. Microstructural characterization of coatings
Cross-sectional transmission electron microscopy (TEM)
was applied to visualize the microstructure of the coatings and
their interfaces with the substrate. Thin lamellae were prepared
perpendicularly to the surface with a Focused Ion Beam instru-
ment of type FEI Strata 200 xP. The lamellae were lifted from the
samples with a micro-manipulator under an optical microscope
and deposited on carbon-coated support grids, before they were
transferred to an Analytical Transmission Electron Microscope
(JEOL 4000 FX) for microstructural investigation and local-
ized chemical analysis by energy dispersive X-ray spectroscopy
(EDS) with a lateral resolution of 20 nm.
2.5. Characterization of wear particles and friction
induced superficial layers
Since coatings of high quality should exhibit only a small
amount of wear debris, we decided to investigate such features
directly at the site where they had formed. Therefore a tribolog-
ical test was performed with a single drop of water as lubricant,
assuming that wear particles would be deposited around the
wear track after the water has evaporated. Target preparation of
thin lamellae (20 ␮m × 10 ␮m × 0.1 ␮m) was performed with
the Focused Ion Beam Instrument (FIB). For the cross-sectional
TEM investigation of the coatings protection of the surface was
achieved by local deposition of a platinum cap layer by PA-
CVD at the site of interest before applying the cutting mode
of the FIB. Wear particles sticking to the surface near the wear
track were first embedded within a droplet of glue before the
platinum cap layer was deposited. The final TEM investiga-
tions were performed in the same way as already described in
Section 2.4.
3. Results
3.1. Tribology
3.1.1. Tribological performance
A series of preliminary experiments was performed with
the objective to select promising coatings for further, more
comprehensive testing. Based on findings obtained with differ-
ent coatings on steel against alumina balls under dry sliding
conditions it is known that DLC coatings usually display a per-
formance which is superior to that of a conventional TiN coating
[24,27]. This led to the criterion that a favourable coating should
resist 30 000 cycles of reciprocating sliding in air at a normal
load of 10 N without having been worn through to the substrate.
Although artificial hip joints are lubricated contacts we wanted
to make sure that in case of a breakdown of lubricant supply the
system does not fail catastrophically.
Table 1 lists the results of the first screening tests. Unfortu-
nately, all multi-layered coatings which were prepared as an
attempt to improve the properties of the standard TiN coat-
ing failed. Coating fragments with diameters of several ␮m
were detected by scanning electron microscopy. These frag-
ments were located in the vicinity of the wear track, suggesting
that failure occurred by delamination.
For the following three coatings in Table 1 the transversal
profiles which had formed in the centre of wear tracks after
30 000 cycles are displayed in Fig. 2. A deep wear track had
formed at the surface of the TiN coating (Fig. 2a), although it
was not yet completely worn through due to its greater thickness.
The 3.5 ␮m thick CrN coating had been worn to a depth of 3 ␮m
(Fig. 2b), but was still intact. The ta-C coating revealed only a
very small amount of wear (Fig. 2c), but the broad profile of the
track suggests that major ball wear must have occurred.

Table 1
First screening of coatings on Ti–6Al–4V in respect to tribological behaviour
Coating Tribological performance (10 N; 30 000 cycles) Microstructure (TEM) Wear debris SEM or TEM

Depth of wear Total coeff. of weara

scar on disk (10−6 m3 /N m)

TiN, TiC, Ti(C,N), CN mono layers of Worn through Columnar TiN, TiC, TiO2
approx. 2 ␮m thickness
TiN/CN-multi-layer (420) Worn through Nanolayer TiN, TiO2
TiN/CN-multi-layer (1800) Worn through Intermixed TiN, TiO2
Ti/C-multi-layer (420) Worn through Nanolayer TiC, TiO2
TiN (9.5 ␮m) Intact; 5.5 ␮m 2.4 Columnar TiN, TiO2
CrN (3.5 ␮m) Intact; 2.9 ␮m 1.3 Columnar Cr2 O3
ta-C Intact; 0.3 ␮m 0.57 Amorphous Graphon, Al2 O3
a-C:H(800), bias voltage: 800 V Intact; 0.2 ␮m 0.06 Amorphous Graphon, Al2 O3
a-C:H(400), bias voltage: 400 V Intact; 0.9 ␮m 0.39 Amorphous
a-C:H(300), bias voltage: 300 V Intact: 1.0 ␮m 0.29 Amorphous
a-C:H(200), bias voltage: 200 V Intact; 0.08 ␮m 0.018 Amorphous Graphon, Al2 O3
a The “total coefficient of wear” is calculated from the sum of volumetric wear at ball and disk, divided by the total sliding distance and the normal force.
 W. Österle et al. / Wear 264 (2008) 505–517 509

