Abrasion resistance of oxidized zirconium in comparison with CoCrMo

and titanium nitride coatings for articial knee joints

Mathias C. Galetz, Ernst W. Fleischmann, Christian H. Konrad, Adelheid Schuetz, Uwe Glatzel
Metals and Alloys, University of Bayreuth, Germany
Received 10 December 2008; revised 16 September 2009; accepted 1 November 2009
Published online 16 February 2010 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jbm.b.31581
Abstract: Most total knee replacement joints consist of a
metal femoral component made from a cobalt-chromium-
molybdenum (CoCrMo)-alloy and a tibial component with
an ultrahigh molecular weight polyethylene (UHMWPE)
bearing surface. Wear of the UHMWPE remains the primary
disadvantage of these implants. The allergic potential
ascribed to CoCrMo-alloys is a further concern. Other me-
tallic alloys with and without ceramic coatings are clinically
used to avoid these problems. This study compared the me-
chanical surface properties of an oxidized zirconium alloy
with those of cast and wrought CoCrMo and TiAlV6-4. Addi-
tionally, the inuence of a titanium nitride (TiN)-plasma
coating on the surface properties was investigated. The
composition of the oxidized zirconium layer was analyzed.
Micro- and macrohardness tests as well as adhesion tests
were used to reveal material differences in terms of their
abrasive wear potential in articial joints. VC
2010 Wiley Period-
icals, Inc. J Biomed Mater Res Part B: Appl Biomater 93B: 244251,
2010
Key Words: abrasion resistance, articial knee joint, cobalt-
chromium (alloys), coating(s), counterpart material
INTRODUCTION
Ultra-high-molecular-weight polyethylene (UHMWPE) has
been the material of choice for articial knee joints since its
introduction 40 years ago. Nevertheless, wear debris, result-
ing from motion of these joints, has invariably been found
when UHMWPE is coupled with metal femoral condylar
components.
1
This wear of UHMWPE is regarded as being
the primary factor that compromises the long-term perform-
ance of joint prostheses.
2
Besides concerns about excessive
wear resulting in mechanical malfunctioning of the joint,
clinical studies have found adverse biological reactions
evoked by wear debris. Polyethylene particles in the sur-
rounding tissue are associated with osteolysis leading to
loosening and failure.
3
Many studies have shown that the
counterpart material clearly inuences the wear of polyeth-
ylene in addition to other factors like the joints design.
Wrought or cast CoCrMo-alloys (e.g., CoCrMo28-6) are
the most common materials in knee joints. However, these
alloys have some disadvantages. Scratches with a depth of
110 lm are often found on the surface of retrieved
CoCrMo-implants, although their hardness is comparatively
high.
46
In vitro scratches of only 2 lm in depth increased
the wear of the polyethylene by a factor of 70.
7
Additionally,
both cobalt and chromium can elicit hypersensitivity. The
nickel content in these alloys is even more relevant. A nickel
concentration below 1% can still be sufcient to cause
severe problems in patients suffering from an allergy to
nickel. Nickel is the most common metal sensitizer in
humans, followed by cobalt and chromium.
8,9
The preva-
lence of metal sensitivity among the general population is
1015%.
10
Therefore, a great effort has been made to de-
velop alternative materials for the femoral component with
minimal allergic potential. The exceptionally biocompatible
titanium would be the material of choice if it was not for its
low scratch resistance, as shown before.
1114
Hence, many
surface hardening and coating techniques have been devel-
oped, such as nitrogen diffusion hardening,
15
thermally oxi-
dized titanium,
16
diamond like carbon coatings
17
and the
clinically used titanium niobium nitride (TiNbN) or titanium
nitride (TiN) plasma coating.
18,19
The gold-colored TiN coat-
ings for knee implants can either be applied on a CoCrMo-
or a titanium-alloy bulk material.
In 2005, a new modication of the counterpart material
was clinically introduced: an oxidized zirconium alloy, which
is biocompatible and has minimal allergic potential.
It was modeled after the successful use of oxide ceramic
balls in articial hip joints. Alumina balls provide better
wear behavior when than CoCrMo alloys do.
20,21
It was
shown for hips in vivo and in vitro that conventional
CoCrMo alloys produce about 1.5 times more wear debris
than oxide ceramic counterparts when paired with poly-
ethylene.
20
Still, the adaptation of monolithic ceramic im-
plants to the knee joint, which is subject to large complex
stresses, is questionable due to the low fracture toughness
of ceramics.
