Wear 255 (2003) 999–1006

A tribological study of cobalt chromium molybdenum alloys used

in metal-on-metal resurfacing hip arthroplasty
J. Cawley a,∗ , J.E.P. Metcalf a , A.H. Jones a , T.J. Band b , D.S. Skupien c
a Sheffield Hallam University, Sheffield, UK
b Midland Medical Technologies Ltd., Midland UK
c Doncaster Centaur Precision Ltd., Doncaster, UK

Abstract
Some modern metal-on-metal bearings have undergone early failure and have exhibited a different microstructure from early hip
replacement systems that produced very long lifetimes. This has led to investigations as to why different microstructural conditions, from
ostensibly the same alloy chemistry, have had differing levels of survival. This paper is concerned with the effect of thermal treatment and
hence the resulting microstructure on the wear properties of coupons using a micro-abrasion test.
A series of cobalt–chromium–molybdenum (CoCrMo) alloy (ASTM F-75 98, ISO 5832-4: 1996; BS 7252: Part 4: 1997) sample coupons
with different combinations of thermal treatments (solution heat treatment, hot isostatic pressing or sintering) were studied.
Metallographic studies have been used to determine the volume fraction of carbide present. The carbide level and morphology varied
markedly between samples with respect to thermal history. This work has established that microstructure and in particular the volume
fraction, size and distribution of carbides is critical to the development of a low wear rate system. As-cast materials were determined to
have greater abrasive wear resistance when compared to single or multiple heat treated materials.
© 2003 Elsevier Science B.V. All rights reserved.
Keywords: CoCrMo; Abrasive wear; Heat treatment; Microstructure

1. Introduction can take decades to achieve. Of the existing materials in

common use CoCrMo alloys are widely used in implants
Total hip arthoplasty places high demands upon the ma- such as prosthetic hips and knees. They are available in
terials used for the load bearing surfaces of orthopaedic im- several different conditions defined primarily by their start-
plants. These materials must provide high wear resistance, ing composition (e.g. low or high carbon content), the
strength, impact resistance and low friction whilst both sur- conditions of manufacture (e.g. casting, forging or powder
viving in the environment of the human body and not sig- metallurgy) and subsequent thermal treatments (solution
nificantly altering the human physiology. heat treatment, hot isostatic pressing or sintering) that are
Metal-on-metal bearing systems for hip joint replace- also time and temperature dependant. Variation of any of
ments have been in use for decades [1,2]. Their early use these factors can significantly alter the materials microstruc-
was abandoned due to manufacturing problems including; ture [10–17] and therefore the mechanical and tribological
inconsistency of geometrical features leading to incongruity, properties.
high frictional torque and inadequate fixation leading to Due to the demands put upon these alloys by the appli-
premature device loosening [3–7]. However, some of these cations, there has been much emphasis on their tribological
early metal-on-metal bearings systems have provided the properties particularly with the resurgence of metal-on-metal
longest clinical histories of any material bearings, with re- bearing devices. The combination of composition, manufac-
trieved components having over 30 years articulation whilst turing process and microstructural condition which gives rise
showing little evidence of wear [8,9]. to the optimum tribological performance is therefore of great
While there are many modern materials with excellent interest. In particular, the goal of developing metal-on-metal
tribological properties, the number of materials which are hip joints with lifetimes of 30 years and more, for younger
currently approved for use in vivo is far more limited. and more active patients, has given added importance to un-
Development, approval and acceptance of new materials derstanding the tribological properties of these materials and
determining which of the many material conditions available
∗ Corresponding author. is the optimum for such applications.

