Effect of Si and Mn on microstructure

of biomedical Co-Cr-Mo-C alloys

Biomaterial

Chemical composition of specimens

Table 2.1 Chemical composition of the CCM-C-Si-Mn alloys used in this study (mass%)

Alloys
0.5Si0Mn
1Si0Mn
2Si0Mn
0.15C1Si
0.35C1Si
0Si1Mn
0Si2Mn
0.5Si0.5Mn
0.75Si0.75Mn
1Si1Mn

Cr
27.24
29.17
28.05
27.06
27.68
27.86
27.07
27.46
28.26
27.96

Mo
5.74
6.22
6.01
5.61
6.04
6.03
5.80
6.01
6.23
6.09

C
0.22
0.23
0.22
0.13
0.38
0.25
0.23
0.29
0.23
0.26

Si
0.58
0.96
2.60
1.33
1.20
0.11
0.07
0.60
0.85
0.98

Mn
0.02
0.08
0.02
0.02
0.01
0.97
1.91
0.48
0.79
1.02

P
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001

S
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001

Co
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.

Table 2.2 Chemical composition of the CCM-C-N-Si-Mn alloys used in this study (mass%)
Alloys
1Si0Mn0.175N
0Si1Mn0.175N
1Si1Mn0.175N
0Si0Mn0.175N

Cr
27.9
27.77
27.67
27.65

Mo
6.17
6.09
6.01
6.22

C
0.25
0.24
0.24
0.25

Si
1.21
<0.001
1.19
<0.001

Mn
0.001
1.15
1.15
0.001

N
0.15
0.19
0.17
0.19

P
0.002
0.002
0.003
<0.001

S
<0.001
<0.001
<0.001
<0.001

Co
Bal.
Bal.
Bal.
Bal.

Specimen preparation
Alloy ingotsdiameter of 34 mm and height of 100 mmwere
prepared by using an induction melting furnace under Ar or N2
atmosphere and casting to a copper mold.

These ingots were cut into disks shape of 5 mm in thickness, and

then cut into four equal parts.

5 mm
100 mm

34 mm
5 mm

Ingot

10 mm
10 mm

Heat treatment
Solution treatment

(a)

Solution temperature, TS (K) : 1448 ~ 1548

Holding time, tH (ks)
: 0 ~ 43.2
Cooling
: Water quench
Atmosphere inside SiO2 ampoule : Ar

TS

tH

W.Q.

(b)
1523 K

Aging
Solution temperature (K)
Solution time (ks)
Aging temperature, TA (K)
Holding time, tA (ks)
Cooling
Gas atmosphere

TA

:
:
:
:
:
:

1523
43.2
873 ~ 1473
0.6 ~ 43.8
Water quench
Ar

43.2 ks

W.Q.

tA

W.Q.

Fig. 2.1 Schematic diagram of

(a) solution treatment and (b)
aging cycles.

Evaluations
Microstructure : Optical microscope (OM)
Scanning electron microscope (SEM)
Transmission electron microscope (TEM)
Electron-probe micro-analyzer (EPMA)
Hardness

: Micro Vickers hardness tester

Precipitates

: Scanning electron microscope (SEM)

X-ray diffraction (XRD) (after electrolytic extraction)

Electrolyte solution
H2SO4 10%

Fig. 2.2 Schematic diagram of

apparatus for electrolytical
extraction.

Microstructure of as-cast alloys

1Si0Mn

0Si1Mn

50 mm

1Si1Mn

50 mm

0Si0Mn

50 mm

50 mm

Fig. 3.1.1 Microstructure of as-cast alloys.

Fig. 3.1.2 Effect of the alloying

elements in as-cast alloys on the
content and size of precipitates.

Dendrite matrix, interdendritic and grain boundary precipitates were

observed in as-cast alloys.
The addition of Si and Mn increased the precipitate content in ascast alloys.

Phase of precipitates in as-cast alloys

X (q)

Table 3.1.1 Crystallographic data of precipitates

Phase
q
h
p

Prototype
M23X6
M6X-M12X
M2T3X

Crystal structure
Cubic
Cubic
Cubic, b-Mn structure

X
= Carbon (C)
M, T = Metallic elements
Table 3.1.2 Precipitates formed in as-cast alloys

Alloys
0Si0Mn
1Si0Mn
0Si1Mn
1Si1Mn

Phase of precipitate
q
h
p

= Main precipitate
Fig. 3.1.3 XRD patterns of precipitates
electrolytically extracted from as-cast alloys.

