Microstructural effects on the wear resistance of wrought
and as-cast Co-Cr-Mo-C implant alloys
A. J. Saldı́var-Garcı́a,1 H. F. López2
1
Instituto Tecnológico de Saltillo, Saltillo, Coahuila, México
2
University of Wisconsin—Milwaukee, Milwaukee, Wisconsin
Received 17 April 2004; revised 2 March 2005; accepted 3 March 2005
Published online 17 June 2005 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jbm.a.30392
Abstract: The tribological behavior of two cobalt-base al-
loys—an as-cast high-carbon and a wrought low-carbon Co
alloy—that are used as hip implant materials is examined in
this work. This work discusses the experimental results of
cobalt– cobalt wear pairs, in wrought and as-cast conditions,
where the amount of hexagonal phase is systematically
modified through an isothermal aging treatment. Fully
FCC and HCP Co alloys are tested versus alloys with
various volume fractions of HCP phase (0.05 to 1.0 vol-
INTRODUCTION
Co-Cr and Co-Cr-Mo alloys are among the safest
materials used in the development of hip and knee
orthopedic prostheses, mainly because of their excel-
lent corrosion properties and mechanical strength.1,2
Another material commonly employed within human
fluid environments is ultrahigh-molecular-weight
polyethylene (UHMWPE) as a countersurface in Co-
UHMWPE hip implants. Yet, in these implants, it is
often found that wear can lead to excessive UHMWPE
polymeric debris, which might not be tolerated by the
human body, resulting in toxic effects on the sur-
rounding tissue.3
In order to minimize wear in hip and knee prosthe-
sis there have been important efforts in controlling the
microstructural features of Co-based alloys. Accord-
ingly, the early versions of Co-Cr-Mo alloys used for
hip implants contained relatively high carbon contents
(0.2%), and they were typically processed by invest-
ment casting.4,5 More recently, low-carbon (0.05%)
wrought versions of the Co-Cr-Mo alloys that main-
tain excellent mechanical properties and corrosion re-
sistance6,7 have been developed.1,5 In particular, these
alloys exhibit superior wear properties as compared to
the cast versions due to a homogeneous microstruc-
Correspondence to: H. F. López; e-mail: hlopez@uwm.edu
© 2005 Wiley Periodicals, Inc.
ume fractions). Preliminary results indicate that Co-Cr-
Mo/Co-Cr-Mo alloy pairs both possessing an HCP matrix
microstructure tend to exhibit outstanding wear proper-
ties. © 2005 Wiley Periodicals, Inc. J Biomed Mater Res
74A: 269 –274, 2005
Key words: tribology; wear; Co-base alloys; phase transfor-
mations; microstructure
ture, and the lack of coarse carbide phases. Accord-
ingly, relatively low rates of production of polymeric
wear debris have been reported8 for implants made
with these alloys.
The tribological properties of hip implants are di-
rectly related to the microstructural features of the
contacting surfaces.9. In Co-Cr-Mo-C alloys, there are
two allotropic crystalline structures, hexagonal closed
packed (HCP), and face-centered cubic (FCC), with
HCP being the thermodynamically stable phase at
room temperature.10,11 According to the literature,12
the wear resistance of single-phase cobalt is signifi-
cantly improved when the crystal structure is fully
hexagonal. Metal-on-metal wear tests carried out by
Buckley12 on HCP Co single crystals indicated that
these pairs lead to relatively low friction coefficients
and reduced wear rates when compared with Co-FCC
single crystals.12,13
In conventional hip implants, the exhibited Co mi-
crostructure consists of secondary carbide phases in a
FCC matrix. The FCC matrix is metastable, but it is
kinetically favored due to the sluggishness of the FCC
3 HCP transformation.10,11,15 However, this transfor-
mation can be isothermally induced; hence, it is pos-
sible to have Co-Cr-Mo-C alloys with various volume
fractions of HCP phase.11,14,15
Accordingly, the potential performance of Co alloys
for applications in the biomedical field can be en-
hanced by designing dual-phase (FCC/HCP), or sin-
gle HCP phase Co-Cr-Mo-C structures. In particular,
270 SALDÍVAR-GARCÍA AND LÓPEZ

TABLE I Wear testing

Chemical Composition of Investigated Co-Base Alloys
(wt %)
Alloys Cr Mo C Ni Fe Si
Cast ASTM
F-75 28.5 5.65 0.25 0.35 0.30 0.5
Wrought
ASTM
F-799 27.9 5.59 0.05 0.21 0.17 0.5
future designs of hip implants where the UHMWPE
polymeric component can be substituted by a cobalt
alloy is a real possibility. Accordingly, in this work the
tribological properties of metal–metal Co-base alloy
pairs were investigated. For this purpose, cast and
wrought Co-Cr-Mo-C implant alloys with either a
fully FCC, an FCC-HCP mixture, or a fully HCP crys-
talline structure were considered.
