Thermodynamic Database
User’s Guide
Copyright © 2000-2013 CompuTherm LLC
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Contents
1. PanAluminum .................................................................................... 1
1.1 Components .................................................................................... 2
1.2 Suggested Composition Range ......................................................... 2
1.3 Phases ............................................................................................. 2
1.4 Key Elements and Subsystems......................................................... 4
1.5 Database Validation ......................................................................... 4
1.6 References ....................................................................................... 8
2. PanCobalt ........................................................................................... 9
2.1 Components .................................................................................. 10
2.2 Suggested Composition Range ....................................................... 10
2.3 Phases ........................................................................................... 10
2.4 Key Elements and Subsystems....................................................... 12
2.5 Database Validation ....................................................................... 12
2.6 References ..................................................................................... 16
3. PanIron ............................................................................................ 17
3.1 Components .................................................................................. 18
3.2 Suggested Composition Range ....................................................... 18
3.3 Phases ........................................................................................... 18
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3.4 Key Elements and Subsystems....................................................... 20
3.5 Database Validation ....................................................................... 20
3.6 References ..................................................................................... 28
4. PanMagnesium ................................................................................. 29
4.1 Components .................................................................................. 30
4.2 Suggested Composition Range ....................................................... 30
4.3 What's new in PanMg2013 ............................................................. 30
4.4 Phases ........................................................................................... 31
4.5 Key Elements and Subsystems....................................................... 33
4.6 Database Validation ....................................................................... 34
4.7 References ..................................................................................... 42
5. PanMolybdenum ............................................................................... 45
5.1 Components .................................................................................. 46
5.2 Suggested Composition Range ....................................................... 46
5.3 Phases ........................................................................................... 46
5.4 Key Elements and Subsystems....................................................... 48
5.5 Database Validation ....................................................................... 49
5.6 Reference ..................................................................................... 544
6. PanNickel ......................................................................................... 55
6.1 Components .................................................................................. 56
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6.2 Suggested Composition Range ....................................................... 56
6.3 Phases ........................................................................................... 56
6.4 Key Elements and Subsystems....................................................... 58
6.5 Database Validation ....................................................................... 59
6.6 References ..................................................................................... 67
7. PanTitanium ..................................................................................... 68
7.1 Components .................................................................................. 69
7.2 Suggested Composition Range ....................................................... 69
7.3 Phases ........................................................................................... 69
7.4 Sub-System Information ................................................................ 70
7.5 Database Validation ....................................................................... 72
7.6 References ..................................................................................... 80
8. PanBMG ........................................................................................... 82
8.1 Components .................................................................................. 83
8.2 Suggested Composition Range ....................................................... 83
8.3 Phases ........................................................................................... 83
8.4 Sub-System Information ................................................................ 85
8.5 Database Validation ....................................................................... 88
8.6 References ..................................................................................... 92
9. ADAMIS ............................................................................................ 93
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9.1 Components .................................................................................. 94
9.2 Suggested Composition Range ....................................................... 94
9.3 Phases ........................................................................................... 94
9.4 Sub-System Information ................................................................ 95
9.5 Database Validation ....................................................................... 98
9.6 Applications ................................................................................. 100
9.7 References ................................................................................... 101
10. MDT Copper ................................................................................... 102
10.1 Components ............................................................................. 103
10.2 Suggested Composition Range ................................................... 103
10.3 Phases ...................................................................................... 103
10.4 Key Elements and Subsystems .................................................. 105
10.5 Database Validation .................................................................. 106
10.6 References ................................................................................ 108
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1. PanAluminum
Thermodynamic database for multi-component Aluminum-rich casting and wrought alloys
Copyright © CompuTherm LLC
Al
Ag B C
Cr
Cu
Fe
Gd
Ge
Hf
Li Mg Mn Ni
Sc
Si
Sn
Sr
Ti
V
Y
Zn Zr
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1.1 Components
Total of 23 components are included in the database as listed here:
Major alloying elements: Al, Cu, Fe, Mg, Mn, Si and Zn
Minor alloying elements: Ag, B, C, Cr, Gd, Ge, Hf, Li, Ni, Sc, Sn, Sr, Ti, V, Y,
and Zr
1.2 Suggested Composition Range
The suggested composition range for each element is listed in Table 1.1. It
should be noted that this comosition range is based on the validation we
performed on commercial alloys. For perticular subsystems, the application
range may be wider. Some subsystems can be applied to the entire
composition arnge as given in section 1.4.
Table 1.1: Suggested composition range
Element Composition Range (wt.%)
Al 80 ~ 100
Cu 0 ~ 5.5
Fe 0 ~ 1.0
Mg 0 ~ 7.6
Mn 0 ~ 1.2
Si 0 ~ 17.5
Zn 0 ~ 8.1
other 0 ~ 0.5
1.3 Phases
Total of 250 phases are included in the database and only a few key phases
are listed in Table 1.2. Information on all the other phases can be found at
www.computherm.com .