Precipitates in as-cast alloys

Fig.3.1.4 Phase map of Co-29Cr-6Mo-0.23C-xN alloy*.

Casting of Co-Cr-Mo alloys s-phase might be formed.

*Y.

Yamashita et al.: Mater. Trans. 51 (2010) 1633-39.

Report of Ramrez et al.

Quenching during thermal analysis
(QTA)
Co-25.23Cr-5.42Mo-0.26C-0.774Si0.325Mn-0.316Fe-0.763Ni-0.049W
alloy

Liquid
0.9 ks

s + C M23C6 + M12C
1473 K
1423 K
1273 K
0.2 K/s

W.Q. W.Q. W.Q.

*L.E. Ramrez et al.: Scr. Mater., 2002, vol. 47, pp. 81116.

Fig. 3.1.5 XRD patterns of extracted

precipitates from QTA specimens*.

Effect of carbon on s-phase

Fig. 3.1.6 XRD pattern surface of precipitate

from as-cast 1Si1Mn alloy

s + C M23X6 + M12X

Fig. 3.1.7 XRD patterns of precipitates

that were electrolytically extracted
from as-cast alloys with various
carbon contents*.

*S. Mineta, S. Namba, T. Yoneda, K. Ueda, and T. Narushima: Metall. Mater. Trans. A, 2010, vol. 41A, pp. 212938.

10

Microstructure evolution during heat treatment

1.8 ks

7.2 ks

43.2 ks
Complete dissolution

1548 K
Starlike

20 mm

1523 K
20 mm

20 mm

20 mm

20 mm

20 mm

Blocky

Blocky

1448 K
20 mm

20 mm

20 mm

Fig. 3.1.8 Microstructure of 1Si0Mn alloy heat-treated at various temperatures

and holding times.

Complete precipitate dissolution was achieved at 1548 K for 43.2 ks.

Blocky precipitates were detected at low temperature.
Starlike precipitates were detected at high temperature.
11

Phase of precipitates formed after heat treatment

q: M23X6, h: M6X-M12X, p: M2T3X, U: Unknown

Fig. 3.1.9 Phases of precipitates formed in as-cast and heat-treated alloys.

The addition of Si increased the holding time for complete precipitate dissolution.
M23X6 type and p-phases were the main precipitate at low and high temperatures,
respectively.
Unknown phase was observed in the boundary of complete-incomplete
dissolution.
12

EPMA of p-phase
Si

10 mm

10 mm

Mo

Co

10 mm

Cr

Elements
at%
Co
33.6
Cr
41.8
Mo
8.7
C
14.9
Si
1.0
Mn
N.D.
(N.D.: Not detected)
Ratio of metallic element:

Rat% =
10 mm

10 mm

(Cr+Mo)
= 1.50
Co

10 mm

Mn

M2T3C

High contents of Mo, Cr and Si

p-phase: 14.9 at%C Theoretically:16.7 at%C
10 mm

Fig. 3.1.10 EPMA images of p-phase in

1Si1Mn alloy heat-treated at 1548K for 0 ks.

13

TEM of p-phase
g-phase

p-phase

p-phase with cubic

b-manganese structure

Fig. 3.1.11 TEM analysis of p-phase in 1Si1Mn alloy heat-treated at 1548 K for
1.8 ks. (a) Bright field image, (b) associated diffraction pattern, and (c)
schematic diagram identifying reflections in (b). Beam directions along [110] of
g-phase and [201] of p-phase.

14

Chemical composition of precipitates

Table 3.1.5 Chemical composition of q and p-phases formed during heat treatment (mass%)
Phase

M23X6 type
p-phase

Alloys
1Si0Mn (1448 K, 1.8 ks)
0Si1Mn (1448 K, 1.8 ks)
1Si1Mn (1448 K, 1.8 ks)
1Si0Mn (1548 K, 1.8 ks)
0Si1Mn (1548 K, 0 ks)
1Si1Mn (1548 K, 1.8 ks)