EXPERIMENTAL PROCEDURE
Materials
The materials used in this work were a commercial,
16-mm-diameter wrought low-carbon Co-Cr-Mo alloy
bar and an as-cast, ASTM F-75 high-carbon Co-Cr-Mo
alloy. The chemical composition of these alloys is
given in Table I.
Wear testing was performed on a three-pin-on-disc
Falex machine. The pins were machined from the
wrought Co-Cr-Mo alloy to 6 mm in diameter and 20
mm in length, and discs of 50-mm diameter and 9-mm
thickness were machined from the as-cast alloy.
Heat treating
The pins were homogenized at 1150°C for 1 h, and
it was followed by water quenching yielding a fully
FCC structure, whereas homogenization followed by
aging at 850°C for either 5.5 or 15 h gave rise to 0.5 and
1.0 HCP phase volume fraction, respectively. In addi-
tion, the wear discs were used in two different condi-
tions, 0.05 HCP volume fraction (as cast condition)
and 0.8 HCP volume fraction (homogenization at
1150°C for 1 h followed by isothermal aging at 850°C
for 24 h). The amount of HCP phase (vol %) trans-
formed from FCC after aging was estimated from the
integrated intensities of the (200)FCC and (101៮ 1)HCP
diffraction peaks using the method developed by Sage
and Gillaud.16
The pin and disc contacting surfaces were polished
Co following standard metallographic techniques. Opti-
cal microscopy, scanning electron microscopy (SEM),
Bal. and energy dispersive X-ray analyses (EDX) were
used for microstructural characterization and element
identification. In addition, a Mitutoyo Surftest Ana-
Bal.
lyzer was used for measurements of surface rough-
ness of the contacting surfaces as a function of wear.
The initial average roughness (Ra) was between 0.03
and 0.05 mm (ASTM Standard F732-82). Weight losses
in the wear couples were measured with the use of a
balance with an accuracy of 0.001 g. Metal-wear vol-
ume losses were determined by dividing the weight
losses by the alloy density (8.287 g/cm3).
Six different pin-on-disc conditions were tested,
where pins containing fully FCC, 50% HCP, or 100%
HCP were systematically placed in contact with wear
discs that were fully FCC or 80% HCP. During testing,
three pins with the same microstructure were loaded
uniformly on each disc, making a perfect contact end-
on, for every test. The applied load P on the three pins
was 266.88 N, corresponding to 3.0-MPa nominal con-
tact stress. The applied stress was close to that recom-
mended by the ASTM F732-82 Standard for hip joints
(3.45 MPa). The rotating disc speed was 168 rpm (300
mm/s), and the main radius R was 17 mm. The total
sliding distance for each disk–pin set was 28 km. The
pin– disc interfacial temperature was monitored with
the use of a thermocouple placed into the disc at less
than 1 mm from the contacting surface. No lubrication
fluids were used during the test.
RESULTS AND DISCUSSION
Figures 1 and 2 show the initial microstructures of
the pins and discs used in the wear tests. Notice from
Figure 1(a) that homogenization followed by water
quenching promotes a single-phase microstructure
(⬎98 wt % FCC) consisting of 50 ␮m equiaxed grains
(measurements as specified by the ASTM E-112 stan-
dard) containing annealing twins.
Homogenization followed by isothermal aging pro-
moted the formation of HCP phase in the pins, which
can be identified as a dark phase of discontinuous
semipearlitic appearance.10,14,15 The matrix (light
gray) can be identified as the FCC polycrystalline
structure, and the increase in HCP phase can be fol-
lowed as a function of aging time [Fig. 1(b,c)]. Figure
1(c) shows a fully transformed HCP structure (⬎98 wt
% HCP).