Fig. 2. Profiles of wear tracks on (a) TiN, (b) CrN and (c) ta-C after 30 000 cycles.

The profiles of wear tracks of three hydrogenated amorphous
carbon coatings mentioned in Table 1 are shown in Fig. 3. In all
three cases only a small amount of coating wear was observed.
The higher amount of ball wear deducted from the profiles in
Fig. 3b and c corresponded to the higher surface roughness
revealed by the profiles next to the wear tracks rather than from
different hardness values, since the hardness of all a-C:H coat-
ings was lower than the hardness of the Al2 O3 ball. In fact these
two sample surfaces, revealing a surface roughness of the order
of 1 ␮m (Fig. 3a and b) had been lapped before coating depo-
sition, whereas usually, and in all further experiments, polished
surfaces were applied. The roughness values of these standard
a-C:H coatings are given in Table 2.
3.1.2. Quantitative evolution of coating wear
Table 2 shows data of the coatings which had been selected
for further wear testing. The evolution of linear wear versus
number of cycles is shown in Fig. 4 for coatings a-C2 and
a-C3. The slope of the Wl versus n curve allows an extrapo-
lation to the number of cycles when the wear front approaches
the interface. Assuming a constant wear rate during the whole
life time and a nominal coating thickness of 2.5 ␮m, extrapola-
tion of the data obtained at 10 000, 30 000 and 100 000 cycles
would yield a life time of 0.25 × 106 for coating a-C2, and
2 × 106 for coating a-C3, respectively. After tests with 10 000
cycles both coatings a-C2 and a-C3 show nearly the same depth
of the wear track (0.18 ␮m), but the subsequent steady state

Table 2
Second screening: DLC coatings on polished Ti–6Al–4V from different suppliers
Specimen Supplier Tribological performance Coating
(10 N; n = 100 000)
Depth of wear scar Total coeff. of wear Thickness Indent. hardness Indent. modulus Ra (nm) Rz (nm)
on disk (␮m) (10−6 mm3 /N m) (␮m) (GPa) (GPa)

a-C:H(800) IST Braunschw. 0.43 0.033 1.7 26 232 19 152

a-C:H(200) IST Braunschw. 0.08 0.006 1.8 16 135 16 138
a-C2 Teer UK 0.97 0.084 ∼2.0 16.5 173 15 156
a-C3 FZ Karlsruhe 1.12 0.120 2.7 13.7 177 9 90
510 W. Österle et al. / Wear 264 (2008) 505–517

Fig. 3. Profiles of wear tracks on different a-C:H coatings after 30 000 cycles.

wear rate was significantly higher for a-C2 compared to a-
C3.
In order to confirm the validity of the extrapolation values,
prolonged tests were performed with 300 000 cycles (41.6 h).
The coating a-C2 failed after 154 000 cycles, i.e. earlier than
expected, while the performance of the coating a-C3 corresponds
well to the extrapolation line.
The results of tests with a-C:H coatings, deposited under dif-
ferent conditions, are shown in Fig. 5. The a-C:H(800) coating
shows a similar behaviour when compared to the coating a-C3
(Fig. 4b) with an estimated life time of four million cycles. An
even better result was noted for the a-C:H(200) coating, which
lacked any increase in linear wear within the scatter band indi-
cating already the double value of the determined measuring