Co
16.9
17.7
15.9
40.6
39.6
36.6

Cr
65.1
63.8
65.3
37.9
39.4
38.8

Mo
12.4
12.3
12.3
18.0
17.9
19.8

C
5.5
5.6
5.7
2.2
2.3
2.7

Si
0.1
N.D.
0.1
1.3
N.D.
1.2

Mn
N.D.
0.6
0.7
N.D.
0.8
0.9

(N.D.: Not detected)

M23X6 type
Extremely high content of Cr
Low content of Co and Si

p-phase
High content of Mo and Cr
Si slightly enriched

15

Morphology of precipitates
Starlike-dense
X

Blocky-dense
M23X6

M23C6 + g
Starlike-stripes
M23X6 + g

2 mm

Fig. 3.1.12 SEM images of precipitates in 1Si0Mn alloy after

heat treatments.

2 mm

Partial melting*

M23X6
Temperature increased

Liquid + p-phase(starlike-dense)
M23X6 + g (starlike-stripes)
M23X6 + g (starlike-stripes)
Temperature decreased

*A.J.T.

Clemow and Daniell: J. Biomed. Mater. Res., 13 (1979) Inst. 265-279.

16

Precipitates formed in as-cast alloys

X (q)

Table 3.2.1 Phases of precipitates formed in

as-cast alloys
Alloys
0.5Si0Mn
1Si0Mn
2Si0Mn
0Si1Mn
0Si2Mn
0.5Si0.5Mn
0.75Si0.75Mn
1Si1Mn
0.15C1Si
0.35C1Si

Phase of precipitate
h
p

c: a-Mn structure (cubic)

Major precipitates
Fig. 3.2.1 XRD patterns of precipitates
electrolytically extracted from as-cast alloys
with various carbon contents.

17

c-phase
X (q)

Andrews [1949]: c-phase precipitates with

a-Mn structure in Cr-Ni-Mo steels
Many researches : intermetallic compound
in Fe-based alloys
Goldschmidt [1957]:
Carbon-containing compound
Carbon can dissolve up to around 5 at%:
the 58 atoms per unit cell with 3 interstitial
carbon atoms
Co
Cr-Mo

Fig. 3.2.2 XRD patterns of the

precipitates electrolytically extracted
from as-cast 0.15C1Si alloy.

Fig. 3.2.3. Schematic presentation of

the structure in c-phase.

18

c-phase formation in 0.15C1Si alloy

q: M23X6 type, h: M6X-M12X type, p: M2T3X

1Mn

0.15C1Si

c
Fig. 3.2.4 Phases of precipitates formed in ascast and heat-treated 0.15C1Si alloys.

Complete-incomplete precipitate
dissolution condition boundary
shows the C-curved shape.
Fig. 3.2.6 TEM micrograph of c-phase formed in
0.15C1Si alloy heat-treated at 1523 K for 0 ks
showing (a) bright field image and (b)
associated diffraction pattern and diffraction of
[175] zone axes.

Fig. 3.2.5 XRD pattern of precipitates

electrolytically extracted from 0.15C1Si
alloy heat treated at 1523 K for 0 ks.

19

Chemical composition and morphology of c-phase

Table 3.2.2 Chemical composition of c-phase (mass%)

Phase

c-phase

Alloys
0.15C1Si (1473 K, 1.8 ks)

Co

Cr

Mo

Si

Mn

47.7

30.0

20.3

2.0

N.D.

*
: almost the same as carbon content in metallic matrix
N.D. : Not detected

c-phase is an intermetallic compound.

(a)

(b)
c-phase
20 mm

Blocky dense
5 mm

Fig. 3.2.7 Morphology of c-phase formed during heat treatment (a) before
and (b) after electrolytic extraction, shown as blocky-dense precipitates.

20

Stability of c-phase
1Mn

Possible reaction

0.15C1Si

Khaenko et al. [1993]:

The c-phase was stable
from the subsolidus to
room temperatures in an
Fe-Cr-W-Mo-C system.
The p-phase was formed
when
partial
melting
occurred.

c + C M23X6 (+ p-phase)

c-phase is considered to be a harmful precipitate in

stainless steel manufacturing processes.
However, it is relatively easy to prevent the formation of the
c-phase in Co-Cr-Mo alloys due to limited heat treatment
variables and alloy composition.