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Table 1.2: Phase name and related information
Name Lattice Size Constituent
Al15_FeMn3Si2 (16)(4)(1)(2) (Al)(Fe,Mn)(Si)(Al,Si)
Al60Cu4Mn11 (0.8)(0.05)(0.15) (Al)(Cu)(Mn)
Al6_FeMn (6)(1) (Al)(Fe,Mn)
Al7Cu2Fe (7)(2)(1) (Al)(Cu)(Fe)
Al8FeMg3Si6 (8)(3)(1)(6) (Al)(Mg)(Fe)(Si)
Al8FeMnSi2 (16)(2)(2)(3) (Al)(Fe)(Mn)(Si)
AlMgMn_T (18)(3)(2) (Al)(Mg)(Mn)
AlMgZn_Tau (26)(6)(48)(1) (Mg)(Al,Mg)(Al,Mg,Zn)(Al)
Alpha_AlFeSi (0.66)(0.19)(0.05)(0.1) (Al)(Fe)(Si)(Al,Si)
Beta_AlFeSi (0.598)(0.152)(0.1)(0.15) (Al)(Fe,Mn)(Si)(Al,Si)
Cu16Mg6Si7 (0.551724)(0.206897) (0.241379)
(Cu)(Mg)(Si)
Fcc (1)(1) (Ag,Al,Cu,Fe,Gd,Ge,Li,Mg,Mn,Sc,Si,Sn,Zn,Cr,Ni,Ti,V,Zr,Hf,Sr,Y)(B,C,Va)
LiZn2 (1)(2) (Li)(Zn)
Liquid (1) (Ag,Al,B,C,Cr,Cu,Fe,Gd,Ge,Hf,Li,Mg,Mn,Ni,Sc,Si,Sn,Sr,Ti,V,Y,Zn,Zr)
Mg2Si (2)(1) (Mg)(Ge,Si)
Q (0.4375)(0.375)(0.1875) (Al)(Mg)(Cu)
S (0.5)(0.25)(0.25) (Al)(Mg)(Cu)
T (26)(6)(48)(1) (Mg)(Al,Mg)(Al,Cu,Mg,Zn)(Al)
V (0.38461)(0.15385) (0.46154)
(Al)(Mg)(Cu)
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1.4 Key Elements and Subsystems
Key elements of the system are listed as: Al-Cu-Fe-Mg-Mn-Si-Zn. The
modeling status for the constituent binaries and ternaries of these key
elements are given in Tables 1.3-1.4. The color represents the following
meaning:
: Full description
: Full description for major phases
: Extrapolation
Table 1.3: Modeling status of key constituent binary systems
Cu Fe Mg Mn Si Zn
Al Al-Cu Al-Fe Al-Mg Al-Mn Al-Si Al-Zn
Cu Cu-Fe Cu-Mg Cu-Mn Cu-Si Cu-Zn
Fe Fe-Mg Fe-Mn Fe-Si Fe-Zn
Mg Mg-Mn Mg-Si Mg-Zn
Mn Mn-Si Mn-Zn
Si Si-Zn
Table 1.4: Modeling status of key constituent ternary systems
Fe Mg Mn Si Zn
Al-Cu Al-Cu-Fe Al-Cu-Mg Al-Cu-Mn Al-Cu-Si Al-Cu-Zn
Al-Fe Al-Fe-Mg Al-Fe-Mn Al-Fe-Si Al-Fe-Zn
Al-Mg Al-Mg-Mn Al-Mg-Si Al-Mg-Zn
Al-Mn Al-Mn-Si Al-Mn-Zn
Al-Si Al-Si-Zn
1.5 Database Validation
Phase Diagrams
Figure 1.1 shows the calculated isotherm of Al-Cu-Mg-Zn at 460ºC with Zn
content of 4wt%. The experimental data of Strawbridge, et al. [1948Str] are
plotted on it for comparison.
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Figure 1.1: Comparison of a calculated isothermal section of Al-Cu-Mg-Zn at 4wt%Zn and at
T=460C with the experimental data of Strawbridge, et al. [1948Str]
Figure 1.2: Comparison of a calculated isopleth of Al-Fe-Mg-Si at 4wt.%Mg and 0.5wt.%Fe
with the experimental data
Figure 1.2 shows the calculated isopleth of Al-Fe-Mg-Si at 4wt.%Mg and
0.5wt.%Fe with experimental data from Phillips [1961Phi].