Fig. 4. Evolution of linear wear for coatings (a) a-C2 and (b) a-C3, life time extrapolation with first three data points and results of prolonged tests (300 000 cycles).
The same error bars correspond to both diagrams indicating the maximum of ±20% uncertainty of profilometric wear determination.
 W. Österle et al. / Wear 264 (2008) 505–517 511

Fig. 5. Evolution of linear wear for coatings (a) a-C:H(800) and (b) a-C:H(200), life time extrapolation with first three data points and results of prolonged tests
(300 000 cycles). The same error bars correspond to both diagrams indicating the maximum of ±20% uncertainty of profilometric wear determination.

uncertainty. The error bars do not show statistical fluctuations

at different locations of the coating surface because only one
test was performed for each data point. On the other hand, all
data, except one (a-C2 after 300 000 cycles), fit to a straight
line within the limit of ±20%, suggesting good reproducibil-
ity of wear measurements at different locations. Hence, our
data indicate no or only minimal increase of wear of the a-
C:H(200) coating subsequent to 10 000 cycles, although this
coating experienced almost the same amount of wear during the
first 10 000 cycles compared to the other three amorphous carbon
coatings.

3.1.3. Friction
The coefficient of friction (COF) is rather constant in Fig. 6. Stationary COF for different coatings in water-lubricated tests.
all tests as long as the coating was not worn through
in the central area of the tribo-contact. After the coating

Fig. 7. Mechanical properties of substrate material, counter-body and selected coatings.

512 W. Österle et al. / Wear 264 (2008) 505–517

has been perforated the COF increased gradually, because
parts of the coating were still in contact with the alumina
ball.
The comparison of friction behaviour is based on the sta-
tionary mean value of COF, which was in all cases recorded in
terms of the average value of the second half of each test prior
to the perforation of the coating. The stationary COF is shown
in Fig. 6. The friction is highest in tests with CrN, slightly lower
for TiN and nearly the same (between 0.07 and 0.09) for all
carbon-based coatings.

Fig. 8. Cross-sectional TEM micrographs and electron diffraction patterns of selected coatings: (a) CrN, (b) TiC/C multi-layer 420, (c) ta-C and (d) a-C:H(800).
 W. Österle et al. / Wear 264 (2008) 505–517 513

3.2. Mechanical properties
Results of indentation tests are shown in Fig. 7. Obviously
the coatings ta-C and TiN displayed greater hardness than the
Al2 O3 balls. All of the other coatings exhibited a lower hardness,
especially the ones which were more favourable from the tribo-
logical point of view (a-C and a-C:H). Their hardness, however,
was greater than that of the substrate material.
3.3. Microstructural investigations
3.3.1. Microstructure of coatings
Fig. 8 shows the transition from a columnar, fully crystalline
structure which is typical for TiN and CrN (Fig. 8a) to a com-
pletely amorphous structure which is represented by an area
without any contrast in the TEM image and only two very broad
and diffuse diffraction rings in the case of a-C:H(800) (Fig. 8d).
The images depicted in Fig. 8b and c represent intermediate
states between the crystalline and amorphous structure.
Alternating layers of crystalline TiC and amorphous C with
single layer thickness of 2 nm lead to a nano-crystalline structure
which shows sharp but continuous rings of the TiC phase in the
diffraction pattern (Fig. 8b). In addition to the very fine multi-
layered structure, the cross-section also showed some coarse
horizontal lamination, which appeared to be caused by instabil-
ities of the deposition process. It cannot be ruled out that such
defects lead to failure during tribological stressing, although
other reasons might be responsible for the inferior tribological
performance of these types of coatings as well.
Although the ta-C coating was considered to be amorphous
based on electron diffraction data, it also displayed a laminated
microstructure in the TEM cross-section (Fig. 8c). Furthermore,