22
Additionally, it is difcult to manufacture
complex shapes like the femoral condyles of knee prosthesis
out of monolithic ceramics. These disadvantages can be
avoided if thin ceramic layers are used instead of bulk
ceramics or metals. Ceramic layers of oxidized Zr or PVD-
deposited TiN for medical implants have a thickness of
Correspondence to: U. Glatzel; e-mail: mathias.galetz@uni-bayreuth.de
244 VC 2010 WILEY PERIODICALS, INC.
about 4 lm, as compared with nontreated metallic surfaces,
which have an oxide layer in the range of only some 10 nm.
The shape and the composition of the applied ceramic coat-
ings can enhance the mechanical surface properties that are
critical for tribological applications.
Abrasive wear, adhesive wear and surface fatigue are the
three basic mechanisms considered to cause wear and sur-
face damage in articial knee joints.
This work focuses on the capability of oxidized zirco-
nium to reduce abrasive wear in comparison with clinically
relevant cobalt-chromium alloys and titanium-nitride coat-
ings. The potential for abrasive wear is a function of three
main parameters:
1. The quality of the pristine polished surface with as little
aws as possible;
2. A high scratch resistance and hardness of the femoral
component to guarantee the preservation of the polished
surface and hence a low abrasive contribution to the
wear of the polyethylene counterpart;
3. The critical inherent adhesion between the coating and
the substrate.
It is reported that TiN-surface coatings often show
improved wear behavior in vitro but are prone to develop delam-
inatios, asperities, and coating breakthrough in vivo.
19,23,24
Hard
wear particles of the femoral component can induce additional
abrasion by third body wear.
The potential of hardness improvements on the micro
and macro scale as well as coating failures of different clini-
cally used counterpart materials were examined. Oxidized
zirconium was compared to plasma vapor depositioned
(PVD) TiN coatings on TiAlV6-4, cast and wrought
CoCrMo28-6 and ZrNb2.5 and to the uncoated metallic sub-
strates in the tests.
MATERIALS
Sample discs with a thickness of 5 mm and a diameter of
50 mm were machined and polished from wrought rods of
three different alloys: CoCrMo28-6 (Zapp Medical Alloys
GmbH), ZrNb2.5Alloy (R60.705 -E.Wagener Gmbh), and
TiAlV6-4 (EVG GmbH). Additional CoCrMo-samples were
prepared from an implant made from cast CoCrMo28-6
(Aequos Endoprothetik GmbH) to compare the hardness
between wrought and cast material.
METHODS
Ceramic layer preparation
PVD-Titanium nitride coatings were applied to the different
discs according to the state of the art of industrial technol-
ogy (DOT Medical Implant Solutions).
ZrNb2.5 can be oxidized to create a hard ceramic ZrO
2
layer at the surface. A thermal oxidation in air was con-
ducted at 600

C by the procedure introduced in

25
to form
an oxide-layer on the Zr-alloy-discs. The samples were then
cooled to room temperature in the furnace to create a cohe-
sive and adherent zirconia surface. The cooling rate was
125 K/h. The parts were polished prior to and after oxida-
tion. All discs were mirror nished to a roughness of less
than 0.1 lm (Table I), controlled by a prolometric mea-
surement with a Perthometer C5D. An oxide layer thickness
of about 4 lm on the zirconium samples was chosen for the
mechanical tests, as this corresponds to the thickness pro-
duced by physical vapor deposition of TiN and the thickness
which is used for implants.
26
Microscopy and spectroscopy
A detailed metallographic analysis was conducted on the
oxidized zirconium. The measurements of the coating thick-
ness and of the surface structure of the metallographic
transverse sections were carried out on a ZEISS Axioplan 2
light microscope. Additionally, scanning electron microscopy
(SEM) images were obtained by a Zeiss 1540 EsB Cross-
Beam
VR
SEM to evaluate the structure within the oxidized
zirconium. The elemental distribution of Zr and Nb was
determined by energy dispersive X-ray spectroscopy.
The oxygen diffusion behavior is important for the bond-
ing of the oxide to the substrate. Therefore, the oxygen
depth distribution on the surface of the oxidized zirconium
was also examined.
Element depth proling was performed with glow dis-
charge optical emission spectroscopy (GDOES, Spectruma
GDA 750) and energy dispersive X-ray spectrometry (EDS).
