ARTICLE IN PRESS

Biomaterials 26 (2005) 4912–4923

www.elsevier.com/locate/biomaterials

Microstructure and corrosion behaviour in biological environments

of the new forged low-Ni Co–Cr–Mo alloys
Sachiko Hiromotoa,, Emi Onoderab, Akihiko Chibab, Katsuhiko Asamic,
Takao Hanawaa,d
a
Reconstitution Materials Group, Biomaterials Center, National Institute for Materials Science, 1-1 Namiki, Tsukuba 305-0044, Japan
b
Faculty of Engineering, Iwate University, 3-18-8 Ueda, Morioka 020-8550, Japan
c
Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku Sendai 980-8577, Japan
d
Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan
Received 9 September 2004; accepted 5 January 2005

Abstract

Corrosion behaviour and microstructure of developed low-Ni Co–29Cr–(6, 8)Mo (mass%) alloys and a conventional
Co–29Cr–6Mo–1Ni alloy (ASTM F75-92) were investigated in saline solution (saline), Hanks’ solution (Hanks), and cell culture
medium (E-MEM+FBS). The forging ratios of the Co–29Cr–6Mo alloy were 50% and 88% and that of the Co–29Cr–8Mo alloy
was 88%. Ni content in the air-formed surface oxide film of the low-Ni alloys was under the detection limit of XPS. The passive
current densities of the low-Ni alloys were of the same order of magnitude as that of the ASTM alloy in all the solutions. The passive
current densities of all the alloys did not significantly change with the inorganic ions and the biomolecules. The anodic current
densities in the secondary passive region of the low-Ni alloys were lower than that of the ASTM alloy in the E-MEM+FBS.
Consequently, the low-Ni alloys are expected to show as high corrosion resistance as the ASTM alloy. On the other hand, the
passive current density of the Co–29Cr–6Mo alloy with a forging ratio of 50% was slightly lower than that with a forging ratio of
88% in the saline. The refining of grains by further forging causes the increase in the passive current density of the low-Ni alloy.
r 2005 Elsevier Ltd. All rights reserved.

Keywords: Forged low-Ni Co–Cr–Mo alloy; Corrosion; Surface composition; Microstructure; Biological solution

1. Introduction wear debris. The wear rate of Co–Cr–Mo-on-Co–Cr–

Co–Cr–Mo alloy is used as a femoral head of joint
prostheses coupled with an ultra high molecular weight
polyethylene (UHMWPE) cup because of the high wear
and corrosion resistance of the alloy. On the other hand,
the UHMWPE wear debris is mainly responsible for
periprosthetic tissue reaction, osteolysis, and eventually,
late aseptic loosening [1]. Then, the joint prosthesis with
a Co–Cr–Mo alloy femoral head coupled with a
Co–Cr–Mo alloy cup is reconsidered to avoid polymer
Corresponding author. Tel.: +81 29 860 4173;
fax: +81 29 860 4714.
E-mail address: hiromoto.sachiko@nims.go.jp (S. Hiromoto).
Mo (metal-on-metal) couple is lower than that of
polymer-on-metal couple although the friction coeffi-
cient of the metal-on-metal couple is higher than that of
polymer-on-metal couple [2].
The problem of the metal-on-metal couple is that the
release of metal ions from the metal-on-metal couple is
larger than that of the polymer-on-metal couple in vivo
[3]. The release of metal ions from the Co–Cr–Mo
metal-on-metal couple prosthesis is continuous over
many years [4]. The continuous release of metal ions
possibly causes the toxicity problem. The metal ions
dissolved from Co–Cr–Mo alloy powder bind serum
proteins much more than those from Ti–6Al–4 V alloy
[5]. The conventional Co–29Cr–6Mo–1Ni alloy (ASTM

0142-9612/$ - see front matter r 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biomaterials.2005.01.028
 ARTICLE IN PRESS
S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923 4913

F75-92) contains 1 mass% of Ni, and the Ni and Co ions
cause an allergy [6]. Especially, Ni causes carcinogeni-
city and the removal of Ni from biometals is a matter of
great concern [7]. The diminishing of Ni from Co–Cr–
Mo alloy is one solution for the toxicity problem of the
metal-on-metal couple.
In order to improve the safety of Co–Cr–Mo alloy,
the low-Ni Co–29Cr–(6, 8)Mo alloys were developed by
Chiba et al. [8,9]. The Ni content of the developed alloy
is less than 0.03 mass% while the conventional Co–Cr–
Mo alloy (ASTM F-75) contains about 1 mass%. The C
content of the developed alloy is same as that of the
conventional alloy. When Ni in Co–Cr–Mo alloy is
reduced, the elasticity and workability of the alloy
generally decreases because Ni as well as Fe and Mn in
the Co–Cr–Mo alloy stabilizes facial-centered cubic
structure (fcc) Co phase and prevents the formation of
stacking faults which cause the decrease of elasticity and
workability [10]. Therefore, in order to save the elasticity
and workability of low-Ni Co–Cr–Mo alloy, grain size
of the alloy was reduced by controlling the forging ratio.
By controlling microstructure, fatigue strength and wear
resistance are generally improved.
In this study, corrosion behaviour of the developed
low-Ni Co–29Cr–(6, 8)Mo alloys was investigated in
saline solution, Hanks’ solution, and cell culture
medium. Crystalline structure and surface composition
were also evaluated.
2. Experimental
2.1. Alloys
The Co–29Cr–6Mo (mass%) alloys with forging
ratios of 50% and 88% and the Co–29Cr–8Mo alloy
with a forging ratio of 88%, developed by Chiba et al.
[8,9], were manufactured. A conventional solution-
treated Co–29Cr–6Mo–1Ni alloy (ASTM F75-92) was
used as a reference and was called ASTM alloy in this
study.
The alloying elements of Co, Cr, and Mo (99.99 at%)
with the compositions of Co–29Cr–6Mo and
Co–29Cr–8Mo were melted using a high-frequency
induction furnace in a vacuum and the melt was casted
in an alumina mold to obtain an ingot with a gross
weight of 45 kg. The ingot was treated at 1573 K in the
air for 43.2 ks and subsequently cooled in the furnace.
The oxide layer covering the ingot was removed and the
ingot was die forged at 1573–1273 K followed by water
quenching. The forging ratio of the ingot was 50%. The
forged alloy was fully packed in a stainless steel pipe
without leaving space. The forged alloy in the pipe was
forged again to have a plate-like shape at 1573 K
followed by water quenching. The forging ratio of the
clad forged alloy against the original ingot was 88%.
The Co–29Cr–6Mo alloy with the forging ratios of 50%
and 88% and the Co–29Cr–8Mo with the forging ratio
of 88% were called 6Mo-1, 6Mo-2, and 8Mo alloy,
respectively. Bulk compositions of the manufactured
alloys and the ASTM alloy are listed in Table 1.
The alloys were cut off in parallel to the forging axis
to use the alloy face perpendicular to the forging axis for
the structural and surface analyses and the polarization
test. The disks of the 6Mo-1 and ASTM alloys were 38
and 20 mm in diameter, respectively, and 1.6 mm in
thickness. The plates of the 6Mo-2 and 8Mo alloys were
8
30 mm2 in area and 1.6 mm in thickness.
2.2. Analyses of structure
2.2.1. X-ray diffraction (XRD)
The surfaces of the 6Mo-1, 6Mo-2, 8Mo, and ASTM
alloys were finished with a 600 grid SiC paper (Beulher)
or an alumina powder with a diameter of 0.05 mm for a
mirror finish. The samples were ultrasonically rinsed in
deionized water and acetone for 300 s. Then, the
surfaces were applied to an X-ray diffraction (XRD)
(Rint 2200, Rigaku). X-ray source was a monochroma-
tized Cu Ka line.
2.2.2. Metallograph
The surfaces of the 6Mo-1, 6Mo-2, 8Mo, and ASTM
alloys were finished with an alumina powder with a
diameter of 0.05 mm. The alloys were ultrasonically
rinsed in deionized water and acetone for 300 s. Then,
the alloys were electropolished in 10% HNO3 solution