The microstructure of the wear disc in the as-cast
condition is typically a dendritic structure with inter-
dendritic carbides [see Fig. 2(a)], which are expected
WEAR RESISTANCE OF Co-Cr-Mo-C IMPLANTS
Figure 1. Microstructures of pins (wrought Co-base alloy)
with various amounts of HCP phase after homogenization
(1150°C for 1 h) followed by water quenching. (a) Water
quench condition (HCP ⬍ 3 %), (b) water quenching ⫹ aging
at 850°C for 5.5 h (HCP ⬃ 50%), and (c) water quenching
plus aging at 850°C for 15 h (HCP ⬎ 98%).
to be M23C6 (M ⫽ Cr, Mo, Co). M23C6-type carbides
are mostly present for similar alloy compositions.17
After disc homogenization and aging, the FCC matrix
transforms to the dual FCC-HCP structure. This aging
treatment of the as-cast Co alloy promotes the devel-
opment of elongated HCP plates along FCC dendrites
271
and a high density of short plates in the surrounding
areas of eutectic carbides, as shown in Figure 2(b,c). It
was found that disc aging for 24 h led to the formation
of approximately 80% HCP phase.
It was found that the wear volume losses in discs
and pins as a function of the sliding distance follows a
linear trend. This behavior is the same for the total
volume losses in each set (three pins and a disc), and
the results are shown in Figure 3. Notice from this
figure that the set composed of both disc and pins with
HCP (HCP-HCP) microstructures exhibited the lowest
volume losses, whereas the one corresponding to FCC
microstructures (FCC-FCC) exhibited the highest vol-
ume losses. The set with intermediate wear resistance
consisted of an HCP disc and biphasic pins. Appar-
ently, the HCP structure improves the wear resistance
of Co-base alloys in metal–metal wear tests.
Nevertheless, the individual behavior of pins and
discs with different microstructures follows a slightly
different tendency. Figure 4 is a histogram showing
wear losses versus the various pin– disc combinations.
Notice that the presence of HCP phase in the wear
pins has a superior effect in reducing the wear losses
than in any other condition.
The resultant hardness of the heat-treated samples
is given in Table II. Notice that as the volume fraction
of HCP phase in the wrought and cast alloys increases,
the hardness also increases. In particular, the highest
hardness values are found in the as-cast alloy due to
the high carbon content and to the presence of eutectic
carbides.
The improved tribological behavior in pairs with
HCP crystal structures is not simply related to the
small hardness differentials (⌬HRC) between contact-
ing surfaces. Figure 5 shows the effect of ⌬HRC on the
wear volume losses. Notice that if the improved tri-
bological response were dictated by ⌬HRC, the ten-
dency would be linear regardless of the microstruc-
tural conditions investigated.
As it stands, it is clear that pairs with FCC discs and
HCP discs have two different tendencies. Under sim-
ilar ⌬HRCs the wear volume losses are lower in pairs
where the wear disc is made mainly of HCP phase.
This particular behavior could be attributed to the
crystallographic nature of FCC and HCP phases; it is
widely known that metals with FCC structures have a
relatively large number of effective slip systems.12
Hence, they are quite ductile, allowing for appreciable
plastic deformation at the contacting surfaces. Con-
versely, HCP metals have few active slip systems (as
low as three), making plastic deformation a difficult
process in these materials. This agrees with the exper-
imental outcome, which indicates that the volume
fraction of debris produced in these wear pairs signif-
icantly drops due to the lack of significant plasticity
exhibited by the HCP comatrix structure.
Because plastic deformation is significantly hin-
272 SALDÍVAR-GARCÍA AND LÓPEZ

Figure 2. As-cast wear disc microstructures with different amounts of HCP phase. (a) As-cast condition (HCP ⬍ 5%), (b)
water quenching plus aging at 850°C for 15 h, (HCP ⬎ 98%), (c) SEM photomicrograph showing a carbide surrounded by
HCP plates embedded on a FCC matrix.

dered in alloys with HCP crystal structures, their wear
properties are expected to be significantly superior to
those exhibited by materials possessing BCC or FCC
structures. In addition, in the case of Co-base alloys
the presence of carbides, their mean carbide sizes, and
carbide volume fractions also contribute to the final
alloy wear resistance. Hence, the variations in wear
volume fractions shown in Figure 5 can be related to
the intrinsic wear properties of the individual pair
system investigated. This in turn can account for the
exhibited differences between the wear volume losses
between the FCC (disc)-HCP (pins) pairs and the HCP
(disc)-FCC (pins) pairs.