0043-1648/03/$ – see front matter © 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0043-1648(03)00046-2
1000 J. Cawley et al. / Wear 255 (2003) 999–1006

There have been many studies on the wear testing of to test results that do not agree from laboratory to labora-
CoCrMo materials for use in artificial hip joints. The test tory and can contradict each other in terms of identifying
methods commonly used can be split into three main cate- the material with the best wear performance.
gories: (i) in vivo studies [4,18–22] through examination of An equally simple but somewhat different test is the
explanted devices; (ii) in vitro hip simulation [3,7,11,23–26] micro-abrasion wear test. This test has rarely been applied
using specially designed hip-simulators; and (iii) in vitro to CoCrMo alloys but this work has shown that the tech-
testing [7,11,12,18,25,27–32] using techniques, such as nique is useful in its ability to distinguish between materials
pin-on-disc or cylinder-on-plate. with similar chemistry but different microstructures and
hence tribological properties. The exact wear mode that
1.1. In vivo studies takes place in vivo is not clear but studies have shown that
an element of abrasive wear is involved [22] and is evident
In vivo studies of prosthetic hip replacements of many as bearing surface scratches on retrieved devices.
types have provided valuable information on the perfor- If abrasive wear is observed on bearing surfaces of
mance of materials in the body. The application of various metal-on-metal devices it is considered detrimental in a
investigation techniques combined with knowledge of prac- number of ways. Plastic ploughing, which is the outcome
tical manufacturing experience allows forensic studies to be of abrasive wear, will basically disturb the geometry of the
carried out on retrieved components. However, such studies bearing surface. This will lead to metal removal and break-
often consist of a relatively small number of samples of down in lubrication film continuity. This effect is regarded
unknown or uncertain metallurgical history. While work at as being significant in terms of degradation of the bearing
our group has been performed to study the microstructures surface. This makes the measurement of abrasive wear re-
of explants and hence determine the metallurgical history sistance a valuable tool in determining the best possible
and relate this to performance, most existing studies do not material condition for wear resistance.
have the benefit of this combined knowledge. In addition,
there are large variations between studies, in the design 1.4. Thermal treatments of CoCrMo alloys
of devices and the conditions under which they were fit-
ted and used (sliding distance and loading). However, it It is well understood and practised that metallic materi-
could be argued that clinical in vivo investigations of wear als may have their microstructures altered by the application
of prostheses represent the most faithful representation of a thermal treatment [10,13,14,17]. Microstructural engi-
of the wear mechanism likely to be experienced by any neering of a metallic material by thermal treatments may
implant. significantly improve its mechanical properties.
Cast materials may have microscopic voids within their
1.2. In vitro hip-simulators structures, often referred to as shrinkage porosity, resulting
in reduced mechanical properties of the material. To close up
In order to assess the performance of materials in a con- these voids, hot isostatic pressing (HIPing) was developed
trolled way, in vitro testing of candidate materials must be whereby a material is heated to near its solidus temperature
carried out. and a pressure, typically 100 MPa (for CoCrMo alloys), is
Many studies have been carried out on hip-simulators us- applied to the cast components. The aim is to achieve full
ing real components under conditions close to that in vivo. densification of the material and hence improve its mechan-
With such tests (as with in vivo explants studies) the varia- ical properties.
tions in test machines, design of components and test condi- Wrought materials are inherently stronger than their cast
tions make a straightforward comparison of results between counterparts. Again, the hot forging, or thermo-mechanical
studies and materials difficult. The same material has been processing of components essentially closes any pre-existing
shown to have an order of magnitude difference in wear rates shrinkage voids and alters the materials grain structures lead-
when tested on different simulators [26]. Therefore, this type ing to superior mechanical and fatigue properties of the same
of testing is best used as a second step after a material’s metallic material.
properties has been evaluated and understood using a far Heat treatments [17], annealing, solution heat treatments
simpler and less expensive test procedure. (homogenisation), thermo-mechanical or HIPing alter the
microstructures of materials, particularly the carbides,
1.3. In vitro test methods phases that strongly influence the tribological properties
of a metal alloy. Hence, a metallic sample with the same
There is a large range of basic tests which can be applied chemistry can have many different microstructures depend-
to study tribology of materials, but the most useful are the ing on its specific thermal history. These being grain size
simple tests which can be easily controlled and the results of the parent metal, size and distribution of the carbide
understood. A widely used test is the pin-on-disc test [28]. phases or the type and volume fraction of carbide phase, for
However, even with such a simple test, the variations pos- example M26 C6 , M7 C3 , M6 C where M can be a complex
sible in terms of test configuration and conditions give rise combination of alloy metals (chromium or molybdenum
 J. Cawley et al. / Wear 255 (2003) 999–1006 1001

