JPEDAV (2014) 35:544–554

DOI: 10.1007/s11669-014-0317-7
1547-7037 ASM International

Experimental Investigation and Thermodynamic

Calculation of the Co-Cr-Mo System
Weilin Wang, Fucheng Yin, Minghua Zhang, Manxiu Zhao, and Zhi Li

(Submitted September 23, 2013; in revised form March 19, 2014; published online May 28, 2014)

The isothermal section of the Co-Cr-Mo system at 1200 K has been investigated experimentally
using scanning electron microscopy coupled with energy dispersive x-ray spectroscopy and x-ray
diffraction. Six three-phase regions exist in the 1200 K isothermal section. The experimental
results indicated that the maximum solubility of Cr in Co-Mo binary compounds Co3Mo and l
at 1200 K is 5.2 and 23.6 at.%, respectively, and that of Mo in Co-Cr binary compound r
is 39.6 at.%. Based on the literature data of the thermodynamic assessment of Co-Mo, Co-Cr,
Cr-Mo binary systems and experimental results of the ternary system, the thermodynamic
calculation for Co-Cr-Mo system was carried out by means of CALPHAD technique. The
computational results and the experimental data are self-consistent reasonably.

systems using the CALPHAD approach has been shown to

Keywords CALPHAD technique, Co-Cr-Mo system, phase dia-
gram
1. Introduction
It is well known that Co-based superalloys exhibit higher
melting temperature, superior hot-corrosion and thermal
fatigue resistance than Ni-based and Fe-based superal-
loys.[1,2] Both Chromium (Cr) and Molybdenum (Mo) are
main constituent elements of Co-based high-temperature
alloys, Cr can improve the resistance against high temper-
ature oxidation and corrosion,[3] while Mo serves to provide
additional strength to the matrix owing to its large atomic
size.[4] The alloys show potential application in the field of
aircraft turbines and combustor section.[5] The other appli-
cation is for surgical implants, such as hip and knee
replacements, bone recovery and dental implants due to its
good biocompatibility.[6] So the Co-Cr-Mo system can be
regarded as an important subsystem for cobalt-based
superalloys. In order to design the new materials and
understand the relationship between microstructures and
properties, the accurate knowledge of phase equilibria in the
Co-based alloy system is necessary. Obtaining such knowl-
edge exclusively from experiments is cumbersome and
expensive. Thermodynamic modeling of multi-component
Weilin Wang, Fucheng Yin, Minghua Zhang, Manxiu Zhao, and
Zhi Li, School of Mechanical Engineering, Xiangtan University,
Xiangtan 411105 Hunan, People’s Republic of China and Key
Laboratory of Materials Design and Preparation Technology of
Hunan Province, Xiangtan University, Xiangtan 411105 Hunan,
People’s Republic of China. Contact e-mail: fuchengyin@xtu.edu.cn.
be a highly efficient tool in this regard.[7,8] In the present
work, the 1200 K isothermal section of the Co-Cr-Mo
ternary system has been determined experimentally using
scanning electron microscopy (SEM) coupled with energy
dispersive x-ray spectroscopy (EDS) and x-ray diffraction
(XRD). Based on the literature data of the thermodynamic
assessment of Co-Mo, Co-Cr, Cr-Mo binary systems and
experimental results of the ternary system, the thermody-
namic calculation for Co-Cr-Mo system was carried out by
means of CALPHAD technique.
2. Literature Data for the Co-Cr-Mo System
Experimental data on constituent binary phase diagrams of
the Co-Cr-Mo system, i.e. Co-Mo,[9,10] Co-Cr,[11] and Cr-Mo[12]
have been reported in the literature.
The phase relations of Co-Cr-Mo system have been
investigated by many researchers.[8,13–20]
Fletcher and Elsea[13] investigated the effects of molyb-
denum (Mo) on the fcc-hcp transformation temperature
range and formation of the r (Co7Cr8) phase in the Co-Cr
binary system using some Co-Cr-Mo alloys. Rideout
et al.[14] determined a part of Co-Cr-Mo ternary isothermal
section at 1473 K experimentally. A ternary intermetallic
R (Co49Cr21Mo30) phase, which is hard and brittle, was
found. The partial liquidus and solidus surfaces were
determined by using some alloys containing more than 50
pct Co and above 1273 K by Metcalfe.[15] Darby et al.[16]
determined the isothermal section at 1573 K and found that
the r (Co7Cr8) phase had a wide composition range and
extended from the Co-Cr side to the Co-Mo side. A new
ternary phase D was found, which had an unknown complex
crystal structure and showed some similarities with that of
the R phase. Darby et al.[17] confirmed that the D phase is
the same as the R phase later. The Co-Cr-Mo system was
first extrapolated based on the results of the thermodynamic