Table 1
Bulk composition of various Co–Cr–Mo alloys (wt%)

Co Cr Mo Ni C Si Mn Cu P Fe
a
6Mo alloy Bal. 27.8 5.88 0.03 0.028 0.01 — — — —
(31.02) (3.56) (0.03) (0.14) (0.02)
8Mo alloy Bal. 29.0 8.45 0.03 0.018 0.01 — — — —
(32.64) (5.15) (0.03) (0.09) (0.02)
ASTM alloy Bal. 28.8 5.92 0.81 0.02 o0.01 o0.01 o0.01 o0.003 o0.02
(32.11) (3.58) (0.80) (0.10) (o0.02) (o0.01) (o0.01) (o0.01) (o0.02)

The number in the parenthesis indicates the atomic concentration.

a
6Mo-1 and 6Mo-2 alloy.

4914 S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923
or 10% H2SO4–90% CH3OH solution at room tem-
perature.
The structure of the alloys was studied with a
differential interference microscope (Carl Zeiss). Mean
grain size was calculated from the number of grain
boundary on a 100 mm pitch rid pattern which was
drawn on the microscopic image containing 100 grains.
2.3. Polarization test
The surfaces of the 6Mo-1, 6Mo-2, 8Mo, and ASTM
alloys were finished with a 600 grid SiC paper (Beulher)
and ultrasonically rinsed in deionized water and acetone
for 300 s. The disks of 6Mo-1 and ASTM alloys were
fixed in an electrode holder with an O-ring. The plates of
6Mo-2 and 8Mo alloys were coated with epoxy resin
leaving the area for measurement. The area for
measurement was 1 cm2. Saline solution (saline, 0.9%
NaCl solution), Hanks’ solution (Hanks), and Eagle’s
minimum essential medium with 10 vol% of fetal bovine
serum (E-MEM+FBS) were employed as the electro-
lytes and nitrogen gas was bubbled to remove dissolved
oxygen through the experiments. The pHs of the saline,
the Hanks, and the E-MEM+FBS aerated at room
temperature were 5.5, 7.3, and 8.3, respectively. The
temperature of the solutions was kept at 310 K. The
compositions of the saline, the Hanks, and the
E-MEM+FBS are listed in Table 2.
A platinum plate and a saturated calomel electrode
(SCE) were used as a counter electrode and a reference
electrode, respectively. The alloys were immersed in the
solutions for more than 1.8 ks and the potential
stabilized during the immersion was employed as the
open-circuit potential (Eocp) of the alloys. The alloys
were anodically and cathodically polarized from the
Eocp with a scanning rate of 20 mV min1. The test was
repeated at least three times with each alloy and
solution.
Table 2
Compositions of saline, Hanks and E-MEM+FBS
Composition Concentration (mol l1)
Saline Hanks
NaCl 1.37
101 1.37
101
KCl — 5.37
103
CaCl2 — 1.26
103
Na2HPO4 — 4.23
104
KH2PO4 — 4.41
104
Mg2SO4 — 7.39
104
NaHCO3 — 4.17
103
Amino acid — —
Protein (g l1) — —
Organic moleculesa (g l1) — —
a
Dextrose, 2Na-Succinate  6H2O, Succinic Acid, Phenol Red, etc.
ARTICLE IN PRESS
2.4. Analysis of surface composition
2.4.1. Composition of the air-formed surface oxide film
The air-formed surface oxide films of the 6Mo-1,
6Mo-2, 8Mo, and ASTM alloys were analysed
using X-ray photoelectron spectroscopy (XPS) (Quan-
tum 2000, Physical Electronics). X-ray source was a
monochromatized Al Ka line and accelerating
voltage was 15 kV. Take-off angle of photoelectron
was 451 to the alloy surface. All binding energies in
this paper are relative to the Fermi level. The composi-
tion and the thickness of the surface oxide film
were calculated according to the method described
elsewhere [11,12]. The empirical data [12–17] of rela-
tive photo-ionisation cross-sections were used for
quantification.
The surfaces of the 6Mo-1, 6Mo-2, 8Mo, and ASTM
alloys were finished with a 600 grid SiC paper (Beulher)
and ultrasonically rinsed in deionized water and acetone
for 600 s. The alloys were kept in a desiccator until the
measurement. Two samples were prepared for each
alloy.
2.4.2. Compositions of the primary and the secondary
passive films of 6Mo-1 and ASTM alloys
The 6Mo-1 and ASTM alloys were polarized from
the Eocp to 0.120 V or to 0.665 V in the E-MEM+FBS.
The polarization procedure was the same as described
above. The 0.120 and 0.665 V were the potentials in
the primary and the secondary passive regions in
the E-MEM+FBS, respectively. The specimen was
immediately removed from the solution, rinsed with
deionized water, and kept in a desiccator. The surface
composition was analysed using an XPS (SSX100,
SSI). X-ray source was a monochromatized Al
Ka line (1486.61 eV) and accelerating voltage and
current were 10 kV and 30 mA, respectively. Take-off
angle of photoelectron was 351 to the alloy surface.
The spectrometer was calibrated against Au 4f7/2
(binding energy, 84.07 eV) and Au 4f5/2 (87.74 eV) of
pure gold and Cu 2p3/2 (932.53 eV), Cu 2p1/2
(952.35 eV), and Cu Auger L3M4,5M4,5 line (kinetic
energy, 918.65 eV) of pure copper. The energy
values were based on published data [18]. The composi-
tion and thickness of the surface oxide film were
MEM+FBS [25] calculated in the same way as in the case of the air-
formed surface oxide film. Two samples were prepared
1.04
101
4.82
103 for each alloy.
1.62
103 The differences between the two different XPS
8.08
104 apparatuses are in the take-off angle and the power of
—
7.30
104
X-ray. The difference in the take-off angles does not
2.14–2.36
102 affect the calculated surface compositions and the film
5.0
103 thickness because the calculation method takes the
o10 factor of take-off angle into consideration. Various
41.2
factors including power of X-ray affect the detection
sensitivity of the XPS apparatus.
 ARTICLE IN PRESS
S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923 4915