A radio frequency power supply and an anode with 4 mm
diameter were used for the measurements of the Zr alloy
performed with GDOES. The power was set to 25 W at a
constant argon pressure of 300 Pa. The anode to cathode
distance was 0.2 mm. The calibration was done using certi-
ed reference materials and well characterized bulk mate-
rial. The analysis was performed at different points of the
sample surface.
Hardness testing
The roughness R
a
and R
z
of the polished surfaces was meas-
ured using an universal testing device (Innowep-UST).
The micro hardness of the surfaces of the materials and
coatings was tested with a Fischerscope H100. A Vickers in-
denter was used with a load of 50 mN leading to indenta-
tion depths of less than 1/10 of the coating thickness of
TiN or ZrO
2
. The unit of the results is Martens (Universal)
hardness.
TABLE I. Surface Roughness
Material CoCrMo (cast) CoCrMo (wrought) ZrNb2.5 TiAl6-4 Ox. Zr CoCrMoTiN ZrTiN TiTiN
Roughness Ra 0.076 0.074 0.072 0.078 0.082 0.079 0.081 0.088
Rz 0.487 0.470 0.485 0.478 0.585 0.627 0.649 0.692
ORIGINAL RESEARCH REPORT
JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | APRIL 2010 VOL 93B, ISSUE 1 245
A Rockwell A (HRA) indentation test was carried out
with 60 kp load, clearly penetrating the hard surface layer.
It allows for an estimation of what might happen if a large
puncturing load is applied to an implant. This HRA-test is
adequate to measure the adhesion strength of the surface
layer to the substrate on the basis of VDI 3198.
27
A Rock-
well C test operated at 150 kp is described in this guideline.
The Rockwell A indentation test with a load of 60 kp was
found to be suitable for the present substrates. A micro-
graph of the indentation is used to evaluate the adhesion by
comparing it to adhesion strength quality maps HF1-HF6
(Figure 1). SEM was used for this purpose instead of the op-
tical microscope according to VDI 3198 as its depth resolu-
tion was far better.
Simulator test
Wear tests were undertaken to characterize the scratch re-
sistance of the counterpart materials at 1 Hz, utilizing a
three station-wheel-on-at testing device.
28
The three
wheels shown in Figure 2 were made of wrought CoCrMo,
TiN-coated CoCrMo and oxidized zirconium. The wheels
were prepared as described for disks in the material and
methods section.
A single axis twin peak type loading curve
29
was applied
through the vertical axis of the simulator (Figure 3). The
exion-extension motion of the knee was realized similar to
that given in ISO-14323-3 by rotating the wheel, while the
anterior-posterior-translation was applied by moving the
at (Figure 2). The rotational movement was omitted,
although it inuences the wear of the polyethylene signi-
cantly, as shown before.
30
In this case the omission was
acceptable, as the focus of this study was on the scratch
resistance of the counterpart materials. The test was con-
ducted under distilled water as a lubricant. Afterwards, the
surfaces of the counterparts were studied with SEM.
RESULTS
Layer characterization and composition
of the ceramic surfaces
The squared coating thickness of the transformed ZrNb2.5
measured from micrographs of metallographic transverse
sections was plotted over time for the oxidation in Figure 4.
Figure 5 shows a combination of a SEM picture of a 6 lm
thick layer of oxidized zirconium and the GDOES element
depth proling. No aws or cracks were found in the sur-
face layer.
The oxide layer in surface vicinity was almost stoichio-
metric ZrO
2
with some niobium incorporated, most likely in
a mixed oxide complex.
31
The niobium content was omitted
FIGURE 1. The different grades of damage according to the VDI 3198 indentation test.
FIGURE 2. Tribological testing device. FIGURE 3. Loading parameters of the tribological testing device.
246 GALETZ ET AL. ABRASION RESISTANCE OF MATERIALS IN ARTIFICIAL KNEE JOINTS
in the diagram, as it showed a constant depth prole. It was
possible to detect the diffusion zone of oxygen under the
fully transformed oxide with EDS, but it could not be quanti-
ed due to the poor sensitivity of this method for light ele-
ments. However, GDOES measurements of the same sample
revealed a slow decrease of the oxygen content over a depth
of 4 lm, which appears as the dark zone in Figure 5.
The surface condition itself is of concern in bearings,
beside the thickness and constitution of the ceramic layer.