for the systems discussed here). It is not uncommon to see Table 1

mixed carbide morphologies of blocky, particulate agglom- Conditions for the micro-abrasion wear testing
erated or lamella eutectoid carbides in materials with the Parameter Value
same chemistry which have undergone different thermal Sliding distance (L, m) 225
treatments. It has been observed that alloying elements Load (FN , N) 0.25
have an effect on CoCrMo alloys microstructure and hence Ball diameter (d, mm) 25
on their mechanical properties [16]. In summary, thermal Liquid media De-ionised water
treatments alter the chemistry and structure of the carbides. Abrasive
The tribological properties of these materials need to be Type SiC
understood in terms of the effect of different thermal treat- Particle size (mean) (␮m) 4.5
Concentration (g cm−3 ) 0.75
ments and hence microstructures of a material for a given
Delivery rate (drop per second) 1
composition. Temperature (◦ C)/humidity (% RH) 22–25/35–45

2. Experimental

The composition of all the samples was from the same

batch of alloy bar stock and was in accordance to the cast
CoCrMo alloy standards [33]. The CoCrMo material se-
lected was classed as a high carbon (0.28%) alloy. Each
thermally treated sample had undergone a particular heat
treatment that represents the typical thermal history of
currently implanted resurfacing materials.

2.1. As-cast (AC)

A cast cobalt chromium molybdenum alloy with compo- Fig. 1. Configuration of the Micro-abrasion wear test machine.
sition in accordance to ASTM F-75 98; ISO 5832-4: 1996;
BS 7252: Part 4: 1997.
the surface of a prosthetic implant to produce a porous sur-
face conducive to osteo integration (bone in-growth) that
2.2. Heat-treated (HT) consequently, promotes implant fixation.
The chemical composition, mechanical properties and
An as-cast sample having a solution annealed heat treat- hardness of each alloy sample were determined.
ment of (1200 ± 10)◦ C in a soft vacuum < 5 × 10−1 mbar, The hardness (HV(20kg) ) of the five grades of material was
for 4 h, then quenched in nitrogen gas from 1200 to 800 ◦ C measured on both transverse and longitudinal cross-sections
at a cooling rate of 50◦ C/min (minimum). taken from the test discs. Each measurement was repeated
five times on each cross-section and a combined average
2.3. HIP (H) taken.
The microstructures of the samples were revealed by
Hot isostatic pressed. The as-cast sample was heated to either carbide staining (4 g potassium permanganate, 4 g
(1200 ± 10) ◦ C in vacuum and subjected to a pressure of sodium hydroxide, 100 ml water) or grain boundary elec-
(103 ± 5) MPa for 4 h then quenched in argon at a cooling trolytic etching (10% ammonium persulphate solution, 6 V).
rate of 8–10 ◦ C/min. The samples were examined using either an optical or
scanning electron microscope (SEM). The morphology of
2.4. HIP and heat-treated (H&HT) the carbides were observed and described. The volume frac-
tions of carbides were estimated from grey scale separation
techniques of the back-scattered electron (BSE) images of
The H and HT are combined.
the polished samples (no etch or stain).
A commercially-manufactured ball-cratering-type test
2.5. Sintered, HIP and heat-treated (ST&H&HT) machine1 was used to conduct micro-abrasive tests using the
conditions indicated in Table 1. The contact configuration
An as-cast material sintered at 1300 ◦ C followed by H and
then HT. 1 Calowear® Micro-Abrasive Test Equipment (CSM Instruments for-
The sintering was performed to simulate the process merly CSEM Systems and Instruments, Pearson Panke Equipment Ltd.,
whereby CoCrMo beads (∼1 mm diameter) are fused to UK).
1002 J. Cawley et al. / Wear 255 (2003) 999–1006