3. Results
γ-fcc ε-hcp (a)

3.1. Crystalline structure

XRD patterns of the #600-polished and the mirror

finished Co–Cr–Mo alloys are shown in Figs. 1 and 2,
(b)
respectively. On all the alloys, XRD peaks originated
from g-fcc and -hexagonal closest packing structure
(hcp) phases are observed. The intensities of (1 1 1)fcc
peak at 44.21 and (1 0 0)hcp peak at 47.31 are used to

Intensity / a.u.
estimate the relative amount of g- and -phase,
respectively. On all the #600-polished alloys, the (c)
intensity of (1 0 0)hcp peak is higher than that of
(1 1 1)fcc peak. After the mirror finish, the intensity of
(1 1 1)fcc peak increases except on the 6Mo-1 alloy.
Especially on the mirror finished 8Mo and ASTM
alloys, the intensity of (1 1 1)fcc peak is higher than that
of (1 0 0)hcp peak. (d)
The differential interference images of the
CoCrMo alloys are shown in Fig. 3. All the alloys
are composed with equiaxial grains. The 6Mo-1, 6Mo-2,
and 8Mo alloys show uniform grain size. Mean grain
sizes of the 6Mo-1, 6Mo-2, 8Mo, and ASTM alloys are 40 50 60 70 80 90 100
2θ /˚
43, 11, 9, and 558 mm, respectively. Deformation twins
and striated structures are observed in some grains on Fig. 2. XRD patterns of the Co–Cr–Mo alloys mirror finished with
all the alloys. The 6Mo-1 alloy has less deformation alumina powder: (a) 6Mo-1, (b) 6Mo-2, (c) 8Mo, and (d) ASTM
twins and striated structures than the 6Mo-2 alloy and alloys.
has black round spots. In the grain boundaries in the
8Mo alloy, black precipitates are observed. The ASTM
alloy has black round spots and its grain boundaries are
γ-fcc ε-hcp (a) electropolished more than those of the other alloys.

3.2. Composition of the air-formed surface oxide film

The XPS spectra of binding energy regions of Co 2p3/2,

(b)
Cr 2p, Mo 3d, Ni 2p, O 1 s, C 1 s, and N 1 s were
analysed on all the alloys. The Ni 2p peaks were not
obtained on any of the alloys. The C 1 s and N 1 s peaks
originated from the contaminant. The XPS spectra of
Intensity / a.u.

Co 2p3/2, Cr 2p, Mo 3d, and O 1 s electrons of the 6Mo-

1 alloy are shown in Fig. 4. The Co 2p3/2 peak is
(c) decomposed into three peaks originating from Co0,
Co2+, and a satellite of Co2+ according to the binding
energy data [19]. The Cr 2p peaks are decomposed into
two doublet peaks originating from Co0 and Cr3+ [19].
The Mo 3d peaks are decomposed into four doublet
(d) peaks originating from Mo0, Mo4+, Mo5+, and Mo6+
[19]. The O 1 s peak is decomposed into peaks
originating from O2, hydroxide or hydroxyl group
(OH), and hydrate and/or adsorbed water (H2O)
according to the binding energy data concerning metal
oxides [13].
40 50 60 70 80 90 100 Composition and thickness of surface oxide film and
2θ /˚
fraction of O2, OH, and H2O and relative ratio of
Fig. 1. XRD patterns of the Co–Cr–Mo alloys polished with #600 SiC OH to O2 ([OH]/[O2]) are shown in Tables 3a and
polishing paper: (a) 6Mo-1, (b) 6Mo-2, (c) 8Mo, and (d) ASTM alloys. 3b, respectively. Composition of the substrate just under
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4916 S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923

100 µm 100 µm
(a) (b)

100 µm 200 µm
(c) (d)

Fig. 3. Differential interference images of the Co–Cr–Mo alloys: (a) 6Mo-1, (b) 6Mo-2, (c) 8Mo, and (d) ASTM alloys.

Co 2p3/2 Cr 2p
Co02p3/2 Cr3+ 2p3/2

Cr0 2p1/2 Cr0 2p3/2

Intensity / a.u..

Intensity / a.u..