The nontreated quasi-metallic surfaces of the polished metal
with an oxide lm of about 10 nm did not show defects
when investigated by dark eld light microscopy at 1000-fold
magnication. Furthermore, no cracks or pores were found
on the surface of the polished oxidized zirconium samples
[Figure 6(a)]. In contrast to this, a lot of small pits and pin-
holes were found on the surface of the TiN [Figure 6(b)].
These defects are typically generated during the growth of
the coating in the PVD process.
32
The distribution and size of
these aws did not differ signicantly between the substrates.
It was the typical surface appearance of all TiN coatings. The
ceramic layer of the oxidized zirconium, on the contrary, was
build more dense and uniformly than the TiN coating.
The different surface appearances were also reected in
the roughness of the samples with and without coatings, as
given in Table I. The pores and pinholes resulted in high R
z
values found for all TiN-coated materials. The tested metal-
alloys, on the contrary, could be polished to very good sur-
face roughness R
z
. The values for oxidized Zr were between
those of pure metals and TiN coatings.
MECHANICAL BEHAVIOR OF THE DIFFERENT SURFACES
Micro- and macrohardness
The results of the microhardness measurement are shown
in Figure 7 as Martens(Universal)-hardness with a load of
50 mN. The cast and the wrought CoCrMo-alloy showed the
highest micro hardness when uncoated metal alloys were
compared. All coated samples had more than three times
the micro hardness of the substrates, which implies an
increased resistance towards scratching.
Additionally the macroscopic hardness from the Rock-
well test is compared for all coated and uncoated materials
in Figure 7. It is obvious that once the coating was pene-
trated, the compound hardness was only affected by the
FIGURE 4. Oxidation depth as a function of time at 600

C.
FIGURE 5. Elemental depth distribution of oxidized zirconium from
GDOES and the related SEM picture of the layer.
FIGURE 6. (a) Darkeld LM picture of the oxidized Zr surface; (b) Dark-
eld LM of the surface of a TiN coating.
ORIGINAL RESEARCH REPORT
JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | APRIL 2010 VOL 93B, ISSUE 1 247
hardness of the substrate. The wrought CoCrMo alloy
showed the highest hardness and thus the smallest impres-
sion, considerably harder than the same alloy as cast.
Although titanium was very prone to micro impressions its
hardness on the macro scale was similar to that of wrought
CoCrMo due to work hardening. Compared with these mate-
rials, the cast CoCrMo-alloy or ZrNb2.5 was considerably
softer.
Adhesion test
Figure 8(ad) show typical imprints from the Rockwell in-
dentation tests on the different coatings. The typical failure
of a TiN coating on wrought CoCrMo is given in Figure 8(a).
Fine cracks with a maximum length of about 50 lm were
found in the indentation area with small delamination in
the vicinity of the crater. This was classied as adhesion
strength quality HF1. The TiN coating on a TiAlV6-4 sub-
strate showed longer radial cracks (up to 200 lm) and
delamination at the edge of the imprint: HF3 [Figure 8(b)].
TiN coated ZrNb2.5 showed even more extensive, longer
(>200 lm) and more devastating lateral cracking, aggra-
vated by circumferential piling up around the indentation
[Figure 8(c)]. This indentation was rated as HF4. An impres-
sion on the oxidized ZrNb2.5 alloy is shown in Figure 8(d).
Fewer but larger cracks were visible in the ZrO
2
layer
(HF3), as compared with those in the TiN coatings. This is
an indication for higher strength of the coating. The
FIGURE 7. Micro hardness (HM 0.5) and macro hardness (HRA 50).
FIGURE 8. (a) CoCrMoTiN - HF1; (b) TiTiN - HF3; (c) ZrTiN - HF4; (d) Oxidized zirconium - H3.
248 GALETZ ET AL. ABRASION RESISTANCE OF MATERIALS IN ARTIFICIAL KNEE JOINTS
adhesion of the oxidized ZrO
2
layer is much better com-
pared to the TiN-coating on the ZrNb2.5 or the TiAlV6-4.
The coating did not show any bonding to the substrate
around the TiN delamination. Instead in the delamination of
the zirconium oxide layer, a crack split the layer parallel to
the surface, which shows that the outer edge of the layer
remained bonded to the substrate [upper left corner of
Figure 8(d)]. The adhesion strength quality of the different
coating and substrate combinations are summarized in
Table II.