Table 2 for each crater) using a travelling microscope to a precision

Elemental composition of the CoCrMo test samples and ASTM F75-98; of 0.01 mm.
ISO 5832-4: 1996; BS 7252: Part 4: 1997 Standards
The abrasive wear factor, Kabr (mm3 N−1 m−1 ), was cal-
Element Test samples ASTM F75-98; ISO 5832-4: 1996; culated using Eq. (1).
(mass%) BS 7252: Part 4: 1997 (mass%)
πb4
Co Balance Balance Kabr = (1)
C 0.280 0.35 maximum 32LFN d
Cr 28.10–28.31 27–30
Mo 5.61–5.92 5–7 where b is the diameter of the wear scar (mm), L the sliding
Si 0.95–0.96 1.00 maximum distance (m), FN the normal force on the sample (N) and d
Mn 0.36–0.40 1.00 maximum the diameter of the sphere (mm).
P <0.005 0.020 maximum
S 0.002–0.004 0.020 maximum
Al <0.01 0.30 maximum
Fe 0.14–0.24 0.75 maximum
3. Results
Ni 0.27–0.73 1.00 maximum
Ti <0.01–0.03 – The chemical compositions, mechanical properties and
W 0.04–0.05 0.2 maximum hardness of the materials are shown in Tables 2 and 3. The
N 0.007–0.010 0.25
chemical composition and mechanical properties of the sam-
B 0.003 0.01 maximum
ples were in accordance with the standards (ASTM F-75 98;
ISO 5832-4: 1996; BS 7252: Part 4: 1997). No mechanical
data was available for sample ST&H&HT.
is depicted in Fig. 1. The rotating steel ball was continually There was no significant difference in the bulk hardness
fed with a slurry solution of silicon carbide and water. of the as-cast and the thermally treated materials.
A sample coupon (30 mm diameter by 7–10 mm thick) of The microstructures of each sample are shown in
each material was tested five times and the diameters of the Figs. 2–6. The carbides of the as-cast material were
resultant wear crater diameters measured (eight diameters rich in chromium and molybdenum, possessing a blocky

Table 3
CoCrMo alloy conditions, sample designation, mechanical properties, hardness and carbide volume fraction determination
Material condition Sample 0.2% Proof UTS (MPa) Elongation (%) R of A (%) Young’s Hardness Carbide
designation strength modulus (HV(20kg) ) volume
(MPa) (GPa) fraction (%)
As-cast AC 510 926 11 13 210 310 ± 6 5 ± 1
Heat-treated HT 527 920 16.5 17 216 300 ± 6 2.5 ± 0.5
HIP H 505 852 10 13 NA 288 ± 5 2.3 ± 0.5
HIP and heat-treated H&HT 506 904 14 13 229 313 ± 6 2.3 ± 0.5
Sintered, HIP and heat-treated ST&H&HT NA NA NA NA NA 313 ± 8 1.8 ± 0.5
ASTM F75-98; ISO 5832-4: – 450 655 minimum 8 minimum 8 minimum – 266–345(10 kg) –
1996; BS 7252: Part 4:
1997
√
Hardness ± 1, S.E. = σn−1 / n.

Fig. 2. SEM micrographs of the as-cast (AC) sample (grain boundary etched and carbide stain).
 J. Cawley et al. / Wear 255 (2003) 999–1006 1003

Fig. 3. SEM micrographs of the heat-treated (HT) sample (grain boundary etched and carbide stain).

Fig. 4. SEM micrographs of the HIP (H) sample (polished, no etch or stain).

Fig. 5. SEM micrographs of the HIP and heat-treated (H&HT) sample (grain boundary etched and carbide stain).

morphology within the grains and at the grain boundaries. ular carbides. All the thermally processed carbides were
The remaining thermally processed samples had similar richer in chromium than molybdenum.
microstructures to each other, consisting of an agglomera- The carbide volume fraction of the as-cast sample was
tion of particulate carbides that had formed within grains the highest at (5 ± 1)%, followed by the heat treated sample
and at the grain boundaries with the exception of sample at (2.5 ± 0.5)%, then by the HIP and HIP & heat-treated
ST&H&HT which also exhibited finely dispersed intergran- both at (2.3 ± 0.5)% and finally the sintered, HIP and
1004 J. Cawley et al. / Wear 255 (2003) 999–1006

Fig. 6. SEM micrographs of the sintered, HIP and heat-treated (ST&H&HT) sample (polished, no etch or stain).