21

Phases of precipitates in heat-treated alloys

0.5Si
0Mn

1Si
0Mn

0Si
1Mn

0Si
2Mn

0.5Si
0.5Mn

0.75Si
0.75Mn

0.15C
1Si

0.35C
1Si

2Si
0Mn

h
1Si
1Mn

q: M23X6 type, h: M6X-M12X

type, p: M2T3X, c: Intermetallic
U: Unknown
Fig. 3.2.8 Summary on complete dissolution and phase of precipitates
formed in the alloys.

22

h-phase

2Si0Mn
(a)

h-phase
10 mm

Fig. 3.2.9 XRD pattern of h-phase

electrolytically extracted from
2Si0Mn alloy heat treated at 1498 K
for 43.2 ks.

(b)

Blocky dense

5 mm

Fig. 3.2.10 Morphology of h-phase formed during

heat treatment at 1498 K for 43.2 ks (a) before and
(b) after electrolytic extraction, shows as blockydense precipitates.

23

Chemical composition of h-phase

Si

2 mm

2 mm

Cr

Co

2 mm

Mo

h-phase
2 mm

2 mm

2 mm

Fig. 3.2.11 EPMA images of

h-phase formed in 2Si0Mn
alloy heat-treated at 1498 K
for 43.2 ks.

Table 3.2.3 Chemical composition of h-phase (mass%)

Phase
h-phase

Alloy
2Si0Mn(1498 K, 43.2 ks)

Co
38.7

Cr
21.8

Mo
31.0

C
2.8

High content of Mo and Si and low content of Cr and Co

Si
5.7

24

h-phase formation
1Si0Mn

2Si0Mn

Ramrez et al. Co-25.23Cr-5.42Mo-0.26C-0.774Si-0.325Mn-0.316Fe[2002]

0.763Ni-0.49W alloy
During solidification;
+ C M23C6 + M12C
M12C () M23C6
Clemow and Daniell Co-28.19Cr-5.42Mo-0.24C-0.77Si-0.77Mn-0.23Fe[1979]
0.19Ni-0.05W alloy
During heat treatment; M23C6 M6C ()
This study 2mass% Si is required for the formation of h-phase.
25

Si contents on precipitates
(CCM-0.25C-xSi)
(CCM-0.25C-xSi-xMn)
(CCM-0.25C-xSi)
(CCM-0.25C-xSi-xMn)
(CCM-0.25C-2Si)
(CCM-0.15C-1Si)

Si was excluded from

q-phase precipitate.
Si was enriched in p, h
and c-phase precipitates.
Fig. 3.2.12 Si contents in precipitates.

26

Effect of Nitrogen on microstructure

of biomedical Co-Cr-Mo-C alloys

Biomaterial

27

Chemical composition of specimens

Table 2.1 Chemical composition of the CCM-C-Si-Mn alloys used in this study (mass%)

Alloys
0.5Si0Mn
1Si0Mn
2Si0Mn
0.15C1Si
0.35C1Si
0Si1Mn
0Si2Mn
0.5Si0.5Mn
0.75Si0.75Mn
1Si1Mn

Cr
27.24
29.17
28.05
27.06
27.68
27.86
27.07
27.46
28.26
27.96

Mo
5.74
6.22
6.01
5.61
6.04
6.03
5.80
6.01
6.23
6.09

C
0.22
0.23
0.22
0.13
0.38
0.25
0.23
0.29
0.23
0.26

Si
0.58
0.96
2.60
1.33
1.20
0.11
0.07
0.60
0.85
0.98

Mn
0.02
0.08
0.02
0.02
0.01
0.97
1.91
0.48
0.79
1.02

P
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001

S
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001

Co
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.

Table 2.2 Chemical composition of the CCM-C-N-Si-Mn alloys used in this study (mass%)
Alloys
1Si0Mn0.175N
0Si1Mn0.175N
1Si1Mn0.175N
0Si0Mn0.175N

Cr
27.9
27.77
27.67
27.65

Mo
6.17
6.09
6.01
6.22

C
0.25
0.24
0.24
0.25

Si
1.21
<0.001
1.19
<0.001

Mn
0.001
1.15
1.15
0.001

N
0.15
0.19
0.17
0.19

P
0.002
0.002
0.003
<0.001

S
<0.001
<0.001
<0.001
<0.001

Co
Bal.
Bal.
Bal.
Bal.