Co2+2p3/2 Co2+2p3/2
(satellite)

Cr3+ 2p1/2

790 785 780 775 592 588 584 580 576 572 570
(a) Binding Energy /eV (b) Binding Energy /eV

Mo 3d O 1s
Mo0 3d5/2

O2-
Mo03d3/2
Mo4+3d5/2
Intensity / a.u..

Intensity / a.u..

Mo4+3d3/2
H2O OH-
Mo5+3d3/2

Mo6+3d3/2
Mo6+3d5/2 Mo5+3d5/2
240 235 230 225 538 536 534 532 530 528 526
(c) Binding Energy /eV (d) Binding Energy /eV

Fig. 4. XPS spectra of Co 2p3/2, Cr 2p, Mo 3d, and O 1 s electrons of the as-polished 6Mo-1 alloy.

the surface oxide film is shown in Table 4. No significant significant difference in the relative [OH]/[O2] ratio of
differences are observed in the composition and the the alloys although the ratios of the 6Mo-1, 6Mo-2, and
thickness of the surface oxide film of all the alloys. Cr ASTM alloys are slightly larger than that of the 8Mo
and Mo oxides are enriched in the film. There is not a alloy. In the composition of substrate just under the film
 ARTICLE IN PRESS
S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923 4917

Table 3a
Composition of the air-formed film of Co–Cr–Mo alloys analysed with Quantum 2000 (at%)

Co Cr Mo Ni O Thickness (nm)

6Mo-1 alloy 6.470.2 21.970.2 0.570.4 0.0 70.770.0 2.571.2

6Mo-2 alloy 6.770.2 19.471.5 1.070.1 0.0 72.871.7 2.470.6
8Mo alloy 5.270.2 21.570.5 1.070.3 0.0 72.370.4 2.370.1
ASTM alloy 7.470.1 22.072.2 1.170.1 0.0 69.572.1 2.471.4

Mean7standard deviation.
Number of experiment ¼ 2.

Table 3b
Fraction of O2, OH, and H2O and the relative ratio of OH to O2 in the air-formed film of Co–Cr–Mo alloys analysed with Quantum 2000

[O2] [OH] [H2O] [OH]/[O2]

6Mo-1 alloy 0.3070.03 0.5270.07 0.1870.04 1.7770.04

6Mo-2 alloy 0.2770.02 0.6470.04 0.0970.04 2.3970.17
8Mo alloy 0.3770.02 0.5470.06 0.0870.02 1.4670.05
ASTM alloy 0.2670.03 0.5670.03 0.1770.00 2.1970.41

Mean7standard deviation.
Number of experiment ¼ 2.

Table 4 3.4. Polarization curves in various solutions

Composition of substrate just under the air-formed film of Co–Cr–Mo
alloys analysed with Quantum 2000 (at%)
Cathodic and anodic polarization curves of the
Co Cr Mo Ni Co–Cr–Mo alloys in the saline, the Hanks, and the
E-MEM+FBS are shown in Figs. 6–8, respectively.
6Mo-1 alloy 57.070.8 40.570.2 3.470.2 0.0 The cathodic current densities show a rather flat
6Mo-2 alloy 59.673.2 36.873.7 3.670.5 0.0
region from the Eocp to 0.7 V and subsequently
8Mo alloy 60.171.3 38.371.6 4.470.1 0.0
ASTM alloy 57.671.6 39.770.8 3.470.1 0.0 increase. No significant differences are observed in the
cathodic current densities depending on the alloys and
Mean7standard deviation. the solutions.
Number of experiment ¼ 2.
All the alloys are spontaneously passivated by the
anodic polarization. The passive current densities of the
of all the alloys, no significant differences are observed. 6Mo-1 and ASTM alloys are slightly lower than those of
Metallic Cr is enriched and Co is depleted in the the 6Mo-2 and 8Mo alloys in the saline. The passive
substrate just under the film. current densities of the low-Ni alloys are of the same
order of magnitude as that of the ASTM alloy in all the
3.3. Eocp in various solutions investigated solutions.
The transpassive potential depends on the solutions
The Eocp values of the Co–Cr–Mo alloys in the but is independent of the alloys. The secondary passive
saline, the Hanks, and the E-MEM+FBS are shown in and transpassive regions are observed in the Hanks and
Fig. 5(a)–(c), respectively. In the saline, the Eocps of the the E-MEM+FBS. Especially in the E-MEM+FBS,
6Mo-1, 6Mo-2, and 8Mo alloys are lower than that of the secondary passive region is clear on the 6Mo-1,
the ASTM alloy. The characteristic effect of the 6Mo-2, and 8Mo alloys. The transpassive potential in
inorganic ions in the Hanks is to reduce the standard the saline is about 0.5 V. The primary transpassive
deviations of Eocp compared with those in the saline and potential in the Hanks is 0.3 V and the secondary passive
the E-MEM+FBS. On the other hand, a significant region from 0.65 V to 0.78 V shows small fluctuations as
change does not occur in the Eocp with the inorganic shown in Fig. 7(c). The primary transpassive potential in
ions on the 6Mo-1, 6Mo-2, and 8Mo alloys. With the the E-MEM+FBS is 0.25 V and the alloys are
biomolecules in the E-MEM+FBS, the Eocp of all the repassivated at 0.53 V to show a clear secondary passive
alloys slightly increases. On the other hand, the standard region to 0.75–0.8 V followed by the secondary trans-
deviations of the Eocp in the E-MEM+FBS are larger passivation as shown in Fig. 8(c). The secondary passive
than those in the saline and the Hanks. current of the low-Ni alloys is lower and their passive
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4918 S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923

-0.2 -0.2 -0.2

Saline Hanks E-MEM+FBS
Eocp/ V vs. SCE

Eocp/ V vs. SCE

Eocp/ V vs. SCE

-0.3 -0.3 -0.3

-0.4 -0.4 -0.4

-0.5 -0.5 -0.5

6Mo-1 6Mo-2 8Mo ASTM 6Mo-1 6Mo-2 8Mo ASTM 6Mo-1 6Mo-2 8Mo ASTM
(a) Alloys (b) Alloys (c) Alloys

Fig. 5. Eocp values of the Co–Cr–Mo alloys in (a) saline, (b) Hanks, and (c) E-MEM+FBS.