0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0 two-phase region
three-phase region
four-phase region
wt.%
(S
i)
wt.% (Mg)
(Al)+AlCu_
(Al)+
(Si)
+A
lCu
_ (A)+Al
5Cu
2Mg
8Si
6+(Si)+AlCu_
(Al)+Al5Cu
2Mg
8Si
6+AlCu_
(Al)+
Mg 2Si+AlC
u_+Al 5
Cu 2Mg 8
Si 6
(Al)+Mg 2
Si+AlCu_
(Al)+Mg 2
Si+S+AlCu_
(Al)+S+AlCu_
(Al)+Mg2Si+S
0 2 4 6 8 10 12 14
400
450
500
550
600
650 Calculation of this work
DTA measurements
T(o
C)
wt.% (Si)
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Solidification
In addition to the validation of phase equilibria, the current database has
also been subjected to extensive validation of solidification data of
commercial aluminum alloys. Figure 1.3 presents the Scheil model predicted
solidification paths of Al-5Cu-0.5Mg-0.5Ag (wt%) and Al-5Cu-0.5Mg-0.5Ag-
1.2Li (wt%) alloys. It is seen that 1.2 wt% of Li has significant effect on this
Al alloy.
Figure 1.3: Scheil-model predicted solidification paths for two Al-Cu-Mg-Ag-(Li) aluminum
alloys: with or without lithium
Partition Coefficient
This database can also supply important parameters for processing
simulation. One of these parameters is partition coefficient. The calculated
partition coefficients have also been subjected to extensive validation.
Examples for Al-Cu-Mg-Zn quaternary alloys are given below. Figures 1.4
and 1.5 show comparisons between calculated and measured partition
coefficient for Al-4Cu-0.9Mg-2.6Zn (wt%) and Al-2.5Cu-1.3Mg-2.63Zn (wt%),
respectively. The good agreement between the experimental and calculated
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
460
480
500
520
540
560
580
600
620
640
660 Al-5Cu-0.5Mg-0.5Ag (wt.%)
Al-5Cu-0.5Mg-0.5Ag-1.2Li (wt.%)
L=(Al)+Al7CuLi+Al
2CuLi+S+AlMgAg
L=(Al)+Al7CuLi+Al
2CuLi+S
L=(Al)+Al7CuLi+Al
2CuLi
L=(Al)+AlCu_S+AlMgAg
L=(Al)+AlCu_S
T(o
C)
fs
L=(Al) L=(Al)+AlCu_
L=(Al)+Al7CuLi
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results, as shown in these figures, indicates the reliability of the current
PanAluminum thermodynamic database in providing thermodynamic input
for processing simulation.
Figure 1.4: Comparison between the calculated and experimentally determined [1998Lia]
partition coefficients of alloy Al-4wt%Cu-0.9wt%Mg -2.6wt%Zn
Figure 1.5: Comparison between the calculated and experimentally determined [1998Lia]
partition coefficients of alloy Al-2.5wt%Cu-1.3wt%Mg-2.63wt%Zn
Pa
rtitio
n c
oe
ffic
ien
t
Temperature celsius
0.0
0.4
0.8
1.2
1.6
540 560 580 600 620
Temperature_celsius
Pa
rtitio
n c
oe
ffic
ien
t
ALCuMgZn Liang
Partition coefficient of Al-2.5wt%Cu-1.3wt%Mg-2.63wt%Zn
540 560 580 600 6200
0.4
0.8
1.2
1.6
Pa
rtitio
n C
oe
ffic
ien
t
Temperature Celsius
0.0
0.4
0.8
1.2
1.6
520 540 560 580 600 620
Temperature_Celsius
Pa
rtitio
n C
oeffic
ien
tAlZnMgCu Liang
Partition coefficient of Al-4wt%Cu-0.9wt%Mg-2.6wt%Zn
520 540 560 580 600 6200
0.4
0.8
1.2
1.6
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Molar Volume
The molar volume data for the major phases within the PanAl database are
modeled. Figure 1.6 shows the calculated density of the Al-6Mg-2Zn-2Cu-
0.1Zr (wt.%) from 650oC to room temperature using line calculation.
Figure 1.6: Calculated density of the Al-6Mg-2Zn-2Cu-0.1Zr (wt.%) using line calculation
1.6 References
[1948Str] Strawbridge D.J., Hume-Rothery W. and Little A. .: J. Inst. Metals 74, 191–225 (1948).
[1961Phi] Phillips H.W.L., Equilibrium diagrams of aluminum alloy systems, The aluminum development association, Information bul, London, Dec. 25, 1961, pp: 105-108
[1998Lia] Liang, P., Tarfa, T., Robinson, J.A., Wagner, S., Ochin, P., Harmelin, M.G., Seifert, H.J., Lukas, H.L., Aldinger, F.,
Experimental investigation and thermodynamic calculation of the Al-Mg-Zn system, Thermochim. Acta 314, 87-110 (1998).