The exhibited microstructure also has an effect on
the resultant friction coefficients. In particular, it is
found that the resultant values of friction coefficients
for FCC-FCC wear pairs are the highest among all the

Figure 3. Wear volume losses of Co-Cr-Mo-C alloy as a Figure 4. Wear volume losses in Co-Cr-Mo-C alloy as a
function of sliding distance. Velocity 300 mm/s, contact function of the HCP content in discs and pins. Wear condi-
stress 3.0 MPa, dry air (pin on disc). tions: Sliding distance 28 km, contact stress 3.0 MPa, dry air.
WEAR RESISTANCE OF Co-Cr-Mo-C IMPLANTS
TABLE II
Resultant Hardness of Wear Testing Samples After Heat
Treating
As-Cast
Disc ASTM Wrought ASTM F-799
F-75 Pins
FCC HCP FCC Biphasic HCP
Disc Disc Pins Pins Pins
HRC Hardness 33.0 41.6 24.8 34.1 39.3
investigated conditions (see Figure 6). Apparently, a
steady state condition is reached in the production of
wear debris that gives rise to the exhibited wear coef-
ficient. In the case of HCP-HCP pairs, the friction
coefficient is initially very low (0.19), but it tends to
increase over time up to values of (0.24). These values
are still below those found in FCC-FCC pairs, and they
can be related to the slow buildup of wear debris in
the pair interface. For the other conditions investi-
gated in this work, this behavior does not follow a
consistent trend, as other factors associated with the
role played by the dissimilar crystal structures on the
overall wear rates are not clearly understood.
An analysis of the resultant wear debris by SEM and
EDX was made in order to find out if oxidation could
influence the tribological response of the contacting
surfaces. Accordingly, it was found that the wear de-
bris consisted mainly of metallic particles combined
with some amount of oxides. An X-ray diffraction
analysis of the metallic debris showed that the cobalt
alloys kept their original crystalline structure. Even in
the FCC-FCC condition there were no HCP diffraction
peaks that would indicate a transformation-induced
HCP process during the test. The presence of metallic
debris (and not only oxides) suggests that during the
test, the metallic surfaces were contacting each other.
In particular, the debris morphology was very similar
in all the cases investigated, suggesting that the wear
Figure 5. Wear volume losses after a sliding distance of 28
km in Co-Cr-Mo-C alloys as a function of ⌬ hardness be-
tween wear components in wear testing pairs (disc on pin).
273
Figure 6. Friction coefficient m as a function of sliding
distance for different wear testing conditions. Metal–metal
pairs with different amounts of HCP phase (pin-on-disc
wear tests).
mechanisms involved are very similar in all the con-
ditions investigated. In particular, the morphology of
the resultant wear debris indicates that some plastic
deformation would be present under the wear condi-
tions employed (metal–metal pin on disc). Figure 7
shows the wear debris, which consists of gray flakes
(identified by EDX as the metallic debris) and some
small white particles containing oxygen, as it was
determined by EDS.
From the above outcome, it is apparent that the
wear behavior of HCP structures has a better tribo-
logical response than the one corresponding to FCC
structures. Accordingly, the wear properties of these
alloys can be improved not only in single pure Co
crystals12 but also in polycrystalline Co-base alloys
through the FCC 3 HCP transformation. This, in turn,
can be used for the development of biomedical devices
with superior tribological properties. In typical hip
Figure 7. Wear debris after a sliding distance of 28 km in
Co-Cr-Mo-C alloys. Metallic debris (gray flakes), oxide
(white particles).
274
implant devices, Co-base alloys are in wear contact
with UHMWPE. However, under these conditions
wear occurs under lubrication, as the implant is ex-
posed to the human fluids and proteins, with the
extent of debris being relatively low. However, the
wear properties of UHMWPE-Co pairs in dry air and
without lubrication are expected to be drastically dif-
ferent.13,18,19
Wear experiments have been carried out on Co-base
alloy pins on either FCC or HCP, on UHMWPE
disks13,18,19 under tribological conditions (nonlubrica-
tion, speed, stress, etc.) similar to the ones employed
in this work. From these tests, it was found that the
amount of UHMWPE debris produced was 70 –75
times the volume losses found in Co-base–Co-base
wear pairs for similar test loads and times. Because
these wear conditions are extremely rigorous, the rel-
atively low wear volume losses exhibited by the HCP-
HCP pairs is a strong indicator of the potential that
this alloy has for the development of high-perfor-
mance hip implants.
Although the idea of developing metal-on-metal or-
thopedic prosthesis is not new, the outcome of the
present work strongly suggests that Co-base alloys
with HCP matrix microstructures can be ideal candi-
dates for the development of advanced hip implants.