-100 100
6Mo-1 Saline
6Mo-2
Current Density / A cm-2

-10-2 10-2

Current Density / A cm-2

8Mo
ASTM
-10-4 10-4

-10-6 10-6

-10-8 10-8

-10-10 10-10
-1.0 -0.8 -0.6 -0.4 -0.2 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1.0
(a) Potenial / V vs. SCE (b) Potenial / V vs. SCE

Fig. 6. Cathodic and anodic polarization curves of the Co–Cr–Mo alloys in saline.

potential region is larger than that of the ASTM alloy. were observed. The C 1 s and N 1 s peaks originated
The current density in the primary transpassive region from the adsorbed biomolecules in the E-MEM+FBS
from 0.3 to 0.8 V in the Hanks is higher than that in the and contaminant. The O 1 s peak originated from the
saline. Also, the current density in the primary surface oxide and the adsorbed biomolecules, causing
transpassive region from 0.25 to 0.53 V in the the overestimation of film thickness due to the calcula-
E-MEM+FBS is higher than those in the Hanks and tion method. The P 2p peak is originated from the
the saline. However, the current densities over 0.8 V of adsorbed phosphate ion in the E-MEM+FBS accord-
all the alloys are of the same order of magnitude in all ing to the binding energy data [16]. The Ca 2p peaks
the solutions. were less than the detection limit. The XPS peaks of Co
2p3/2, Cr 2p, Mo 3d, Ni 2p, and O 1 s are decomposed
3.5. Composition of the primary and secondary passive into metallic and oxidic states as described above.
film in the E-MEM+FBS Composition and thickness of the primary and
secondary passive films of the 6Mo-1 and ASTM alloys
The significant difference in the polarization curves of are shown in Table 5. Composition of the substrate just
the low-Ni alloys and the ASTM alloy appears in the under the film is shown in Table 6. Cr and Mo oxides are
secondary passive behaviour in the E-MEM+FBS as enriched in the primary passive film. The concentrations
shown in Fig. 8. In order to examine the difference of Cr and Mo oxides in the secondary passive film are
between the low-Ni alloys and the ASTM alloy, smaller than in the primary passive film. The film
composition of the primary and the secondary passive thickness of the secondary passive film is larger than
film in the E-MEM+FBS was investigated. that of the primary passive film. There is not a
XPS spectra of binding energy regions of Co 2p3/2, Cr significant change in the compositions of the substrate
2p, Mo 3d, Ni 2p, O 1 s, C 1 s, N 1 s, P 2p, and Ca 2p just under the primary passive film and the secondary
 ARTICLE IN PRESS
S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923 4919

-100 100
6Mo-1 Hanks
6Mo-2 10-2
-10-2
Current Density / A cm-2

Current Density / A cm-2

8Mo
ASTM
-10-4 10-4

-10-6 10-6

-10-8 10-8

-10-10 10-10
-1.0 -0.8 -0.6 -0.4 -0.
-0.2 -0.6 --0.4 -0.2 0 0.2 0.4 0.6 0.8 1.0
(a) Potential / V vs. SCE (b) Potential / V vs. SCE
10-2

Current Density / A cm-2

10-3

10-4

10-5
0.5 0.6 0.7 0.8 0.9 1.0
(c) Potential / V vs. SCE

Fig. 7. Cathodic and anodic polarization curves of the Co–Cr–Mo alloys in Hanks.

passive film. On the other hand, Cr oxide concentration
in the secondary passive film of the 6Mo-1 alloy is larger
than that of the ASTM alloy.
4. Discussion
4.1. Corrosion resistance and biocompatibility of the new
forged low-Ni Co– Cr– Mo alloys
The passive current densities of the new low-Ni
Co–Cr–Mo alloys are of the same order of magnitude
as those of the ASTM alloy in all the investigated
solutions. The new low-Ni alloys show slightly lower
Eocps and slightly higher passive current densities than
the ASTM alloy in the saline. The difference in passive
current density between the new low-Ni alloys and the
ASTM alloy becomes negligible when inorganic ions
and biomolecules are added. Especially in the
MEM+FBS, the current densities in the potential
region from 0.55 to 0.8 V of the new low-Ni alloys are
lower than those of the ASTM alloy. Those indicate that
the new low-Ni alloys can show as high corrosion
resistance as that of the conventional ASTM alloy in the
human body.
Ni contents in the air-formed surface oxide film and
the primary and the secondary passive films of the new
low-Ni alloys are under the detection limits of the XPS
apparatuses as well as those of the ASTM alloy. This
result indicates that the toxicity caused by Ni of the low-
Ni alloys is equivalent or less than that of the ASTM
alloy under static condition. On the other hand, the
Co–Cr–Mo alloy is generally used in a sliding part
because of the high wear resistance, meaning that the
exposure of bare metal surface and the formation of
wear particles are the main causes for the dissolution of
alloying elements. By reducing Ni content in the bulk
composition, the gross amount of Ni dissolved should
be reduced. Therefore, the advantage of the new low-Ni
alloys is that the much lower Ni content can reduce the
toxicity of dissolved metal ions. Further investigation,
such as toxicity test and wear test, should be performed
to evaluate the advantage of the new low-Ni Co–Cr–Mo
alloys.
4.2. Microstructure of the alloys and compositions of the
air-formed surface oxide films
Asperities of the deformed layer formed by polishing
with a SiC polishing paper could be removed by
 ARTICLE IN PRESS
4920 S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923

-100 -100
E-MEM+FBS
6Mo-1
-10-2 6Mo-2 -10-2

Current Density / Acm-2

Current Density / Acm-2

8Mo
ASTM
-10-4 -10-4

-10-6 -10-6

-10-8 -10-8

-10-10 -10-10
-1.0 -0.8 -0.6 -0.4 -0.2 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1.0
(a) Potenial / V vs. SCE (b) Potential / V vs. SCE
-10-2

Current Density / Acm-2

-10-3

-10-4

-10-5

-10-6
0.4 0.6 0.8 1.0
(c) Potential / V vs.SCE

Fig. 8. Cathodic and anodic polarization curves of the Co–Cr–Mo alloys in E-MEM+FBS.