544 Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014

assessment of the binary systems for the purpose on the heat
treatments of cobalt-based surgical implant by Rajan.[18]
Gupta[19] made a critical review of the phase equilibria and
pointed out that partially known phase boundaries should be
reinvestigated in the Co-Cr-Mo ternary system. Zhao[8,20]
determined the phase relations at 1373 K using the diffu-
sion-multiple technique. In his work, the r (Co2Mo3) phase
was not reported, which occurs between 1273 and 1893 K
in the Co-Mo binary system. The binary and ternary phases
of the Co-Cr-Mo system and their structure data are shown
in Table 1.
by a D/max-rA x-ray diffractometer, operating at 40 kV and
100 mA with Cu Ka radiation.
4. Thermodynamic Models
In the present work, the thermodynamic models of the
phases in the Co-Cr-Mo system are chosen based on the
experimental information of the phase equilibria and the
crystal structures. The used models of phases in the Co-Cr-
Mo ternary system are listed in Table 1.

4.1 Solution Phases

3. Experimental Procedures The Gibbs free energies of the liquid, fcc, bcc, and hcp
phases in the Co-Cr-Mo system are described by the
The phase relationship of the Co-Cr-Mo ternary system subregular solution model. According to this model, the
at 1200 K was determined using equilibrated alloys. They molar Gibbs free energy of solution phase in the Co-Cr-Mo
were prepared using Co, Mo chunks and Cr particles system is given by:
(Particle size = 1 to 5 mm). The purity of the raw materials X X
is 99.99 wt.%. The three elements were mixed and melted GUm ¼ x0i GU
i þ RT xi lnxU ex U
i þ G þ
mg U
G
in an arc furnace under high purity argon atmosphere i¼Co;Cr;Mo i¼Co;Cr;Mo
using a non-consumable tungsten electrode. The buttons ðEq 1Þ
were re-melted five times to improve their homogeneities.
The sample weight was 5 g and the weight loss during where GU i is the molar Gibbs free energy of pure element i
melting was generally less than 1% of the sample weight. in the structure U (liquid, fcc, bcc, and hcp) phase, and the
The alloys were sealed in an evacuated quartz tube and then term ex GU is the excess free energy, which is expressed by
annealed at 1200 K for 50 days. At the end of the treatment, the Redlich–Kister polynomials[21] as:
the alloys were quenched into water to preserve the
equilibrium state at annealing temperature. The quenched
ex
GU ¼ xCo xMo LU U U
Co;Mo þ xCo xCr LCo;Cr þ xCr xMo LCr;Mo
samples were cut into two parts. One piece was prepared for þ xCo xMo xCr LU
Co;Cr;Mo
metallographic examination and the other for x-ray diffrac-
tion analyses. Two kinds of chemical etchant, which consist
of (60 ml HCl, 15 ml HNO3, 15 ml CH3COOH, 15 ml X
n
LU
i;j ¼
m U
Li;j ðxi  xj Þ m
H2O) and (4 g KMnO4, 4 g NaOH 100 ml H2O), respec-
m¼0
tively, were used for metallographic examination of all
specimens. Detailed metallographic examinations and com-
position analyses of various phases in the samples were LU 0 U 1 U 2 U
Co;Cr;Mo ¼ xCo LCo;Cr;Mo þ xMo LCo;Cr;Mo þ xCr LCo;Cr;Mo
performed using a JSM-6360LV scanning electron micro- ðEq 2Þ
scope coupled with energy-dispersive spectrometry (SEM-
EDS). The constituent phases of the alloys were further where LUi;j is the interaction parameter in the i-j binary
determined by analyzing x-ray diffraction patterns generated system, and the LU Co;Cr;Mo corresponds to the interaction

Table 1 The structures and the used model of phases in the Co-Cr-Mo ternary system
Phase Composition Pearson symbol Space group Structure type Prototype Thermodynamic model

Liquid … … … … … (Co,Cr,Mo)
eCo Co hP2 P63/mmc hcp_A3 Mg (Co,Cr,Mo)
aCo Co cF4 Fm-3 m fcc_A1 Cu (Co,Cr,Mo)
r Co7Cr8 tP30 P42/mm D83 r CrFe (Co,Cr,Mo)8(Cr,Mo)4(Co,Cr,Mo)18
Co2Mo3 tP30 P42/mm D83 r CrFe
(Mo) Mo cI2 Im-3 m bcc_A2 W (Co,Cr,Mo)
(Cr) Cr cI2 Im-3 m bcc_A2 W (Co,Cr,Mo)
l Co7Mo6 hR13 R-3 m D85 Fe7W6 (Co,Cr,Mo)7(Cr,Mo)2(Co,Cr,Mo)4
e Co3Mo hP8 P63/mmc D019 Ni3Sn Co3(Cr,Mo)1
R Co49Cr21Mo30 hR53 R3 … R(Co,Cr,Mo) (Co,Cr,Mo)27(Cr,Mo)14(Co,Cr,Mo)12

Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014 545

parameters in the Co-Cr-Mo ternary system. The coefficient the same structure as that in the Fe-Mo binary system,[32]
of n LU
Co;Cr;Mo was evaluated in the present work. which has been modeled as (Fe)27(Mo)14(Fe,Mo)12.
In the Co-Cr-Mo ternary system, the magnetic contribu- The crystal structure R phase was investigated by
tion to Gibbs free energy for the fcc and hcp phases is Komura et al.[33] and suggested that Co could occupy the
considered because magnetic transformation occurs in these sublattices of Fe. Meanwhile, the Cr occupied the second
phases. The termmg GU is expressed as follows: and third sublattices of Mo, which is similar with the
l phase, and the occupied of Cr and Mo in the first
mg
GU ¼ RT lnðbU þ 1Þf ðsU Þ; sU ¼ T=TU
c; ðEq 3Þ site were deduced by the present and previous experi-
mental work. Therefore, the ternary R phase is described
where TcU is the critical Curie or Neel temperature and bU
by a three-sublattice model of (Co,Cr,Mo)27(Cr,Mo)14
the magnetic moment per mole of atoms. The term f(s)
(Co,Cr,Mo)12.
represents a polynomial obtained by Hillert and Jarl.[22]
The intermetallic of the Co3Mo phase in the Co-Mo
binary systems was treated as stoichiometric phase and
4.2 Intermetallic Phase Model
modeled with the sublattice model, e.g. (Co)3(Mo). Accord-
The r (Co7Cr8), l (Co7Mo6) and R (Co49Cr21Mo30) ing to the experimental phase diagram data in the Co-Cr-Mo
phases are the intermetallic phases which have compli- ternary system, the compounds of the Co3Mo is modeled
cated crystalline structures and larger solubility range. The with the sublattice model, e.g. (Co)3(Cr,Mo)1.
r (Co7Cr8, Co2Mo3) phase is D83 structure as the CrFe All the three three-sublattice models for the phases of r,
type.[23] In the assessed Co-Mo and Co-Cr binary l, R and Co3Mo are described as a general formula
systems, the r (Co7Cr8, Co2Mo3) phases were modeled (A,B,C)x(A,B,C)y(A,B,C)z. The Gibbs energy of the phase
with (Co)8(Mo)4(Co,Mo)18 and (Co)8(Cr)4(Co,Cr)18 / (/ = r, l, R and Co3Mo) can be described by the
sublattices respectively.[24–28] Based on the description following expression:

XXX X X X
GU ¼ yi I yIIj yIII
k
0
Gi:j:k þ xRT yIi ln yIi þ yRT yIIj ln yIIj þ zRT yIII III
k ln yk
i j k i j k
" # " #
XXX X
k XXX X
k
þ yIi1 yIi2 yIIj yIII
k
n
Li1 ;i2 :j:k ðyIi1  yIi2 Þn þ yIi yIIj1 yIIj2 yIII
k
n
Li:j1 ;j2 :k ðyIIj1  yIIj2 Þn ðEq 4Þ
i1 ;i2 j k n i j1 ;j2 k n

XXX X
k
III n
þ ½yIi yIIj yIII y
k1 k2
III n
Li:j:k1 ;k2 ðyIII
k1  yk2 Þ 
i j k1 ;k2 n

of the r phase in the Co-Mo and Co-Cr binary systems where 0Gi:j:k is the Gibbs free energy of the / phase when
and four ternary experimental isothermal sections, a large the first sublattice is occupied by the element i (i = Co, Cr
amount of Mo can be dissolved in the r (Co7Cr8) phase or Mo), the second by the element j (j = Co, Cr or Mo), and
and the Cr and Mo occupied in the first site were the third by the element k (k = Co, Cr or Mo); n Li1 ;i2 :j:k is the
deduced. In the present work the r phase is formulated as interaction parameter between element i1 and i2 (i1, i2 = Co,
(Co,Cr,Mo)8 (Cr,Mo)4(Co,Cr,Mo)18. Cr or Mo and i1 „ i2) when the second sublattice is
The l (Co7Mo6) phase is D85 structure with the Fe7W6 occupied by the element j (j = Co, Mo or Cr), and the third
type.[29] In the Co-Mo binary system, the l phase was modeled by the element k (k = Co, Mo or Cr); The parameters
by a three-sublattice model of (Co,Mo)7(Mo)2(Co,Mo)4.[24–26] n
Li:j1 ;j2 :k and n Li:j:k1 ;k2 are described in the same way.
From the experimentally determined single-phase field in the
previous work on the Fe-Cr-Mo system by Andersson and
Lange[30] and Co-Cr-W system by Yang et al.,[31] it is obvious
that molybdenum and tungsten atoms can be replaced by 5. Results and Discussion
chromium atoms by keeping the cobalt or iron content
relatively constant. In this work, the model to the ternary sys-
5.1 Experimental Determination
tem is thus suggested and applied as (Co,Cr,Mo)7(Cr,Mo)2
(Co,Cr,Mo)4. A total of 19 alloys were prepared to determine the
The ternary intermetallic compound R (R = D) has been isothermal section at 1200 K of the Co-Cr-Mo system. The
reported in the Co-Cr-Mo system around the composition of design compositions of the alloys are listed in Table 2. All
Co49Cr21Mo30.[14,16,17] It has been known that the R phase has phases in the alloys, together with the chemical