Fig. 9. Cross-sectional TEM micrographs and electron diffraction patterns of selected wear debris on: (a) TiN, showing TiN-micro-crystals and nano-crystalline
TiO2 (rutil), (b) CrN, showing nano-crystalline Cr2 O3 and (c) ta-C, showing nano-crystalline graphon as well as Al2 O3 .
514 W. Österle et al. / Wear 264 (2008) 505–517

the latter coating contained a large number of growth defects,
which are well-known features in the case of arc sputtering. One
of these defects is shown in the centre of the cross-sectional TEM
micrograph (Fig. 8c). Nano-indentation measurements on this
coating revealed major differences in hardness caused by these
type of defects. This coating demonstrates a rather favourable
tribological performance, except for the high amount of ball
wear, which might have been caused by the abrasion effect of
the hard micron-sized particles present in the growth defects.
3.3.2. Microstructure of wear debris
All coatings with inferior wear properties lead to coarse
wear particles comprising fragments of the corresponding coat-
ing. Low wear rates, on the other hand, normally corresponded
to agglomerates of nano-crystalline particles of a third body
which differs in structure and composition from first and sec-
ond bodies, i.e. coating and alumina ball, respectively. Fig. 9a
shows a mixture of particles generated by both types of wear
mechanism, namely micron-sized crystals of TiN (diffraction
spots) and nano-crystalline rutil (TiO2 ) on top of the TiN-layer.
The latter phase produced rings in the electron diffraction pat-
tern. On the CrN coating a rather thick third-body layer has
formed, as shown in Fig. 9b. The diffraction rings correspond
to nano-crystalline Cr2 O3 (hex, a = 0.49 nm, c = 1.35 nm). The
third micrograph, Fig. 9c, shows the microstructure of a wear
particle which was found at the end of a wear track on the ta-C
coating. It is an agglomerate of two nano-crystalline species,
Al2 O3 and graphite, as revealed by the electron diffraction pat-
tern and corroborated by EDX (not shown here). Micro- or
nano-crystalline graphite, also termed graphon, has extended