Simulator Test
Severe scratches in the direction of movement could be
found on the CoCrMo-alloy after 1 million cycles already
[Figure 9(a)]. Very small scratches were observed on the
oxidized zirconium [Figure 9(b)], while the surface of the
TiN-coating was completely unaffected, showing no
scratches at all [Figure 9(c)]. This nding reects the results
from the microhardness measurements and the resistance
of a hard coating against abrasive wear. Even after cleaning,
polyethylene debris could still be found in the pinholes of
the TiN as well as in the scratches of the CoCrMo; this is an
indication that polyethylene is susceptible to damage when
running against counterbodies with awed or rough
surfaces.
DISCUSSION
ZrNb2.5 can be oxidized by thermal treatment in air. The
growth of the oxide layer (Figure 4) follows approximately
Tammanns equation for the parabolic layer growth.
31
The
shifted zero crossing results from oxidation during cooling
within the furnace. This nding correlates well with the
coating growth reported by
25
and.
32
Deviations from meas-
urements can be explained by variations in grain orienta-
tion
37
and grain size
38
as well as inuences from a different
temperature gradient during heating and cooling.
The depth distribution of oxygen under the fully trans-
formed layer is important for the adhesion to the substrate.
To our knowledge this is the rst time the oxygen diffusion
underneath a fully transformed layer was measured with
GDOES, whereas it was already shown before that the hard-
ness of the alloy is affected some micrometer under the ox-
ide layer.
26
When the microhardness of the bare metals is com-
pared, CoCrMo shows a higher micro hardness, which
makes it less vulnerable to scratching than TiAlV6-4 or,
even worse, ZrNb2.5. This is one reason why CoCrMo alloys
have been so successful in articial joints for the past 30
years. Even small local loads result in large imprints in the
titanium and zirconium alloy. This conrms that neither
TiAlV6-4 nor ZrNb2.5 must be used without a coating. This
nding agrees with the poor resistance of titanium alloys to
scratching as mentioned in the introduction, and suggests a
similar behavior for bare zirconium. It projects a devastating
outcome whenfor any reasonsthe coating fails and the
bare metal is exposed. This can occur in vivo as shown in
the case of a metal contact due to dislocation of an acetabu-
lar liner made of oxidized zirconium. The protective layer is
destroyed and the resulting wear is disastrous compared
with CoCrMo-alloys.
39,40
A higher micro hardness and scratch resistance of the
articulation surface can be achieved by both, a transformed
ZrO
2
ceramic layer and a TiN coating. At small loads, the
inuence of the underlying substrate is low as can be seen
by comparing the TiN-coatings on the different metallic sub-
strates. The bulk materials are only elastically deformed
under the coating.
It is a completely different matter when the materials
are exposed to higher loads. It was shown by the Rockwell
hardness test, that once a coating is penetrated, the plastic
deformation is dominated by the macro hardness of the
substrate. For example neither the TiN nor the ZrO
2
layer
truly protects the surface from plastic deformation in the
macro hardness test. The macro hardness values are closely
related to the yield strength of the bulk metal materials.
Values of the yield strength of the metals as well as the
moduli are shown in Table II.
Unfortunately, extraordinary high loads can occur in vivo
even under normal service conditions. Some researchers
have found scratches up to 10-lm deep on cast CoCrMo
that can only result from high local loads.
41,42
A better
bonding of ZrO
2
on ZrNb2.5 compared with TiN layers on
all investigated substrates was found in the Rockwell inden-
tation tests. It leads to the assumption that the diffusion
zone measured with GDOES secures a good adhesion to the
zirconium substrate.
The hard ceramic lms exhibit small cracking when sub-
jected to indentation tests at loads exceeding a certain level.
In case of a breakthrough, the strength and the hardness of
the bulk material determines the deformation. This
TABLE II. Comparison of Material Properties (From [33-36])
Yield Strength
(Substrate) [MPa]
Modulus
(Substrate) [GPa]
Modulus
(Layer) [GPa]
Modulus Ratio
(Bulk)/(Layer)
Adhesion
Strength
CoCrMoTiN 550 (cast)
800 (wrought)
220 550 0.4 HF1
ZrNb2.5TiN 506 95 550 0.17 HF4
TiAlV6-4TiN 860 105 550 0.19 HF3
Ox. Zr 506 95 199 0.48 HF3
ORIGINAL RESEARCH REPORT
JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | APRIL 2010 VOL 93B, ISSUE 1 249
deformation causes a bulging and pile-up at the edges of
the crater that in return results in high stresses in the ce-
ramic layer surrounding the indentation. Delamination
occurs in the interlayer due to high stresses combined with
the brittle nature of the hard lms on a rather soft sub-
strate. Therefore, besides the hardness of the layer and its
adhesion to the bulk, the properties of the substrate itself
play a critical role. This is obvious when the adhesion of
TiN - coatings on wrought CoCrMo, TiAl6-4 and ZrNb2.5 are
compared. The generated stresses in the coating decrease
with the deformation of the bulk metal and less damage is
observed. The TiN layer cannot comply with a substrate
that has a much higher propensity to plastic deformation.