546 Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014

Table 2 The designed alloys and corresponding phase compositions of the Co-Cr-Mo ternary system
at 1200 K (at.%)*
EDS result (at.%)

Phase1 Phase2 Phase3

Equilibrated phase
Simple Design composition Phase1 / Phase2 / Phase3 Mo Cr Mo Cr Mo Cr

A1 55Co-44Cr-1Mo fcc / hcp / r 2.4 36.3 0.5 62.2 1.9 53.4

A2 60Co-35Cr-5Mo fcc / r 3.7 31.9 9.8 43.7
A3 60Co-30Cr-10Mo fcc / r / R 5.9 28.8 14.2 38.4 28.0 27.1
A4 55Co-20Cr-25Mo fcc / l / R 8.1 24.9 37.8 16.8 30.7 22.4
A5 60Co-15Cr-25Mo fcc / l 9.7 18.6 36.5 13.0
A6 77Co-9Cr-14Mo fcc / l / Co3Mo 12.6 10.3 37.3 9.1 20.9 5.2
A7 81Co-2Cr-17Mo fcc / Co3Mo 10.1 3.1 24.9 1.2
A8 69Co-1Cr-30Mo l / Co3Mo 42.3 1.7 26.1 0.9
A9 43Co-39Cr-18Mo r/R 17.6 41.0 31.3 27.7
A10 37Co-40Cr-23Mo r/R 22.6 41.4 31.7 29.4
A11 20Co-50Cr-30Mo bcc / r 38.7 56.1 30.0 48.1
A12 20Co-40Cr40Mo bcc / r 60.6 34.6 37.3 40.6
A13 15Co-70Cr-15Mo bcc / r 10.8 84.3 16.3 63.0
A14 20Co-35Cr-45Mo bcc / r / R 77.9 17.5 39.6 38.4 37.7 33.0
A15 20Co-20Cr-60Mo bcc / R /l 83.3 14.9 39.4 29.9 40.2 23.6
A16 20Co-10Cr-70Mo bcc / l 89.3 6.3 50.0 11.5
A17 35Co-6Cr-59Mo bcc / l 88.8 4.1 48.3 7.8
A18 30Co-15Cr-55Mo bcc / l 82.8 10.6 45.4 17.5
A19 24Co-2Cr-74Mo bcc / l 92.6 1.0 51.1 2.2

*The uncertainty of the phase compositions is less than ± 0.5 at.%

chemical constitution analyzed by SEM-EDS. However, the

Fig. 1 Experimentally determined isothermal section at 1200 K
of Co-Cr-Mo system
compositions determined by SEM-EDS, are also listed in
the same table. The tabulated composition values represent
the average of at least five measurements. The phases in the
alloys can be easily differentiated by their topography and
true identities of the phases were determined by the x-ray
diffraction patterns.
Based on the SEM-EDS analyses results, combined with
the information of the binary and ternary systems in
relevant literature, the 1200 K isothermal section of the
Co-Cr-Mo ternary system is constructed as Fig. 1. Six
three-phase regions have been identified. i.e., fcc + hcp +
r, fcc + r + R, fcc + l + R, fcc + l + Co3Mo, bcc + r + R
and bcc + l + R. Figure 2 is typical microstructures corre-
sponding to different three-phase fields. The tie lines
shown are from the EDS results and because of the
associated uncertainties may diverge from the point with
the nominal alloy composition.
Figure 2a is the microstructure of alloy A1. SEM-EDS
analyses indicated that it consists of three phases, hcp, fcc and
r. The large raised block hcp phase and the dark block fcc
phase were buried in the r matrix. The microstructure of alloy
A3 is shown in Fig. 2b, in which the fcc, R and r phases
coexist. The large gray block is r phase, the light block is R
phase and the dark matrix is fcc phase. Figure 2c shows the
microstructure of the alloy A4, which indicates alloy A4
belongs to (fcc + l + R) three-phase region, The microstruc-
ture of alloy A6 is shown in Fig. 2d, where there exists a three-
phase equilibrirm (fcc + l + Co3Mo), in which the l phase is
white and relatively small, and the EDS analyses suggest that
Cr solubility in the Co3Mo phase is 5.2 at.%. Alloy A14
locates in the bcc, R and r three-phase region. Figure 2e is the

Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014 547

Fig. 2 The typical microstructures corresponding to different three-phase fields. (a) alloy A1, fcc + hcp + r, (b) alloy A3, fcc + r + R,
(c) alloy A4, fcc + l + R, (d) alloy A6, fcc + l + Co3Mo, (e) alloy A14, bcc + r + R and (f) alloy A15,bcc + l + R

microstructure of this alloy, the experiment results indicate the Cr in Co-Mo binary compound l phase at 1200 K is about
solubility of Mo in the r (Co7Cr8) phase is 39.6 at.%. The 23.6 at.%.
three-phase microstructure of the alloy A15 is shown in The x-ray diffraction patterns of alloys A1, A3, A4, A6,
Fig. 2f. The EDS analyses suggest the maximum solubility of A14 and A15 are shown in Fig. 3 which clearly indicates

548 Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014

Fig. 3 The XRD patterns produced by alloy A1, A3, A4, A6,A14 and A15, which further confirmed the results obtained by SEM-EDS
analysis
the three-phase equilibrium states described above expect
alloy A1 and A6. For alloy A1, it is difficult to identify the
fcc and hcp structure in effect, because the fcc phase is not
possible to maintain the high temperature form due to the
solid state transformation of fcc to hcp during cooling. For
Alloy A6, as can be seen in Fig. 2d, the amount of the
l phase is limited, so the diffraction peaks cannot be found
in the x-ray pattern.
5.2 Thermodynamic Calculation
The phase diagram of the Co-Mo binary system was
thermodynamically assessed by Davydov[24,25] and Oikawa
et al.[26] This system consists of three terminal solid
solutions, hcp (cCo), fcc (aCo) and bcc (Mo) and three
intermetallic compounds e (Co3Mo), l (Co7Mo6) and
r (Co2Mo3). Recently, Oikawa et al.[26] used the order/
disorder formalism of Compound Energy Formalism (CEF)
to describe the fcc phase. The benefit from Oikawa’s
approach is that this description can be directly incorpo-
rated into a thermodynamic database for c/c’ superalloys
without the need of having to develop parameters for
describing the c’ (L12 structure) phase. In the present
work, in order to reduce the number of thermodynamic
modeling parameters during calculating, the results of
Davydov[25] are applied. The calculated Co-Mo phase
diagram is shown as Fig. 4a. The Co-Cr phase diagram
had been optimized by Kusoffsky and Jansson[27] and
Oikawa et al.[28] It showed four phases in Co-Cr system,
i.e., hcp (cCo) fcc (aCo) r (Co7Cr8) and bcc (Cr), the
present thermodynamic descriptions of the Co-Cr binary
system was reported by Oikawa et al.[28] as shown in
Fig. 4b. In comparison with Co-Mo and Co-Cr binary
systems mentioned above, the Cr-Mo binary system is very
simple, which consists of a liquid (L) and a bcc (Cr, Mo)
solid solution. A thermodynamic analysis of this system
had already been carried out by Frisk.[12] In this study,
Frisk’s assessed thermodynamic parameters were adopted.
Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014
The calculated Cr-Mo binary phase diagram is shown in
Fig. 4c.
Based on the present and previous experimental data, the
thermodynamic parameters of each phase in the Co-Cr-Mo
ternary system were evaluated using Thermo-Calc soft-
ware.[34] The complete set of thermodynamic parameters
describing all phase equilibria in the ternary Co-Cr-Mo
system is given in Table 3. A series of phase diagrams,
including isothermal sections, vertical sections, and the
projection of the liquidus surface were calculated, which
were compared with the experimental data, to test the
rationality of this thermodynamic description.
Figure 5a-d are the calculated isothermal sections at
1200, 1373, 1473 and 1573 K, in which the calculated
results are compared with the present and the previous
experimental data. All the phase relationships can be
reproduced by the calculations. The maximum solubilities
of Cr in binary compound l at 1200, 1373, 1473 and
1573 K calculated from the present thermodynamic descrip-
tion are about 22.3, 20.4, 18.7 and 17.5 at.%, respectively.
Mo can also dissolve in the r (Co7Cr8) phase and form a
continuous solid solution with the Co2Mo3 phase. The
presently calculated results are in reasonable agreement with
the experimental data. However, it is noteworthy that the r
phase is not stable above 1556 K in the Co-Cr binary
system. Gupta[19] predicted that the r phase should have
three-phase equilibrium with fcc and bcc phases at 1573 K
in the region of the Co-Cr binary system, which is
confirmed by present calculated results. It is inferred that
the addition of Mo raised the stable existing temperature of
the r phase as discussed above.
Figure 6 presents two vertical sections with the Co-Cr
ratios fixed as 80:20 and 68:32 compared with the experi-
mental data due to Fletcher and Elsea.[13] According to the
present Co-Cr binary system, there is no sigma phase at the
above proportionable composition. Hence the experimental
data was compared with the calculation as reference. It is
worthwhile note that the phase boundaries between fcc and
hcp are mostly agree with the experiment.
549
Fig. 4 The calculated phase diagrams of Co-Mo (a), Co-Cr (b) and Cr-Mo (c) binary systems according to the works of Davydov,[25]
Oikawa et al.[28] and Frisk et al.,[12] respectively