28

Microstructure of as-cast alloys without N

1Si0Mn

0Si1Mn

50 mm

1Si1Mn

50 mm

0Si0Mn

50 mm

50 mm

Fig. 3.1.1 Microstructure of as-cast alloys.

Fig. 3.1.2 Effect of the alloying

elements in as-cast alloys on the
content and size of precipitates.

Dendrite matrix, interdendritic and grain boundary precipitates were

observed in as-cast alloys.
The addition of Si and Mn increased the precipitate content in ascast alloys.

29

Microstructure of as-cast alloys

1Si0Mn0.175N

Interdendritic
precipitation

1Si1Mn0.175N

0Si1Mn0.175N

0Si0Mn0.175N

Grain boundary
precipitates

Fig. 4.1 Microstructure of as-cast alloys.

Dendrite matrix, interdendritic and grain boundary precipitates were

observed in as-cast alloys.
30

Microstructure of as-cast alloys

1Si0Mn0.175N

0Si1Mn0.175N

Blocky
dense

1Si1Mn0.175N

0Si0Mn0.175N

Lamellar
cellular
precipitation

Blocky
dense

Fig. 4.2 SEM images of precipitates formed in as-cast alloys.

Blocky dense precipitates in the alloys with Si addition.

Lamellar cellular precipitation in the alloys without Si addition.

31

Morphology of precipitate in as-cast alloys

p-phase

M2X type

1Si0Mn0.175N alloy

(a)

0Si0Mn0.175N alloy

(b)
Blocky-dense
Plate-like

Fig. 4.3 SEM images of the (a) p-phase and (b) M2X type precipitates formed in as-cast alloys.

32

Phase of precipitates in as-cast alloys without N

X (q)

Table 3.1.1 Crystallographic data of precipitates

Phase
q
h
p

Prototype
M23X6
M6X-M12X
M2T3X

Crystal structure
Cubic
Cubic
Cubic, b-Mn structure

X
= Carbon (C)
M, T = Metallic elements
Table 3.1.2 Precipitates formed in as-cast alloys

Alloys
0Si0Mn
1Si0Mn
0Si1Mn
1Si1Mn

Phase of precipitate
q
h
p

= Main precipitate
Fig. 3.1.3 XRD patterns of precipitates
electrolytically extracted from as-cast alloys.

33

Phase formed in as-cast alloys

Table 4.1 Phases of precipitates formed in
as-cast alloys

Alloys

Phase
p

M2X type

1Si0Mn0.175N

0Si1Mn0.175N

1Si1Mn0.175N

0Si0Mn0.175N

M2X type: Hexagonal

M: Metallic element
X: Carbon and nitrogen
Major precipitate
Fig. 4.4 XRD patterns of precipitates
electrolitycaly extracted from as-cast
alloys.

34

TEM analysis
(a)
(b) M2X precipitate
(c) Co-based metallic
g-phase

50 nm

(c)

(b)

220
101
021

000

120

111

000

111

Fig. 4.5 TEM micrograph of lamellar cellular precipitation formed in as-cast

0Si0Mn0.175N alloy showing (a) bright field image and associated diffraction pattern
of (b) [212] zone axes for M2X type, and (c) [112] zone axes for g-phase.
35

Lamellar cellular precipitation

Lamellar cellular
precipitation

g1

M2X

g2

Rosenthal et al. [2010] reported

the formation of coarse lamellar
cellular colonies (M23X6 and gphases) in as-cast Co-28Cr-6Mo0.25C alloy.

g1 g2 + M2X
1 mm
Fig. 4.6 SEM image of the a lamellar
cellular colony of M2X type precipitates
formed in as-cast 0Si0Mn0.175N alloy.

g1,g2 : FCC Co-based metallic

phases

Precipitation of the cellular colonies

on the grain boundary supports the
discontinuous reaction mechanism.
36

Phases of precipitates in heat-treated alloys

X

0Si1Mn
0.175N

1Si0Mn
0.175N
M

1Si1Mn
0.175N

0Si0Mn
0.175N

Fig. 4.7 Summary on phase of precipitates formed in the alloys.

-phase is the main phase at low temperature in the alloy containing Si.