However, the layer performance of a TiN coating is worse
on TiAlV6-4 than on wrought CoCrMo, although the substrate
hardness is similar. This is ascribed to the difference in the
elastic moduli of the substrates that becomes important when
the ratio of the moduli between bulk and layer is low (Table
II). This ratio determines the absolute stresses in the strained
parts of the surface.
43
have shown by nite element calcula-
tion that increasing the modulus of a coating from 300 GPa to
540 GPa can result in an increase in tension of up to 100%.
If the difference in moduli is high, like in the case of TiN on
ZrNb2.5, it bears the risk that the bonding layer might fail
even if small elastic loads are cyclically applied.
From this point of view, zirconium oxide has a more favor-
able modulus (closer to that of the metallic alloys) and it
shows therefore less stresses at the interface to the substrate.
It is also the only layer that provides a gradient interface of
chemically bonded material. The hexagonal a-Zr, that is the
major phase at room temperature, remains stable at the oxida-
tion temperature of 600

C and exhibits a very high solubility

for oxygen. This dissolved oxygen enhances the strength of the
alloy.
44
Its steady decline of oxygen content suggests a moder-
ate change in the modulus from the layer to the bulk material.
The layer is denser than TiN, leading to a lower surface
roughness. Asperities are linked to worse tribological behav-
ior as the wear process of polyethylene is accelerated by a
higher roughness of the counterpart.
45,46
Still, the relatively soft zirconium alloy substrate remains
a weak point. Once the layer is destroyed, the load leads to
high deformations of the substrate that in turn induces high
stresses around the impression with the potential to cause
severe damage to the ceramic layer.
CONCLUSIONS
Uncoated ZrNb2.5 and TiAlV6-4 have a low micro hardness
and cannot be used without a coating. CoCrMo28Mo6 per-
forms better as far as micro hardness is concerned, with the
wrought alloy behaving similar to the cast version. When
macro hardness is taken into account, the wrought material
offers higher mechanical properties and is therefore favor-
able. This suggests a superior applicability of wrought
CoCrMo over other uncoated metal alloys in implants.
Oxidized ZrNb2.5 offers a smoother surface appearance
after processing compared with PVD TiN. This consideration
is irrelevant for pure metals with a dense surface that can
be polished to mirror nish.
Oxidized zirconium shows the best adhesion to the sub-
strate, followed by TiN on wrought CoCrMo. This is ascribed
to an oxygen diffusion zone and the comparatively small dif-
ference in the elastic moduli.
The ratio between the modulus of the layer and the sub-
strate plays a crucial role as does the resistance against
plastic deformation of the substrate. Therefore, TiN shows
FIGURE 9. (a) SEM picture of the scratches on wrought CoCrMo after
tribological testing; (b) SEM picture of the scratches on oxidized Zr
surface after tribological testing; (c) SEM picture of the scratches on
TiN coated CoCrMo after tribological testing.
250 GALETZ ET AL. ABRASION RESISTANCE OF MATERIALS IN ARTIFICIAL KNEE JOINTS
the best adhesion to wrought CoCrMo if only TiN PVD coat-
ings are taken into account.
The oxidized zirconium layer is very promising owing to
its high hardness, good bonding, and a modulus in the range
of the metal. Unfortunately, the properties of the alloy
underneath are the poorest of all materials investigated.
REFERENCES
1. Wang A, Sun DC, Stark C, Dumbleton JH. Wear mechanisms of
UHMWPE in total joint replacements. Wear 1995;181-183:241249.
2. Dumbleton JH, Manley MT, Edidin AA. A literature review of the
association between wear rate and osteolysis in total hip arthro-
plasty. J Arthroplasty 2002;17-15:649661.
3. Amstutz H, Campbell P, Kossovsky N, Clarke I. Mechanism and
clinical signicance of wear debris-induced ostheolysis. Clin Or-
thop Relat Res 1992;276:718.
4. Barrack RL, Castro FP Jr, Szuszczewicz ES, Schmalzried,TP. Analy-
sis of retrieved uncemented porous-coated acetabular compo-
nents in patients with and without pelvic osteolysis. Orthopedics
2002;25:13731378.