Table 4
Kabr and carbide volume fraction
Material Kabr (10−3 mm3 N−1 m−1 ) σ n−1 S.D. (10−3 mm3 N−1 m−1 ) Number of craters S.E. (10−3 mm3 N−1 m−1 ) Carbide volume
measured (n) fraction (%)
AC 0.95 0.068 4 0.03 5 ± 1
HT 1.03 0.038 5 0.02 2.5 ± 0.5
H 1.12 0.104 5 0.05 2.3 ± 0.5
H&HT 1.26 0.077 4 0.04 2.3 ± 0.5
ST&H&HT 1.24 0.126 5 0.06 1.8 ± 0.5
√
Kabr S.E. = σn−1 / n.

Fig. 7. Graph showing the relationship between the micro-abrasion wear factor and the carbide phase volume fraction for the CoCrMo samples.

heat-treated sample at (1.8 ± 0.5)%. Table 4 summarises 4. Discussion

the micro-abrasive wear factor and the determined carbide
volume phase fraction for each sample. It is important to recognise that this paper is concerned
The results of the abrasive wear tests versus the carbide with microstructural properties of materials and has taken
volume phase fraction are shown graphically in Fig. 7. no account of geometry, environment (in the physiological
 J. Cawley et al. / Wear 255 (2003) 999–1006 1005

sense) or other variables. Rather, it has concentrated on the materials resistance to wear and have not been studied in
relationship between structural properties and a relatively this work.
simple test of micro-abrasive wear resistance. Carbides are The simplistic nature of the approach had been discussed
known to affect wear rate and it is the measure of carbide above, nevertheless the results obtained have shown that the
volume fraction that has been used to compare the perfor- microstructure of the material and specifically the volume
mance of the various untreated and treated samples. fraction of carbides in this case had a marked effect on the
Furthermore, the volume fraction of carbides was mea- micro-abrasion wear-rate, the materials resistance to abra-
sured using scanning electron microscopy and BSE imaging sive wear.
thus an atomic number contrast mechanism was utilised to
distinguish them.
Using the cobalt matrix as the datum the chromium rich 5. Conclusions
carbides appeared darker (i.e. lower atomic number) than
the matrix whilst the molybdenum rich carbides appeared • The micro-abrasion test has proved to be an effective
lighter (i.e. higher atomic number). All features having a method of establishing a comparison of wear-rate versus
BSE signal different to that of the matrix were counted a microstructural parameter, such as carbide volume frac-
as carbides and the results must be viewed in the light of tion.
this. • Wear-rates as defined by Kabr (mm3 N−1 m−1 ) ranged
Whilst not reported in this paper, energy despersive X-ray from 0.95 × 10−3 to 1.26 × 10−3 for CoCrMo alloys of
analysis used in conjunction with a SEM has shown that the the same composition but with different thermal process-
carbides became richer in chromium following heat treat- ing histories.
ment. This is not regarded as proof of identity of the car- • There was a correlation between carbide volume fraction
bides and as such ’carbide’ in this context means a complex and wear-rate with the highest carbide volume fraction
compound of chromium, molybdenum, carbon and possibly giving the lowest wear-rate.
nitrogen. • The as-cast microstructural condition was determined to
There were little differences in the mechanical proper- have the highest carbide volume fraction and the lowest
ties of the samples when comparing the standard mechan- wear.
ical property data for the as-cast material with the various • Mechanical properties, including hardness, were not gen-
heat-treatments and thermo-pressure treatments. erally affected by the carbide volume fraction of the ther-
Hardness values compared well with the mechanical data mal and thermo-pressure treated samples.
and did not indicate any real differences in mechanical prop-
erties between the thermally processed materials. However,
it is significant to note that hardness does not appear to cor- Acknowledgements
relate with carbide volume fraction showing that the sample
with the highest carbide volume fraction (sample AC) was
The authors express their gratitude for the support of this
statistically indistinguishable from the sample with the low-
work by Doncaster Centaur Precision Ltd., UK, Midland
est carbide volume fraction (sample ST&H&HT).
Medical Technologies Ltd., UK and the ERDF.
The results of the micro-abrasion tests given in Table 4 and
represented graphically in Fig. 7 showed that the wear-rate
was related to the carbide volume fraction such that the
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