Fig. 10. (a) Cross-sectional TEM micrograph of wear debris on the optimised coating a-C:H(200), (b) electron diffraction pattern showing at least two rings of
nano-crystalline graphon and (c) EDX-spectrum, revealing mainly carbon and additionally the presence of Al2 O3 and further unidentified species containing sulphur.
 W. Österle et al. / Wear 264 (2008) 505–517
lattice spacings (a = 0.247 nm, c = 0.693 nm) compared to larger
graphite crystals [28].
Finally, we had to examine the wear debris of the optimised a-
C:H coating, which was difficult because the wear rate seemed
to drop to zero after a short running-in procedure (Fig. 5b).
From one of the tiny particles which were observed on the opti-
cal microscope at the end of the wear track, a TEM-lamella
was prepared with the FIB instrument. Fig. 10 shows the TEM
micrograph (a), the electron diffraction pattern (b) and the EDX-
spectrum (c) of this feature, which is lying on the amorphous
coating surface (lower part) and had been embedded in the amor-
phous platinum cap layer by a PA-CVD process in the FIB.
The EDX-spectrum revealed that the wear debris contained the
following elements: C, Al, O and S. This was in addition to
various artefacts, i.e. Pt resulting from the cap layer, Ga from
the ion source, Cu from the support grid and Ti from the sub-
strate. These data indicate that the wear debris consisted mainly
of carbon resulting from the a-C:H(200) coating. In addition
also a minor amount of aluminium oxide resulting from the ball
and sulphur from the environment was present. The diffraction
pattern (Fig. 10b) showed two rings, which were attributed to
graphon. Two additional rings were present which could not be
attributed to a known phase. It is noteworthy that they did not
correspond to either graphon or ␣-Al2 O3 .
4. Discussion
Generally high hardness is considered desirable for wear
resistant coatings. The findings of the current study however
suggest that the performance of softer coatings is superior to
those of high or even medium hardness. In fact, it is not hardness
alone, but the combination of hardness with low elastic modu-
lus which is most important for a good tribological performance
[16]. Furthermore, the elastic modulus should match the sub-
strate material [29]. Thus, according to Leyland and Matthews
[16], the H/E ratio should provide a better correlation between
mechanical properties and tribological behaviour. Indeed, the
Fig. 11. Ranking of coatings according to their H/E ratios.
515
graph in Fig. 11 shows ranking of coatings with increasing
H/E ratio which corresponds quite well to the tribological test
results. This is especially true for the wear data of the coat-
ings selected after the first screening tests, which are outlined in
Table 2. Although the ta-C coated disk showed low wear, it was
excluded from further tests due to the high ball wear. The amor-
phous carbon coatings show structural differences ranging from
a diamond-like structure (ta-C [22]) to a graphite-like structure
(a-C [33]) and finally to a polymer-like structure (a-C:H [11]).
The microstructural investigations of wear debris and super-
ficial layers at the wear surfaces revealed that a third body
had formed which differed in structure and chemical composi-
tion from both articulating counterparts, i.e. the ball and coated
flat sample. If the coating was a hard nitride like TiN or CrN,
the third body was an Oxide, i.e. TiO2 or Cr2 O3 , respectively,
in accordance with previous findings in the literature [30,31].
If the coating contained amorphous carbon, nano-crystalline
graphite was observed in the wear debris, also in accordance
with previous findings [30,32]. For one of the coatings, a-C2,
evidence of alignment of graphite basal planes parallel to the
wear surface was observed by Teer [33] and Young et al. [34].
In this case Cr-doping was used to reduce coating hardness and
increase toughness, and the explanation given in [33] was that
cross-linking between graphite-like planes was reduced. A sim-
ilar explanation may also be accountable for the reduction of
hardness which was noted in our study for the a-C:H coatings
when increasing the hydrogen content with decreasing bias volt-
age during the deposition procedure. Poorly developed graphite
and alumina nano-crystals mixed with polymer-like wear debris
were formed in this instance, whereas a polymer-like transfer