Table 5
Composition and thickness of the primary and the secondary passive film of 6Mo-1 and ASTM alloys in E-MEM+FBS analysed with SSX100 (at%)

Polarization region Co Cr Mo Ni O P Ca Thickness (nm)

6Mo-1 alloy Eocp–0.120 V 2.8 22.3 2.8 0.0 72.0 0.0 0.0 2.9
70.5 72.9 70.4 73.0 70.2
Eocp–0.665 V 5.6 19.1 1.9 0.0 73.0 0.4 0.0 4.2
70.1 70.0 70.1 70.3 72.0 70.4
ASTM alloy Eocp–0.120 V 2.6 21.0 2.0 0.0 72.8 1.5 0.0 3.0
70.4 70.1 70.4 70.6 70.0 70.4
Eocp–0.665 V 6.3 13.5 1.3 0.0 78.9 0.0 0.0 4.7
70.3 71.1 70.3 71.1 70.4

Mean7standard deviation.
Number of experiment ¼ 2.

Table 6
Composition of substrate just under the primary and the secondary passive film of 6Mo-1 and ASTM alloys analysed with SSX100 (at%)

Polarization region Co Cr Mo Ni

6Mo-1 alloy Eocp–0.120 V 56.877.3 36.979.2 6.372.0 0.0

Eocp–0.665 V 64.071.1 29.272.4 6.871.3 0.0
ASTM alloy Eocp–0.120 V 57.873.3 35.474.0 6.870.7 0.0
Eocp–0.665 V 42.2714.1 50.3715.6 7.571.5 0.0