Accordingly, from the amount of wear debris pro-
duced in HCP-HCP wear pairs, it is expected that fully
metallic hip implants with HCP microstructures will
not wear at all within the human fluids as lubrication
is present. Besides, Co-base alloys exhibit excellent
corrosion resistance, so wear-corrosion interactions
are expected to be kept to a minimum.
CONCLUSIONS
In this work, metal-on-metal wear tests were carried
out with the use of the three pins on disc technique.
The alloys considered were typical Co-Cr-Mo-C in the
as-cast and wrought conditions, as they are commonly
used in the design of hip implants. These alloys were
heat treated to various conditions which included a
fully HCP matrix and a fully FCC matrix. It was found
that minimal wear volume losses were achieved in
HCP-HCP pin-on-disc pairs. In contrast, the highest
values of mass losses and greatest friction coefficients
corresponded to FCC-FCC pairs. Intermediate values
(mm3/km) where found in FCC-HCP pairs for the
wear conditions used in this work.
Moreover, it was found that the exhibited wear
SALDÍVAR-GARCÍA AND LÓPEZ
volume losses do not follow a single linear trend with
the hardness differential ⌬HRC. Apparently, the mi-
crostructural features of the contacting surfaces play
an important role in the tribological response, and
HCP wear discs perform better than FCC wear discs.
Under the wear conditions employed (metal–metal
pin on disc) the dominant mechanism involved some
plastic deformation on the contacting surfaces, and it
included some oxidation of the wear debris.
Finally, it is suggested that future developments in
hip implants should consider prototypes that are fully
metallic with HCP matrix microstructures, as they
tend to exhibit very low wear rates on contact.
References
1. Agrawal CM. Reconstructing the human body using biomate-
rials. JOM 1988;31–35.
2. Mears DC. Metals in medicine and surgery. Int Metals Rev
1977;119 –155.
3. McKee GK. Proc Inst Mech Eng 1984;181:1966 –1967.
4. Rose RM. Materials for internal prostheses. In: 1974 Yearbook
of Science and Technology. New York: McGraw Hill; 1974.
5. Salinas A, Lopez HF. The effect of carbon on the mechanical
strength of heat treated cast Co27Cr5Mo alloys. In: Proc. Fifth
Intl. Symp. on Processing and Fabrication of Advanced Mate-
rials, TMS/ASM Fall Meeting, Cincinnati, OH; 1996. p 69 –79.
6. Devine TM, Wulff J. J Biomed Mater Res 1975;9:151–167.
7. Holt RT, Wallace W. Mech Eng Report MS-143. Ottawa: Na-
tional Research Council; 1980.
8. Medley JB, Krygier JJ, Bobyn JD, Chan FW, Tanzer M. Trans-
actions 21st Annual Meeting of the Society for Biomaterials;
1995. p 47.
9. Clarke C, Campbell P, Kossovsky N. Particulate debris from
medical implants. Mechanisms of formation and biological
consequences. In: K.R. St. John, editor. ASTM STP 1144. Phil-
adelphia: American Society for Testing Materials; 1992. p 7–26.
10. Rajan K. Phase transformations in a wrought Co-Cr-Mo-C
alloy. Metal Trans A 1982;13A:1161–1166.
11. Cong N, Morphy D. Rajan K. Kinetics of the martensitic FCC-
HCP transformation in Co-Cr-Mo alloy powders. Acta Metal
1984:32;1317–1322.
12. Buckley DH. Cobalt. 1968;38:20. Cited in Crystal structure. In:
Sarker AD, editor. Wear of metals. New York: Pergamon Press;
1976. p 93–95.
13. Huang P. Thesis. Milwaukee: University of Wisconsin–Mil-
waukee; 1997.
14. Saldı́var-Garcı́a AJ. Thesis. Mexico City: CINVESTAV-IPN,
Unidad Saltillo; 1998.
15. Saldı́var-Garcı́a AJ, Manı́ AM, Salinas-Rodrı́guez A. Metal Ma-
ter Trans A 1999;30:1177–1184.
16. Sage M, Gillaud C. Methode d’analyse quantitative des varités
allotropiques du cobalt par les rayons X. Rev Metal 1950;47;
139 –145.
17. Taylor RNJ, Waterhouse RB. J Mater Sci 1986;21:1900 –1906.
18. Huang P, Lopez HF. Mater Sci Tech 1999;15:1324 –1329.
19. Saldı́var-Garcı́a AJ. Unpublished research. Milwaukee: Univer-
sity of Wisconsin—Milwaukee; 2000.