5. Jasty M., Bragdon CR, Lee K, Hanson A, William H, Harris J. Sur-
face damage to cobalt chrome femoral head prostheses. Bone
Joint Surg B 1994;76:7377.
6. Levesque M, Livingston BJ, Jones WM, Spector M. Scratches on
condyles in normal functioning total knee arthroplasty. Trans
Orthopedic Res Soc 1998;23:247.
7. Fisher J, Firkins P, Reeves EA, Hailey JL, Isaac GH. The inuence
of scratches to metallic counterfaces on the wear of ultra high molec-
ular weight polyethylene. Proc Inst Mech Eng [H] 1995;20:263264.
8. Hallab N, Merritt K, Jacobs JJ. Metal sensitivity in patients with
orthopaedic implants. J Bone Joint Surgery 2001;83:428436.
9. Gawkrodger DJ. Nickel sensitivity and the implantation of ortho-
paedic prostheses. Contact Dermatitis 1993;28:257259.
10. Basketter DA, Briatico-Vangosa G, Kaestner W, Lally C, Bontinck
WJ. Nickel, cobalt and chromium in consumer products: A role in
allergic contact dermatitis. Contact Dermatitis 1993;28:1525.
11. Agins HJ, Alcock NW, Bansal M, Salvati EA, Wilson PD, Pellici
PM, Bullough PG. Metallic wear in failed titanium-alloy total hip
replacements. A histological and quantitative analysis. J Bone
Joint Surg 1988;70:347356.
12. McKellop HA, Sarmiento A, Schwinn CP, Ebramzadeh E. In vivo
wear of titanium-alloy hip prostheses. J Bone Joint Surg 1990;72:
512517.
13. Bischoff UW, Freeman MA, Smith D, Tuke MA, Gregson PJ. Wear
induced by motion between bone and titanium or cobalt-chrome
alloys. J Bone Joint Surg B 1994;76:713716.
14. Hirakawa K, Bauer TW, Stulberg BN, Wilde AH, Secic M. Characteri-
zation and comparison of wear debris from failed total hip implants
of different types. J Bone Joint Surg A 1996;78:12351243.
15. Rodriguez D, Gil FJ, Planell JA. Wear resistance of the nitrogen
diffusion hardening of the Ti6Al4V alloy. J Biomech 1998;31:49.
16. Dong H, Bell T. Enhanced wear resistance of titanium surfaces by
a new thermal oxidation treatment Wear 2000;238:131137.
17. Saikko V, Ahlroos T, Calonius O, Keranen J. Wear simulation of
total hip prostheses with polyethylene against CoCrMo, alumina
and diamond-like carbon. Biomaterials 2001;22:15071514.
18. Pappas MJ, Makris G, Buechel FF. Titanium nitride ceramic lm
against polyethylene. A 48 million cycle wear test. Clin Orthop
1995;317:6470.
19. Ward LP, Subramanian C, Strafford KN, Wilks TP. Sliding wear stud-
ies of selected nitride coatings and their potential for long- term use
in orthopaedic applications. Proc Inst Mech Eng [H] 1998;212:303315.
20. Clarke IC, Gustafson A. Clinical and hip simulator comparisons of
ceramic-on-polyethylene and metal-on-polyethylene wear. Clin Ortho
Rel Res 2000;379:3440.
21. Schuller HM, Marti RK. Ten-year socket wear in 66 hip arthroplas-
ties ceramic versus metal heads. Acta Orthop Scand 1990;61-3:
240243.
22. Rahaman MN, Yao A, Sonny Bal B, Garino JP, Ries MD. Ceramics
for prosthetic hip and knee joint replacement. J Am Ceram Soc
2007;90-71:965988.
23. Raimondi MT, Pietrabissa R. The in-vivo wear performance of
prosthetic femoral heads with titanium nitride coating. Biomateri-
als 2000;21:907913.
24. Harman MK, Banks SA, Hodge WA. Wear analysis of a retrieved
hip implant with titanium nitride coating. J Arthroplasty 1997;
12-18:938945.
25. Davidson JA, Asgian CM, Mishra AK, Kovacs P. Zirconia (ZrO2)-
coated zirconium-2.5 Nb alloy for prosthetic knee bearing applica-
tions. In: Yamamuro KT, Nakamura T, editors. Bioceramics. Vol. 5.