Figure 7 presents the calculated liquidus projection, in
which we compare the results of calculation with the
experimental data obtained by Metcalfe.[15] In the similar
composition range, there are two four-phase reactions.
One is the ternary eutectic reaction L M fcc + l + R
occurring at 1324 C at the composition of 15 at.% Cr
and 21 at.% Mo. Compared with the experimental results
of the Metcalfe[15] where the reaction occurs at 1325 C
at the composition of 14 at.% Cr and 24 at.% Mo, the
calculated results are reasonable. The second one is
peritectic reaction L + r + l M R which occurs at 1454 C
at the composition surrounding 19 at.% Cr and 31 at.%
Mo, but the temperature of the second reaction is higher
than the experimental data of the Metcalfe,[15] the
obtaining of the accurate reaction temperature needs
further experiment.

550 Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014

Table 3 The optimized parameters describing the phase relations of the Co-Cr-Mo system
Liquid Model ðCo; Cr; MoÞ
0 liquid
LCo;Cr;Mo ¼ 26400
bcc A2; Model ðCo; Cr; MoÞðVAÞ
0 bcc
LCo;Cr;Mo ¼0
1 bcc
LCo;Cr;Mo ¼ 155341:04þ114:45T
2 bcc
LCo;Cr;Mo ¼ 231681:64þ157:99T
hcp A3; Model ðCo; Cr; MoÞðVAÞ
0 hcp
LCo;Cr;Mo ¼ 3800 þ 18T
1 hcp
LCo;Cr;Mo ¼ 13T
fcc A1; Model ðCo; Cr; MoÞðVAÞ
0 fcc
LCo;Cr;Mo ¼ 106000  82T
1 fcc
LCo;Cr;Mo ¼ 50000
R ðCo49 Cr21 Mo30 Þ; Model ðCo; Cr; MoÞ27 ðCr; MOÞ14 ðCo; Cr; MoÞ12
0
GRCo:Mo:Cr ¼ 270 Gfcc 0 bcc 0 bcc
Co þ14 GMo þ12 GCr  440959:79  37:53T
0
GRCo:Mo:Mo ¼ 270 Gfcc 0 bcc 0 bcc
Co þ14 GMo þ12 GMo  129054
0
GRCr:Mo:Mo ¼ 270 Gfcc 0 bcc 0 bcc
Cr þ14 GMo þ12 GCo  200000
0
GRCr:Mo:Cr ¼ 270 Gfcc 0 bcc 0 bcc
Cr þ14 GMo þ12 GCr  116000
0
GRCr:Mo:Mo ¼ 270 Gfcc 0 bcc 0 bcc
Cr þ14 GMo þ12 GMo þ15730
0
GRMo:Mo:Cr ¼ 270 Gfcc 0 bcc 0 bcc
Mo þ14 GMo þ12 GCr  335174:50þ286:68T
0
GRMo:Mo:Mo ¼ 270 Gfcc 0 bcc 0 bcc
Mo þ14 GMo þ12 GMo þ120000
0
GRCo:Mo:Co ¼ 270 Gfcc 0 bcc 0 bcc
Co þ14 GMo þ12 GCo þ796473:78  351:40T
r ðCo2 Mo3 ; Co7 Cr8 Þ; Model ðCo; Cr; MoÞ8 ðCr; MoÞ4 ðCo; Cr; MoÞ18
0
GrCo:Mo:Cr ¼ 80 Ghcp 0 bcc 0 bcc
Co þ4 GMo þ18 GCr  86898
0
GrCo:Cr:Mo ¼ 80 Ghcp 0 bcc 0 bcc
Co þ4 GCr þ18 GMo  35000 + 82T
0
GrCr:Mo:Mo ¼ 80 Gbcc 0 bcc 0 bcc
Cr þ4 GMo þ18 GMo þ100000
0
GrMo:Mo:Cr ¼ 80 Gbcc 0 bcc 0 bcc
Mo þ4 GMo þ18 GCr þ200000
0
GrMo:Cr:Mo ¼ 80 Gbcc 0 bcc 0 bcc
Mo þ4 GCr þ18 GMo þ187000
0
GrMo:Mo:Mo ¼ 80 Gbcc 0 bcc 0 bcc
Mo þ4 GMo þ18 GMo þ 252000
0 r
LCo:Mo:Co;Mo ¼ 143792:37
0 r
LCo:Cr;Mo:Cr ¼ 121530
0 r
LCo:Mo:Cr;Mo ¼ 505512:71  370:24T
0 r
LCo:Cr:Cr;Mo ¼  71300
0 r
LCo:Cr:Co;Mo ¼  280530
l ðCo7 Mo6 Þ; Model ðCo; Cr; MoÞ7 ðCr; MoÞ2 ðCo; Cr; MoÞ4
0
GlCr:Mo:Cr ¼ 70 Gbcc 0 bcc 0 bcc
Cr þ2 GMo þ4 GCr þ 53000
0
GlCo:Mo:Cr ¼ 70 Ghcp 0 bcc 0 bcc
Co þ2 GMo þ4 GCr  115739:25þ33:55T
0
GlCr:Mo:Mo ¼ 70 Gbcc 0 bcc 0 bcc
Cr þ2 GMo þ4 GMo þ150000
0
GlCr:Mo:Co ¼ 70 Gbcc 0 bcc 0 bcc
Cr þ2 GMo þ4 GCo þ140000
0 l
LCo:Cr;Mo:Mo ¼ 257271:60
eðCo3 MoÞ; Model ðCoÞ3 ðCr; MoÞ1
0
GCo 3 Mo 0 bcc 0 bcc
Co:Cr ¼ 3 GCo þ GCr þ5000
0 Co3 Mo
LCo:Mo;Cr ¼ 10100