layer was observed at the ball surface. This is in agreement with
findings described by Hauert [9].
Since extremely low wear rates are likely to produce very
small wear particles, a nano-crystalline microstructure of the
third body is essential for the desired application. Tribo-
oxidation as well as graphitisation of thin superficial layers are
the micro mechanisms which lead to a nano-crystalline third
516 W. Österle et al. / Wear 264 (2008) 505–517
Fig. 12. Cross-sectional TEM micrograph at the ball surface, showing superfi-
cial zone of deformed Al2 O3 and 10 nm thick transfer film, marked by arrows
(presumedly graphon).
body which also will be transferred to the counter-body in the
form of a thin layer, as shown in Fig. 12. Especially, if the coat-
ing is harder than the alumina ball, wear of the counterpart will
occur, leading to a wear debris of mixed graphite and Al2 O3
nano-particles, as shown in Fig. 9c. Nano-crystalline alumina
layers and corresponding wear particles are produced during
mechanical polishing of the alumina ball [35]. Even in the case
of the relative soft a-C:H(200) coating some transfer of alumina
to the wear debris appeared to have taken place (Fig. 10). On the
other hand, a carbon layer was detected in the contact area of the
Al2 O3 ball (Fig. 12), which certainly contributes to preventing
further ball wear.
5. Summary and conclusions
In conclusion, our findings demonstrated that from the tri-
bological point of view a favourable coating should meet the
following requirements: (I) Good adherence to the substrate.
(II) The hardness needs to be slightly lower compared to that of
the counterpart material but sufficiently tough to avoid fracture.
(III) The coating needs to exhibit an elastic modulus which is
similar to that of the substrate material. (IV) Furthermore, the
coating needs to possess the ability to form soft surface films on
both counterparts. The hydrogenated DLC coating a-C:H(200)
met all four criteria. Moreover it demonstrated the highest H/E
ratio and best match of elastic modulus with the substrate mate-
rial, Ti–6Al–4V. The tribological performance was excellent.
In fact it was the only coating which showed the potential to
resist reciprocating sliding for more than five million cycles, at
least at the contact points where the tests had been performed.
A more dedicated decision requires the performance of hip sim-
ulation tests according to ISO standard 14242. Future studies
will involve hip simulation tests of the a-C:H(200) coating in
comparison to the more conventional CrN coating.
Since the wear debris of all coatings which rendered promis-
ing tribological results revealed a nano-crystalline wear debris,
it is essential to perform detailed studies regarding the effect
of nano-particles on cell function. In this context it has to be
considered that within the limits of our tribological tests the
excellent coatings did not yield a sufficient amount of wear
particles for performing the required series of biological exper-
iments. Therefore, commercial nano-particles of ␣-Al2 O3 and
carbon black had to be used, as well as Cr2 O3 nano-particles.
As demonstrated by our TEM investigations, these type of par-
ticles were noted in the wear debris derived from DLC- and
CrN-coatings, respectively. Furthermore, Tipper et al. detected
Al2 O3 nano-particles when examining a ceramic-on-ceramic
joint utilizing a hip joint simulator allowing micro-separation
[35]. This was in addition to a fraction of micro-particles. These
findings are in agreement with observations reported by Hat-
ton et al. who identified nano-sized Al2 O3 particles in tissues
retrieved at revision surgery of a total hip replacement [36].
Although the results of the biological evaluation will be pub-
lished separately [21], the most important findings regarding the
effect of various particles on macrophage behaviour are sum-
marized as follows: (I) Al2 O3 particles elicited less cytokine
formation by macrophages compared to when identical cells
were grown in the presence of carbon black and Cr2 O3 . (II)
Macrophages cultured in the presence of Cr2 O3 particles showed
a significantly decreased cell vitality. This was related to Cr6+ -
impurities in the commercial product which is not supposed
to occur in the wear debris of the medical grade CrN coating.
However, this issue needs to be addressed in future studies. (III)