37

Phases of precipitates in heat-treated alloys

CCM-0.25C-1Si

CCM-0.25C0.175N-1Si

No nitrogen

With nitrogen

q: M23X6, h: M6X-M12X, p: M2T3X, U: Unknown

The amount of h-phase increased by nitrogen addition

Escobedo et al. [1996]

ASTM F 75 alloy with nitrogen content of 0.035 to 0.15mass%
The promotion of the formation of the h-phase by the
addition of nitrogen

38

Chemical compositions of precipitates

Table 4.2 Chemical compositions of q-phase,
h-phase, p-phase and M2X type precipitate
(mass%)
Phase
Co
Cr
Mo
q-phase 16.5 69.0 11.1
p-phase 34.4 38.1 21.7
h-phase 32.5 21.6 38.6
M2X type 4.2 79.0 10.0

C
5.7
2.7
2.3
3.5

N
Si
Mn
N.D. N.D. 0.1
0.7 1.3 1.1
1.0 4.0 N.D.
6.4 N.D. N.D.

(N.D.: Not detected)

M2X type
High content of Cr and N
Low content of Co and Si
q (M23X6 type) carbide
p and h phase carbon-riched carbonitride
M2X nitrogen-riched carbonitride

Fig. 4.8 Nitrogen contents on precipitates.

39

e/g ratio
As-cast alloys
without nitrogen

As-cast alloys
with nitrogen

f hcp = 0

f hcp = 0.28
f hcp = 0.02

f hcp = 0.36

hcp = 0

Hcp *

=
I

f hcp = 0

hcp
1011

hcp

1011

+ 1.5 I

fcc
200

f hcp = 0

Fig. 4.9 XRD pattern of bulk specimens for as-cast alloys with
and without N addition.
*

M. Sage and Ch. Gillaud: Rev. Metall. 49 (1950) 139-145.

40

Effect of Si and Mn on microstructure

of biomedical Co-Cr-Mo-C alloys
during aging

Biomaterial

41

Microstructure evolution during aging

2.4 ks

7.8 ks

43.8 ks

22.2 ks

1073 K

1Si0Mn

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

20 mm

1373 K

1073 K

0Si1Mn
1373 K

1073 K

1Si1Mn
1373 K

Fig. 5.1 Microstructure evolution during aging.

42

Precipitates formed during aging

1Si0Mn

0Si1Mn

1Si1Mn

Fig. 5.2 TTP diagrams of alloys during aging.

Taylor [1983] and Mineta et al. [2008] M23X6 type

Kurosu et al. [2007] s-phase (Co-28Cr-6Mo-1Ni alloy)
Cr2N (Co-27Cr-5Mo-0.16N alloy)
This study M23X6 type and h-phase

The addition of Mn decreased the precipitation area in the

TTP diagram as compared to the Si addition.
The addition of Si increased the precipitation area of h-phase. 43

Morphology of precipitates in 1Si0Mn aged alloy

Rod-like

Blocky

Fig. 5.3 Morphology of precipitates in 1Si0Mn alloy aged at 1073 K 1373 K for 43.8 ks.

44

Hardness after aging

1Si0Mn

After
treatment
Aftersolution
solution
treatment

0Si1Mn

1Si1Mn

After solution treatment

After solution
treatment

After
treatment
Aftersolution
solution
treatment

Fig. 5.4 Effect of aging on hardness of CCM-C alloys with addition of Si and Mn.

Increasing in hardness caused by fine

precipitation of M23X6 type and h-phase.
45

Wear test, Stattic immersion test,

Corrosion test

Biomaterial

46

Pin and disk in wear test

Pin
As-cast and heat-treated:
CCM-0.25C-0.2N-0Si-0Mn (0Si0Mn0.2N)
CCM-0.25C-0.2N-1Si-1Mn (1Si1Mn0.2N)
CCM-0.25C-0N-1Si-1Mn (1Si1Mn0N)
Table 6.1 Chemical composition of Co-Cr-Mo-C alloys (mass%)
Alloy
0Si0Mn0.2N
1Si1Mn0.2N
1Si1Mn0N

Cr
29.97
28.10
27.92

Mo
5.70
5.78
5.83

C
0.24
0.23
0.23

N
0.20
0.20
0.02

Si
Mn
<0.001 <0.001
1.17
1.15
1.22
1.16

Ni
0.01
0.01
0.01

Co
Bal.
Bal.
Bal.