Kobunski Kankokai: Kyoto Publishing, 1992. pp 389401.
26. Long M, Riester L, Hunter G. Nano-hardness measurements of
oxidized Zr-2.5Nb and various orthopaedic materials. Trans Soc
Biomaterials 1998;21:528.
27. Heinke W, Leyland A, Matthews A, Berg G, Friedrich C, Broszeit E.
Evaluation of PVD nitride coatings using impact, scratch and
Rockwell-C adhesion tests. Thin Solid Films 1995;270:431438.
28. Galetz M, Dietel S, Theile B, Glatzel U. Potential for adhesive
wear in friction couples of UHMWPE running against oxidized zir-
conium, titanium nitride coatings and cobalt-chromium alloys. J
Biomed Mater Res: Part B. (Forthcoming)
29. Paul JP. Loading on normal hip and knee joints and on joint
replacements. In: Schaldach M, Hohmann D, editors. Advances in
Articial Hip and Knee Joint Technology. Berlin: Springer; 1976.
30. Barnett PI, Fisher J, Auger DD, Stone MH, Ingham E. Comparison
of wear in a total knee replacement under different kinematic con-
ditions. J Mater Sci Mat Med 2001;12:10391042.
31. Hobbs LW, Rosen V, Benezra M, Stephan P, Treska M, Hunter G.
Oxidation microstructures and interfaces in the oxidized zirco-
nium knee. Int J App Ceram Technol 2005;2-3:221246.
32. Jehn HA. Improvement of the corrosion resistance of PVD hard
coating-substrate systems. Surface Coat Technol 2000;125:212217.
33. Breme J, Biehl V. Metallic biomaterials. In: Black J, Hastings G,
editors. Handbook of Biomaterials Properties.London:Chapman
and Hall; 1998.
34. Datasheet CoCrMo28-6 Zapp Medical Alloys.
35. Eichler J, Eisele U, Roedel J. Mechanical properties of monoclinic
zirconia. J Am Ceram Soc 2004;87-7:14011403.
36. Stone DS, Yoder KB, Sproul WD. Hardness and elastic modulus
of TiN based on continuous indentation technique and new corre-
lation. J Vacuum Sci Tech A 1991;9-4:25432547.
37. Bu rgel R. Handbuch Hochtemperatur-Werkstofftechnik Vieweg; 1998.
38. Goedjen JG, Shores DA. The effect of alloy grain size on the tran-
sient oxidation behaviour of an alumina-forming alloy. Oxidat
Metals 1992;37:125142.
39. Kop AM, Whitewood C, Johnston DJL. Damage of oxinium femo-
ral heads subsequent to hip arthroplasty dislocation three re-
trieval case studies. J Arthroplasty 2007;22:775779.
40. Evangelista GT, Fulkerson E, Kummer F, DiCesare PD. Surface
damage to an oxinium femoral head prosthesis after dislocation.
J Bone Joint Surg 2007;89:535537.
41. Levesque M, Livingston BJ, Jones WM. Scratches on condyle in
normal functioning total knee arthroplasty. Trans Orthop Res Soc
1998;23:247.
42. Jasty M, Bragdon CR, Lee K, Hanson A, Harris WH. Surface dam-
age to cobalt-chrome femoral head prostheses. J Bone Joint Surg
1994;76:7377.
43. Holmberg K, Laukkanen A, Ronkainen H, Wallin K, Varjus S, Kos-
kinen J. Tribological contact analysis of a rigid ball sliding on a
hard coated surface. II. Material deformations, inuence of coat-
ing thickness and Youngs modulus. Surface Coat Technol 2006;
200:1213:38103823
44. Pangopoulos CN. Surface oxide strengthening of zirconium.
Mater Lett 1989;8:216219.
45. Dawson D, El-Hadi Diab MM, Gillis BJ, Atkinson JR. Inuence of
counterface topography on the wear of ultra high molecular
weight polyethylene under wet or dry conditions. In: Polymer
Wear and Its Control. Lee LH, editor. Washington, DC: Am Chem
Soc; 1985. pp 171187.
46. Gispert MP, Serro AP, Colac o R, Pires E, Saramago B. The effect
of roughness on the tribological behavior of the prosthetic pair
UHMWPE/TiN-coated stainless steel. J Biomed Mater Res B Appl
Biomater 2008;84-1:98107.
ORIGINAL RESEARCH REPORT
JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | APRIL 2010 VOL 93B, ISSUE 1 251