Nano-particles of ␣-Al2 O3 and carbon black induced greater
cykotine production by macrophages compared to when iden-
tical cells were grown in the presence of micro-sized particles
of the same chemical species. Although aluminum oxide and
carbon are generally considered as being materials of high
biocompatibility, our knowledge regarding particles with diam-
eters below 40 nm is still limited. These particles may detach
from the agglomerates which usually are formed in cell cul-
ture media. Furthermore, recent studies [35,36] indicate that
wear debris tends to form clusters of nano-particles both in vitro
as well as in vivo. As a result, fundamental research involving
appropriate cell culture experiments is required for evaluating
the potential of these particles to elicit adverse cell and tissue
responses.
Acknowledgments
Financial support by the German Research Foundation
(DFG-grants OS 77/8-1 and GR 770/5-1) is gratefully acknowl-
edged.
 W. Österle et al. / Wear 264 (2008) 505–517
Furthermore, the authors would like to thank numerous col-
leagues who supported this work: Mr. M. Hartelt and Mr. B.
Pohlmann (tribo testing), Mrs. A. Krause (photographic work),
Mrs. Ch. Neumann (profilometry), Mr. W. Gesatzke and Mrs.
H. Rooch (FIB), Mrs. I. Dörfel and Mrs. I. Urban (TEM), Mr.
A. Dück (PVD).
References
[1] G. Willmann, Oxide ceramics for articulating components of total hip
replacements, in: L. Sedel, C. Rey (Eds.), Bioceramics, vol. 10, Elsevier,
1997, pp. 123–126.
[2] H. Liang, B. Shi, A. Fairchild, T. Cale, Applications of plasma coatings in
artificial joints: an overview, Vacuum 73 (2004) 317–326.
[3] A.-S. Loir, F. Garrelie, C. Donnet, J.-L. Subtil, M. Belin, B. Forest, F.
Rogemond, P. Laporte, Mechanical and tribological characterization of
tetrahedral diamond-like carbon deposited by femtosecond pulsed laser
deposition on pre-treated orthopaedic biomaterials, Appl. Surf. Sci. 247
(2005) 225–231.
[4] J. Fisher, X.Q. Hu, J.L. Tipper, T.D. Stewart, S. Williams, M.H. Stone, C.
Davies, P. Hatto, J. Bolton, M. Riley, C. Hardakar, G.H. Isaac, G. Berry,
E. Ingham, An in vitro study of the reduction in wear of metal-on-metal
hip prostheses using surface-engineered femoral heads, Proc. Inst. Mech.
Eng., Part H: J. Eng. Med. 216 (2002) 219–230;
J. Fisher, X.Q. Hu, J.L. Tipper, T.D. Stewart, S. Williams, M.H. Stone, C.
Davies, P. Hatto, J. Bolton, M. Riley, C. Hardakar, G.H. Isaac, G. Berry,
E. Ingham, An in vitro study of the reduction in wear of metal-on-metal
hip prostheses using surface-engineered femoral heads, Proc. Inst. Mech.
Eng., Part H: J. Eng. Med. 217 (2003) 155–163.
[5] J. Fisher, X.Q. Hu, S. Williams, J.L. Tipper, E. Ingham, M.H. Stone, P.
Hatto, G. Berry, C. Hardakar, G.H. Isaac, New bearing surfaces: what does
the future hold? Semin. Arthroplasty 14 (2003) 131–139.
[6] J. Fisher, X.Q. Hu, T.D. Stewart, S. Williams, J.L. Tipper, E. Ingham, M.H.
Stone, C. Davies, P. Hatto, J. Bolton, M. Riley, C. Hardakar, G.H. Isaac, G.
Berry, Wear of surface engineered metal-on-metal hip prostheses, J. Mater.
Sci.: Mater. Med. 15 (2004) 225–235.
[7] A. Sokolowska, J. Rudnicki, P. Niedzielski, A. Boczkowska, G. Bogus-
lawski, T. Wierzchon, S. Mitura, TiN-NCD composite coating produced
on the Ti6Al4V alloy for medical applications, Surf. Coat. Technol. 200
(2005) 87–89.
[8] G. Dearnaley, J. Arps, Biomedical applications of diamond-like carbon
(DLC) coatings: a review, Surf. Coat. Technol. 200 (2005) 2518–2524.
[9] R. Hauert, An overview on the tribological behaviour of diamond-like car-
bon in technical and medical applications, Tribol. Int. 37 (2004) 991–1003.
[10] A. Bruinink, A. Schroeder, G. Francz, R. Hauert, In vitro studies of the
effect of delaminated a-C:H film fragments on bone marrow cell cultures,
Biomaterials 26 (2005) 3487–3494.
[11] P.D. Maguire, J.A. McLaughlin, T.I.T. Okpalugo, P. Lemoine, P. Papakon-
stantinou, E.T. McAdams, M. Needham, A.A. Ogwu, M. Ball, G.A. Abbas,
Mechanical stability, corrosion performance and bioresponse of amorphous
diamond-like carbon for medical stents and guidewires, Diamond Relat.
Mater. 14 (2005) 1277–1288.
[12] S.K. Field, M. Jarrat, D.G. Teer, Tribological properties of graphite-like
and diamond-like carbon coatings, Tribol. Int. 37 (2004) 949–956.
[13] S. Zhang, D. Sun, Y. Fu, H. Du, Toughening of hard nanostructural thin