Mean7standard deviation.
Number of experiment ¼ 2.
 ARTICLE IN PRESS
S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923
finishing with an alumina powder. It means that the
XRD patterns on the #600-polished surfaces originate
from the deformed layer while those on the mirror
finished surfaces originate from the surface layer close to
bulk of the alloys. On the #600-polished alloys, the -hcp
phase is dominant. When removing the deformed layer
with alumina powder finishing, the g-fcc phase is
dominant on the 6Mo-2, 8Mo, and ASTM alloys. These
results indicate that the strain-induced martensitic trans-
formation from g-fcc phase to -hcp phase can easily
occur on the low-Ni Co–Cr–Mo alloy by polishing.
The g-fcc phase is stabilised with Ni [10] and
martensite starting temperature increases with the
decrease in C content. The alloy surface does not
contain Ni (Table 3a) and the C contents of the alloys
are less than 0.05 wt% (Table 1). The strain-induced
martensitic transformation by polishing is probably
promoted owing to low Ni and low C contents.
The XRD peaks of -hcp phase do not decrease with
alumina powder finishing on the 6Mo-1 and 6Mo-2
alloys. It is suggested that the martensitic transforma-
tion on the 6Mo-1 and 6Mo-2 alloys occurs more than
on the 8Mo alloy and the deformed layers on the 6Mo-1
and 6Mo-2 alloys are thicker than the 8Mo alloy.
The grain boundaries on the 8Mo alloy are black and
conspicuous. When Mo content of Co–Cr–Mo alloy
increases, precipitation of s-phase can occur. Also, with
the increase in forging ratio, re-agglomeration of pre-
cipitate can occur. These results indicate that the s-phase
may precipitate in grain boundaries of the 8Mo alloy. The
round black spots observed on the 6Mo-1 and ASTM
alloys are probably formed during electrolytic polishing.
The composition of the air-formed oxide film of the
Co–Cr–Mo alloys does not depend on the microstruc-
ture and the bulk composition because the obtained
data by XPS is the average composition of a certain
area. However, the microstructures of the alloys are
different, suggesting that there should be local differ-
ences in the composition and the structure of surface
oxide film.
4.3. Effect of forging on Eocp and passive current density
The Eocps and the current densities vary depending on
the alloys although the compositions and the fractions
of oxygen of the air-formed oxide film of the alloys are
almost the same. This suggests that the microstructure
of the alloy should affect the corrosion behaviour of the
Co–Cr–Mo alloys.
The Eocps of the low-Ni alloys are slightly lower than
that of the ASTM alloy. Passive current densities of the
low-Ni alloys are slightly higher than that of the ASTM
alloy in the saline. These results indicate that the
corrosion resistance of the low-Ni alloys is slightly
lower than that of the ASTM alloy in the solution
without inorganic ions and biomolecules. The increase
4921
of grain boundaries due to grain refining can accelerate
the anodic reaction on the forged low-Ni alloys, leading
to the negative shift of their Eocps compared to that of
the ASTM alloy.
Among the new alloys, the Eocps of the 6Mo-1 alloy
with larger grain size are slightly lower than those of the
6Mo-2 and 8Mo alloys with smaller grain size. Also, the
Eocps of the 8Mo alloy with precipitates in grain
boundaries are higher than those of the 6Mo-2 alloy
without precipitates. Generally, the increase in grain
boundaries with grain refining leads to the increase in
anodic reaction and causes the negative shift of Eocp.
Also, the precipitates in grain boundaries generally form
the local defects of passive film that could cause the
decrease in Eocp. In this study, the positive shift of Eocp
with the decrease in grain size regardless of the
precipitates indicates that the grain size and the
precipitates in grain boundaries are not dominant to
determine the Eocp of the forged low-Ni alloys. When
the low-Ni alloys are forged, the stacking faults increase
and the precipitate is dispersed. The 6Mo-2 and 8Mo
alloys probably have more stacking faults and precipi-
tate than the 6Mo-1 alloy. When the steel is cold
worked, the dispersion of carbide and nitride, which
work as cathode, causes the increase in the local-active
cells between the precipitate and the mother phase,
leading to the increase in gross cathodic reaction and the
increase in corrosion rate [20]. Those indicate that the
forging of the Co–Cr–Mo alloy can cause the increase in
the local-active cells. The increase in local-active cells by
further forging causes the increase in the gross amount
of the cathodic reaction, leading to the slight increase in
Eocp of the forged low-Ni alloys. However, further
investigations are necessary to understand the shift of
Eocp and to evaluate the corrosion rate at Eocp.
The passive current density around 0.3 V of the 6Mo-
1 alloy in the saline is lower than those of the 6Mo-2 and
8Mo alloys, indicating that the protectiveness of passive
oxide film of the 6Mo-1 alloy is higher than that of the
6Mo-2 and 8Mo alloys. The increase in grain bound-
aries by grain refining and the precipitates in grain
boundaries cause the decrease in protectiveness of the
passive oxide film. However, there is contradiction
between the higher protectiveness of passive oxide film
and the lower Eocp of the 6Mo-1 alloy than those of the
6Mo-2 and 8Mo alloys. These contradictive results
indicate that, when the potential of the alloys is
controlled, the effect of stacking faults and dispersed
precipitates on the passive oxide film is smaller than that
of the grain boundaries.
4.4. Effect of inorganic ions and proteins
The Eocps of the alloys in the Hanks and the
E-MEM+FBS do not show significant differences from
those in the saline. Also, the passive current densities in
 ARTICLE IN PRESS
4922 S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923
the potential region from Eocp to transpassive potential
in the Hanks and the E-MEM+FBS are of the same
order of magnitude as those in the saline. These results
indicate that the inorganic ions in the Hanks and
the proteins and amino acids (biomolecules) in the
E-MEM+FBS do not apparently affect the corrosion
resistance of the Co–Cr–Mo alloys.
On the other hand, the standard deviations of Eocp in
the Hanks are smaller than in the saline and the
E-MEM+FBS. When the ASTM alloy is immersed in
the Hanks for 7 days, Ca and P precipitate [18].
Although Ca and sometimes P are not detected on the
primary and the secondary passive films using the XPS
(SSX 100), Ca and P are detected in the primary passive
film when the other XPS apparatus (Quantum 2000) is
used (unpublished data). This is because the detection
sensitivity of Quantum 2000 may be higher than that of
SSX 100. Adsorption of trace amount of Ca and P on
the surface may be responsible for the less scatter of the
Eocp in the Hanks.
On the other hand, the standard deviations of Eocp in
the E-MEM+FBS are large while the averages of Eocp
in the E-MEM+FBS are as same as those in the Hanks.
Bovine albumin, contained in the E-MEM+FBS,
accelerates the dissolution of pure Co [21]. The
biomolecules adsorb on the ASTM alloy in the
E-MEM+FBS [19] and the adsorption amount, con-
formation, and the kind of protein change according to
the immersion time [22]. The preferential dissolution of
Co with proteins can cause the decrease in Eocp while the
adsorption of proteins can cause the increase in Eocp by
working as a diffusion barrier. The competition of
preferential dissolution of Co with proteins and the
diffusion barrier with proteins can sensitively affect the
Eocp of the Co–Cr–Mo alloy.
4.5. Transpassive region in various solutions
The potential of biometals is expected to change by
biomolecules and the substances generated by cells in
the human body. For example, active oxygen generated
by macrophage may raise Eocp of biometals by increas-
ing cathodic reaction of oxygen reduction reaction.
However, the potential range of biometals in the human
body is not yet revealed. Therefore, the polarization
behaviour of the biometals in a wide potential range
including transpassive potential region is not negligible