In J/(mol of atom); temperature (T) in Kelvin. The Gibbs energies for the pure elements are from the SGTE compilation.[35] The thermodynamic parameters in
the Co-Mo, Co-Cr and Cr-Mo systems are taken from Ref 12,25,28, respectively. The ternary parameters not listed in the table are assumed to be zero

Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014 551

Fig. 5 The calculated isothermal sections of the Co-Cr-Mo system at 1200 K (a), 1373 K (b), 1473 K (c) and 1573 K (d) compared
with the experiment data

552 Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014

Fig. 6 Calculated vertical sections at 80 and 68 wt.% of the Co-Cr-Mo system, compared with the experimental data as reported by
Fletcher and Elsea.[13]

Fig. 7 The liquidus projection of the Co-Cr-Mo system; the calculation (a) and the experiment data (b) as reported by Metcalfe.[15]

6. Conclusions 23.6 at.%, respectively, and that of Mo in Co-Cr binary

Based on SEM-EDS analyses and x-ray diffraction
results, the 1200 K isothermal section of the Co-Cr-Mo
ternary system has been determined in the present work. The
results showed that the maximum solubility of Cr in Co-Mo
binary compound Co3Mo and l at 1200 K is about 5.2 and
compound r is 39.6 at.%. Based on the literature data of the
thermodynamic assessment of the related binary systems
and the experimental results of the ternary system, the phase
relations of the Co-Cr-Mo system are calculated by
CALPHAD technique. A set of self-consistent reasonably
thermodynamic modeling for this system is obtained.

Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014 553

Acknowledgements
This investigation is supported by the National Science
Foundation of the China (No. 51071135), the Ph.D.
Programs Foundation of Ministry of Education of China
(No. 20114301110005) and Scientific Research Fund of
Hunan Provincial Educational Department (No. 12A128).
References
1. Q.Y. Huang and H.K. Li, The High-Temperature Alloys,
Metallurgical Industry Press, Beijing, 2000, p 10-13
2. C.T. Sims and W.C. Hagel, The Superalloys, Wiley, New
York, 1972, p 145-170
3. K. Frisk and A. Markstrom, Effect of Cr and V on Phase
Equilibria in Co-WC Based Hardmetals, Int. J. Mater. Res.,
2008, 99(3), p 287-293
4. R. Liu, S.Q. Xi, S. Kapoor, and X.J. Wu, Investigation of
Solidification Behavior and Associate Microstructures of
Co-Cr-W and Co-Cr-Mo Alloy Systems Using DSC Tech-
nique, Mater. Sci., 2010, 45, p 6225-6234
5. D.L. Klarstrom, Wrought Cobalt-Base Superalloys, J. Mater.
Eng. Perform., 1993, 2(4), p 523-530
6. T.M. Devine and J. Wulff, Cast vs. Wrought Cobalt-Chromium
Surgical Implant Alloys, J. Biomed. Mater. Res., 1975, 9, p 151-167
7. N. Saunders and A.P. Miodownik, CALPHAD (Calculation of
Phase Diagrams): A Comprehensive Guide, Elsevier, Oxford,
1998, p 299-408
8. J.C. Zhao, Methods for Phase Diagram Determination, 1st
ed., Elsevier, Amsterdam, 2007, p 246-291
9. T.J. Quinn and W. Hume-Rothery, The Equilibrium Diagram
of the System Molybdenum-Cobalt, J. Alloys Compd., 1963,
5, p 314-324
10. C.P. Heijwegen and G.D. Rieck, Determination of the Phase
Diagram of the Mo-Co, J. Alloys Compd., 1972, 34, p 309-314
11. K. Ishida and T. Nishizawa, The Co-Cr (Cobalt-Chromium)
System, J. Phase Equilib., 1990, 11(4), p 357-370
12. K. Frisk and P. Gustafson, An Assessment of the Cr-Mo-W
System, CALPHAD, 1988, 12(3), p 247-254
13. E.E. Fletcher and A.R. Elsea, Effects of Tungsten or
Molybdenum Upon the Alpha-Beta Transformation and
Gamma Precipitation in Cobalt-Chromium Alloys, Trans.
AIME., 1951, 191, p 897-902
14. S. Rideout, W.D. Manly, E.L. Kamen, B.S. Lement, and P.A.
Beek, Intermediate Phases in Ternary Alloy Systems of
Transition Elements, Trans. AIME., 1951, 191, p 872-876
15. A.G. Metcalfe, Thermal and Dilatometric Investigation of the
Alloys of Cobalt with Chromium and Molybdenum, Trans.
AIME., 1953, 197, p 357-364
554 Journal of Phase Equilibria and Diffusion Vol. 35 No. 5 2014
16. J.B. Darby, Jr, and P.A. Beck, Intermediate Phase in the
Cr-Mo-Co System at 1300 C, Trans. AIME., 1955, 203,
p 765-766
17. J.B. Darby, Jr., B.N. Das, Y. Shimomuro, and P.A. Beck, Notes
on R-Phase, Trans. AIME., 1958, 212, p 235-236
18. K. Rajan, Thermodynamic Assessment of Heat Treatments for
a Co-Cr-Mo Alloy, J. Mater. Sci., 1983, 18, p 257-264
19. K.P. Gupta, The Co-Cr-Mo (Cobalt-Chromium-Molybdenum)
System, J. Phase Equilib., 2005, 26(1), p 87-92
20. J.C. Zhao, The Diffusion-Multiple Approach to Designing
Alloys, Annu. Rev. Mater. Res., 2005, 35, p 51-73
21. O. Redlich and A.T. Kister, Algeraic Representation of
Thermodynamic Properties and the Classification Solutions,
Ind. Eng. Chem. Res., 1948, 40(2), p 345-348
22. M. Hillert and M. Jarl, A Model for Alloying in Ferromagnetic
Metals, CALPHAD, 1978, 2(3), p 227-238
23. J.M. Joubrt, Crystal Chemistry and Calphad Modeling of the
r Phase, Prog. Mater. Sci., 2008, 53(3), p 528-583
24. A. Davydov and U.R. Kattner, Thermodynamic Assessment of
the Co-Mo System, J. Phase Equilib., 1999, 20(1), p 5-15
25. A. Davydov, Revised Thermodynamic Description for the
Co-Mo System, J. Phase Equilib., 2003, 24(3), p 209-211
26. K. Oikawa, U.R. Kattner, J. Sato, T. Omori, M. Jiang, K.
Anzai, and K. Ishida, Experimental Determination and Ther-
modynamic Assessment of Phase Equilibria in the Co-Mo
System, Mater. Trans., 2012, 53(8), p 1425-1435
27. A. Kusoffsky and B. Jansson, A Themodynamic Evaluation of
the Co-Cr and C-Co-Cr Systems, CALPHAD, 1997, 21(3),
p 321-333
28. K. Oikawa, G.W. Qin, T. Ikeshoji, R. Kainuma, and K. Ishida,
Direct Evidence of Magnetically Induced Phase Separation in
the fcc Phase and Thermodynamic Calculations of Phase
Equilibria of the Co-Cr System, Acta Mater., 2002, 50,
p 2223-2232
29. K.C. HariKumarb, I. Ansara, and P. Wollantsb, Sublattice
Modeling of the l-Phase, CALPHAD, 1998, 22(3), p 324-334
30. J.O. Andersson and N. Lange, An Experimental Study and a
Thermodynamic Evaluation of the Fe-Cr-Mo System, Metal.
Trans. A, 1988, 19, p 1385-1394
31. S.Y. Yang, M. Jiang, H.X. Li, and L. Wang, Thermodynamic
Assessment of Co-Cr-W Ternary System, Trans. Nonferr. Met.
Soc., 2011, 21, p 2270-2275
32. J.O. Andersson, A Thermodynamic Evaluation of the Fe-Mo-C
System, CALPHAD, 1988, 12(1), p 9-23
33. Y. Komura, W.G. Sly, and D.P. Shoemaker, The Crystal Struc-
ture of R Phase, Mo-Co-Cr, Acta Cryst., 1960, 13, p 575-585
34. B. Sundman, B. Jansson, and J.O. Andersson, The Thermo-
Calc Databank System, CALPHAD, 1985, 9(2), p p153-p190
35. A.T. Dinsdale, SGTE Data for Pure Elements, CALPHAD,
1991, 15(4), p p317-p425