films: a critical review, Surf. Coat. Technol. 198 (2005) 2–8.
[14] Y.T. Pei, D. Galvan, J.Th.M. De Hasson, A. Cavaleiro, Nanostructured
TiC/a-C coatings for low friction and wear resistant applications, Surf.
Coat. Technol. 198 (2005) 44–50.
[15] A. Dück, N. Gamer, W. Gesatzke, M. Griepentrog, W. Österle, M. Sahre, I.
Urban, Ti/TiN multilayer coatings: deposition technique, characterization
and mechanical properties, Surf. Coat. Technol. 142–144 (2001) 579–584.
517
[16] A. Leyland, A. Matthews, On the significance of the H/E ratio in wear con-
trol: a nanocomposite coating approach to optimize tribological behaviour,
Wear 246 (2000) 1–11.
[17] W. Gulbinski, S. Mathur, H. Shen, T. Suszko, A. Gilewicz, B. Warcholinski,
Evaluation of phase, composition, microstructure and properties in TiC/a-
C:H thin films deposited by magnetron sputtering, Appl. Surf. Sci. 239
(2005) 302–310.
[18] A.A. Voevodin, J.S. Zsbinski, Nanocomposite and nanostructured tribo-
logical materials for space applications, Compos. Sci. Technol. 65 (2005)
741–748.
[19] M. Scherge, J.M. Martin, K. Pöhlmann, Characterization of wear debris
of systems operated under low wear-rate conditions, Wear 260 (2006)
458–461.
[20] G. Oberdörster, E. Oberdörster, J. Oberdörster, Nanotoxicology: an emerg-
ing discipline evolving from studies of ultrafine particles. In: Environmental
Health Perspectives, vol. 113, no. 7, (2005), pp. 823–839.
[21] I. Kranz, J. B. Gonzales, C. Knabe, I. Dörfel, M. Gemeinert, M. Griepen-
trog, D. Klaffke, W. Österle, U. Gross, Biological response to micron- and
nanometer-sized particles known as potential wear products from artificial
hip joints, J. Biomed. Mater. A, in review.
[22] B. Schultrich, H.-J. Scheibe, D. Drescher, H. Ziegele, Deposition of super-
hard amorphous carbon films by pulsed vacuum arc deposition, Surf. Coat.
Technol. 98 (1998) 1097–1101.
[23] T. Witke, T. Schuelke, J. Berthold, C.F. Meyer, B. Schultrich, Deposition
of hard amorphous carbon coatings by laser and arc methods, Surf. Coat.
Technol. 116–119 (1999) 609–613.
[24] D. Klaffke, M. Hartelt, Tribological characterization of thin hard coatings
by reciprocating sliding tests, Tribol. Lett. 1 (1995) 265–276.
[25] S. Williams, J.L. Tipper, E. Ingham, M.H. Stone, J. Fisher, In vitro analy-
sis of the wear, wear debris and biological activity of surface-engineered
coatings for use in metal-on-metal total hip replacements, Proc. Inst. Mech.
Eng., Part H: J. Eng. Med. 217 (2003) 155–163.
[26] D. Klaffke, Fretting wear of ceramics, Tribol. Int. 22 (2) (1989) 89–101.
[27] D. Klaffke, A. Skopp, I. Lenke, Tribological characterization of coatings
by oscillating sliding testing, Surf. Coat. Technol. 74–75 (1995) 877–
883.
[28] P.H. Gamlen, J.W. White, Structure and dynamics of microcrystalline
graphite, graphon, by neutron scattering, J. Chem. Soc., Faraday Trans.
2 (72) (1976) 446–455.
[29] S. Ramalingam, L.-S. Zheng, Film–substrate interface stresses and their
role in the tribological performance of surface coatings, Tribol. Int. 28
(1995) 145.
[30] W. Österle, M. Griepentrog, D. Klaffke, Microstructural characterization
of wear particles formed during tribological stressing of TiC and Ti(C,N)
coatings, Tribol. Lett. 12 (2002) 229–234.
[31] Q. Luo, P.E. Hovsepian, Transmission electron microscopy and energy
dispersive X-ray spectroscopy on the worn surface of nano-structured
TiAlN/VN multilayer coating, Thin Solid Films 497 (2006) 203–
209.
[32] Y. Liu, A. Erdemir, E.I. Meletis, An investigation of the relationship
between graphitization and frictional behaviour of DLC coatings, Surf.
Coat. Technol. 86–87 (1996) 564–568.
[33] D.G. Teer, New solid lubricant coatings, Wear 251 (2001) 1068–1074.
[34] S. Young, X. Li, N.M. Renevier, D.G. Teer, Tribological properties and
wear mechanism of sputtered C/Cr coating, Surf. Coat. Technol. 142–144
(2001) 85–93.
[35] J.L. Tipper, A. Hatton, J.E. Nevelos, E. Ingham, D. Doyle, R. Streicher, A.B.
Nevelos, J. Fisher, Alumina–alumina artificial hip joints. Part II. Character-
ization of the wear debris from in vitro hip joint simulations, Biomaterials
23 (2002) 3441–3448.
[36] A. Hatton, J.E. Nevelos, A.B. Nevelos, R.E. Banks, J. Fisher, E. Ingham,
Alumina–alumina artificial hip joints. Part I. A histological analysis and
characterization of wear debris by laser capture microdissection of tissues
retrieved at revision, Biomaterials 23 (2002) 3429–3440.