to evaluate the corrosion behaviour of biometals.
The transpassive potentials of the alloys in the saline,
the Hanks, and the E-MEM+FBS are 0.6, 0.3, and
0.25 V, respectively. The inorganic ions and biomole-
cules in the Hanks and the E-MEM+FBS affect the
transpassive behaviour of the Co–Cr–Mo alloy. The
anodic current densities over 0.8 V were the same in all
the solutions. The anodic current over 0.8 V is attributed
to the decomposition of water [23].
Transpassive potential of the Co–28Cr–6Mo (ASTM)
alloy in the tris(hydroxymethyl)aminomethane buffered
saline (pH 7.4) is 0.2–0.4 V, and the oxidation dissolu-
tion of Cr oxide, strong thickening of the film, and the
dissolution of all alloying elements occur in this
potential region [24]. In this study, the Cr and Mo
concentrations in the secondary passive film are smaller
than in the primary passive region. This indicates that
the oxidation dissolution of Cr oxide and dissolution of
alloying elements occurs in the transpassive region from
0.25 to 0.4 V. The decrease in the transpassive potential
with inorganic ions and biomolecules indicates that the
presence of inorganic ions such as HxPO4n and SO2 4
and biomolecules, and/or the difference of pH may
accelerate the reactions in this potential region.
The significant secondary passive region appears at
the potential region from 0.6 to 0.8 V in the E-
MEM+FBS. Bovine albumin and fibrinogen accelerate
the dissolution of pure metal powder of Co, Cu, Cr, and
Ni, especially Co [21]. In the E-MEM+FBS, the
preferential dissolution of Co proceeds due to the serum
proteins, leading to the relative increase in Cr concen-
tration in the film. In the transpassive potential region,
formation and dissolution of the Cr3+ concomitantly
occur and the current does not increase for a certain
time under static condition [24]. On the surface of the
Co–Cr–Mo alloy polarized at 0.7 V of the transpassive
potential, oxide and hydroxide of Cr3+ are observed
using XPS [24]. These results indicate that the formation
of hydroxide of Cr3+ can occur in transpassive potential
region. Also, when the Cr concentration increases high
enough to form passive film, the secondary passive
region appears. The delay of the current increase in the
transpassive potential region is mass transport depen-
dent because the delay does not occur with using a
rotating electrode specimen [24]. Biomolecules adsorb to
the Co–Cr–Mo alloy [19]. The adsorbed biomolecules
can cause the retardation of mass transport in the
boundary between the alloy surface and the solution,
leading to the further accumulation of Cr3+ on the
surface.
The secondary passive region of the low-Ni alloys
is larger than that of the ASTM alloy in the
E-MEM+FBS. The Cr concentration in the secondary
passive region of the 6Mo-1 alloy is almost as same as
that in the primary passive region and higher than that
of the ASTM alloy. The increase in grain boundaries by
forging may accelerate the dissolution rate of the
alloying elements and promote the enrichment of Cr in
the surface oxide film.
5. Conclusions
Corrosion behaviour and microstructure of the
developed forged low-Ni Co–29Cr–(6, 8)Mo alloys were
 ARTICLE IN PRESS
S. Hiromoto et al. / Biomaterials 26 (2005) 4912–4923
examined in saline, Hanks’, and E-MEM+FBS solu-
tions. A conventional Co–Cr–Mo alloy (ASTM F75-92)
was used as a reference material. Following conclusions
were drawn:
1. Ni content in the air-formed surface oxide films of the
low-Ni alloys and the ASTM alloys are under the
detection limit of XPS and the surface compositions
of the low-Ni alloys are similar to that of the ASTM
alloy.
2. The passive current densities of the low-Ni alloys are
slightly higher than that of the ASTM alloy in saline
solution ; however, they are almost equal in Hanks ’
and E-MEM+FBS solutions.
3. Among the forged low-Ni alloys, the alloy with low
forging ratio has a lower passive current density. The
open-circuit potential of the alloys slightly increases
with the increase in forging ratio.
4. The increase in grain boundaries by forging causes
the decrease in corrosion resistance of the forged low-
Ni alloy.
References
[1] National Institutes of Health. Total hip replacement, vol. 12(5).
NIH Consensus Statement, Bethesda, MD, September 12–14,
1994. p. 1–31.
[2] LaBerge M. Wear. In: Black J, Hastings G, editors. Handbook
of biomaterial properties. London: Chapman & Hall; 1998.
p. 364–405.
[3] Savarino L, Granchi D, Ciapetti G, Cenni E, Pantoli AN, Rotini
R, Veronesi CA, Baldini N, Giunti A. Ion release in patients with
metal-on-metal hip bearings in total joint replacement: a
comparison with metal-on-polyethylene bearings. J Biomed
Mater (Appl Biomater) 2002;63:467–74.
[4] Savarino L, Granchi D, Ciapetti G, Cenni E, Greco M, Rotini R,
Veronesi CA, Baldini N, Giunti A. J Biomed Mater Res
2003;66A:450–6.
[5] Hallab NJ, Skipor A, Jacobs JJ. Interfacial kinetics of titanium-
and cobalt-based implant alloys in human serum: metal release
and biofilm formation. J Biomed Mater Res 2003;65A:311–8.
[6] Nakayama H. Dentistry and metal allergy. In: Inoue M,
Nakayama H, editors. Dentistry and metal allergy. London:
Dental-Diamond Co; 1997. p. 22–7.
[7] IARC Working Group on the Evaluation of Carcinogenic Risks
to Humans: in IARC Monographs on the Evaluation of
Carcinogenic Risks to Humans, vol. 74. IARC Press, Lyon
1999. 113–71, 241–2.
4923
[8] Chiba A, Kumagai K, Takeda H, Noto K. Hot forgeability of
Mo-enriched Co–Cr alloy for medical applications. Proceedings
of the 17th European society for biomaterials conference,
Barcelona, Spain, 2002. p. 194.
[9] Chiba A, Kuamgai K, Takeda H, Nomura N. Mechanical
properties of forged low Ni and C-containing Co–Cr–Mo
biomedical implant alloy. Mater Sci Forum, in preparation.
[10] CoCr-based alloys. In: Black J, Hastings G, editors. Handbook of
biomaterial properties. London: Chapman & Hall; 1998.
p. 167–78.
[11] Asami K, Hashimoto K, Shimodaira S. XPS determination of
compositions of alloy surfaces and oxides on mechanically
polished iron–chromium alloys. Corros Sci 1977;17:713–23.
[12] Asami K, Hashimoto K. An XPS study of the surfaces on Fe–Cr,
Fe–Co and Fe–Ni alloys after mechanical polishing. Corros Sci
1984;24:83–97.
[13] Asami K, Hashimoto K. X-ray photoelectron-spectra of several
oxides of iron and chromium. Corros Sci 1977;17:559–70.
[14] Asami K, Hashimoto K, Shimodaira S. XPS determination of
compositions of alloy surface oxide on mechanically polished
iron–chromium alloys. Corrs Sci 1977;17:713–23.
[15] Teramoto K, Asami K, Hashimoto K. The composition of passive
films of ferritic 30Cr stainless steels in H2SO4. Boshoku Gijyutsu
(Corrs Eng) 1978;27:57–61.
[16] Hashimoto K, Kasaya M, Asami K, Masumoto T. Electro
chemical and XPS study on corrosion behavior of amorphous
Ni–Cr–P–B alloys. Boshoku Gijyutsu (Corrs Eng)
1977;26:445–52.
[17] Hashimoto K, Asami K, Teramoto K. An X-ray photo-electron
spectroscopic study on the role of molybdenum in increasing the
corrosion resistance of ferric stainless steels in HCl. Corrs Sci
1979;19:3–14.
[18] Asami K. Precisely consistent energy calibration method
for X-ray photoelectron-spectroscopy. J Electron Spectrosc
1976;9:469–78.
[19] Hanawa T, Hiromoto S, Asami K. Characterization of the
surfaced oxide film of a Co–Cr–Mo alloy after being located in
quasi-biological environment using XPS. Appl Surf Sci
2001;183:68–75.
[20] Uhlig HH. Effect of stress. In: Corrosion and corrosion control.
Tokyo: Sangyo Thosho Pub.; 1963. p. 107–31 [Trans by Okamoto
G, Matsuda S, Matsushima I].
[21] Clark GCF, Williams DF. The effects of proteins on metallic
corrosion. J Biomed Mater Res 1982;16:125–34.
[22] Wahlgren M, Arnebrant T. Protein adsorption to solid surfaces.
Trends Biotechnol 1991;9:201–8.
[23] Pourbaix M. Atlas of Electrochemical Equilibria in Aqueous
Solutions. Houston, TX: National Association of Corrosion
Engineers; 1974. p. 97–105 [Trans Franklin JA].
[24] Hodgson AWE, Kurz S, Virtanen S, Fervel V, Olsson COA,
Mischler S. Passive and transpassive behaviour of CoCrMo in
simulated biological solutions. Electrochim Acta 2004;49:
2167–78.
[25] Eagle H. Amino acid metabolism in mammalian cell cultures.
Science 1959;130:432.