Pin size: f5 mm 40 mm, Ra < 0.05 mm

Heat treatment conditions: 1508 K, 86.4 ks (W.Q.)
Complete precipitate dissolution

Disk
Specimen: alumina (99.9%)
Disk size: f40 mm 5 mm, Ra < 0.05 mm

Fig. 6.1 Schematic

illustration of the pin.

47

Wear test conditions and analysis

Wear test conditions
Contact stress : 107.5 MPa
Lubricant : 1mass% lactic acid (pH 2.28)
Kokubo (pH 7.4)
Table 6.2 Chemical composition of Kokubo solution used in this study (mM)

Lubricant volume: 20 ml
Speed: 25 mm/s

Temperature: 310 K
Time: 259.2 ks

Analysis
Pin
Surface observation: SEM
Lubricant
Elution of metallic ions: ICP-AES, ICP-MS

Fig. 6.2 Schematic illustration

of the pin-on-disk type wear
test.

48

Phase of precipitates in as-cast alloys

Table 6.3 Phases of precipitate extracted from
as-cast alloys
Phase
Alloys
M2X type
p
q
0Si0Mn0.2N

1Si1Mn0N

1Si1Mn0.2N

M = Metallic element, X = Carbon and nitrogen

Major precipitate

As-cast

5 mm

Heat-treated

400 mm

Fig. 6.3 Precipitate content in as-cast specimen.

Fig. 6.4 Typical microstructures in

as-cast and heat-treated 0Si0Mn0.2N
alloy.

49

Concentration of eluted metallic ions

As-cast ~ Lactic acid

Heat-treated ~ Lactic acid

As-cast ~ Kokubo

Fig. 6.5 Concentration of metallic ions in the 1mass% lactic acid and Kokubo
solutions after wear test.

Elution of metallic ions in Kokubo solution was much less that

in 1mass% lactic acid solution.
Ratio of the amount of eluted ions in 1mass% lactic acid
solution corresponded to the alloy compositions.
Concentration of Cr were less than to that of Mo in Kokubo
solution.
50

Pin surface after wear test in 1mass% lactic acid

0Si0Mn0.2N

As-cast

1Si1Mn0.2N

1Si1Mn0N

Detachment

5 mm

Heattreated
Fig.6.6 SEM images of pin surface after wear test in 1mass% lactic acid
solution for 259.2 ks.

The detachment of precipitates after wear test was observed

on metallic matrix of 0Si0Mn0.2N alloy contained lamellar
cellular precipitation.

51

Static immersion test

Specimens
As-cast :
0Si0Mn0.175N alloy (M2X type and M23X6 type )
1Si1Mn0.175N alloy (p-phase)
2Si0Mn alloy (p-phase, h-phase and M23X6 type )
0.5Si0.5Mn alloy (M23X6 type )

Conditions
Solution: 1mass% lactic acid (pH 2.28)
Lubricant volume: 10 ml Temperature: 310 K
Time: 259.2 ks
Shaking peed: 16 rpm

Analysis
Lubricant
Elution of metallic ions: ICP-MS
Fig. 6.7 Schematic illustration
of the static immersion test.

52

Concentration of eluted metallic ions

Fig. 6.8 Concentration of metallic ions eluted from as-cast

alloys in the 1mass% lactic acid after static immersion test.

The amount of ions elution in static immersion test was much

less than to that of in wear test.
53

Corrosion test
Specimens
Heat-treated :
Single p-phase (0.75Si0.75Mn alloy, 1548 K, 0 ks)
Single c-phase (0.15C1Si alloy, 1523 K, 0 ks)
Single h-phase (2Si0Mn alloy, 1498 K, 43.2 ks )
Single M23X6 type (0.5Si0.5Mn alloy, 1473 K, 1.8 ks)

Conditions

Solution
Polarization voltage
Immersion time
Temperature:

: Kokubo (pH 7.4)

: 0.85 V vs SCE
: 0.12 ks
: 310 K

Analysis
Surface observation: OM and SEM
Fig. 6.9 Schematic illustration of the corrosion test.

54

Surface conditions after polarization test

0.75Si0.75Mn

0.15C1Si

c-phase

p-phase
2Si0Mn

0.5Si0.5Mn

h-phase
q-phase
Fig. 6.10 The surface of solution-treated alloys after polarization
test for 0.12 ks.

The corrosive area was observed in the surface of

alloy containing c-phase and q-phase.

55