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2. PanCobalt
Thermodynamic Database for Cobalt-Based Superalloys
Copyright © CompuTherm LLC
Co
Al B
C
Cr
Fe
Mo Ni
Pt
Re
Ta
W
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2.1 Components
Total of 12 components are included in the database as listed here:
Major alloying elements: Al, Co, Cr, Fe, Mo, Ni, Pt, Re, Ta, and W
Minor alloying elements: B and C
2.2 Suggested Composition Range
The suggested composition range for each element is listed in Table 2.1. It
should be noted that this comosition range is based on the validation we
performed on commercial alloys. For perticular subsystems, the application
range may be wider. Some subsystems can be applied to the entire
composition range as given in Table 2.4.
Table 2.1: Suggested composition range
Element Composition range (wt.%)
Co 50-100
Al 0-50
B, C 0-10
Cr 0-30
Mo 0-20
Ni 0-100
Fe 0-20
Pt, Re 0-20
Ta 0-20
W 0-20
2.3 Phases
Total of 126 phases are included in the current database. The names and
thermodynamic models of the major phases are given in Table 2.2.
Information on all the other phases can be found at www.computherm.com .
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Table 2.2: Phase name and related information
Name Lattice Size Constituent
B2 (1)(1) (Al,Co,Cr,Fe,Mo,Ni,Re,Ta,W) (Co,Cr,Fe,Mo,Ni,Re,Ta,W,Va)
Bcc (1)(3) (Al,Co,Cr,Fe,Mo,Ni,Re,Ta,W)(Va)
Chi (24)(10)(24) (Cr,Fe,Mo,Ni,Re)(Cr,Mo,Re,Ta,W) (Cr,Fe,Ni,Re,Ta,W)
Disorder (1) (Al,Co,Cr,Fe,Mo,Ni,Re,Ta,W)
Fcc (1)(1) (Al,Co,Cr,Fe,Mo,Ni,Re,Ta,W)(Va)
Hcp (1)(0.5) (Al,Co,Cr,Fe,Mo,Ni,Re,Ta,W)(Va)
L12 (0.75)(0.25) (Al,Co,Cr,Fe,Mo,Ni,Re,Ta,W) (Al,Co,Cr,Fe,Mo,Ni,Re,Ta,W)
Laves_C14 (2)(1) (Al,Co,Cr,Fe,Mo,Ni,Ta)(Al,Co,Cr,Fe,Mo,Ni,Ta,W)
Laves_C15 (2)(1) (Al,Co,Cr,Ni,Ta)(Co,Mo,Ta)
Laves_C36 (2)(1) (Al,Co,Ta)(Co,Mo,Ta)
Liquid (1) (Al,Co,Cr,Fe,Mo,Ni,Re,Ta,W)
Mu (7)(2)(4) (Al,Co,Cr,Fe,Mo,Ni,Ta,W)(Mo,Ta,W) (Co,Cr,Fe,Mo,Ta,W)
NiMo (24)(20)(12) (Co,Ni)(Al,Co,Mo,Ni,Ta,W)(Mo,Ta,W)
R_Phase (27)(14)(12) (Co,Cr,Fe,Mo,W)(Cr,Mo,W)(Co,Cr,Fe,Mo,W)
Sigma (8)(4)(18) (Al,Co,Cr,Fe,Ni,Re,Ta,W)(Cr,Fe,Mo,Ta,W) (Al,Co,Cr,Fe,Mo,Ni,Re,Ta,W)
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2.4 Key Elements and Subsystems
Key elements of the system are listed as: Co-Al-Cr-Fe-Mo-Ni-Re-Ta-W. The
current modeling status for the constituent binaries and ternaries are given
in Tables 2.3-2.4. The color represents the following meaning:
: Full description
: Full description for major phases
: Extrapolation
Table 2.3: Key binary systems for the Co-Al-Cr-Fe-Mo-Ni-Re-Ta-W System
Co Cr Fe Mo Ni Re Ta W
Al Al-Co Al-Cr Al-Fe Al-Mo Al-Ni Al-Re Al-Ta Al-W
Co Co-Cr Co-Fe Co-Mo Co-Ni Co-Re Co-Ta Co-W
Cr Cr-Fe Cr-Mo Cr-Ni Cr-Re Cr-Ta Cr-W
Fe Fe-Mo Fe-Ni Fe-Re Fe-Ta Fe-W
Mo Mo-Ni Mo-Re Mo-Ta Mo-W
Ni Ni-Re Ni-Ta Ni-W
Re Re-Ta Re-W
Ta Ta-W
Table 2.4: Key Ternary Systems for the Co-Al-Cr-Fe-Mo-Ni-Re-Ta-W System
Cr Fe Mo Ni Ta W
Co-Al Co-Al-Cr Co-Al-Fe Co-Al-Mo Co-Al-Ni Co-Al-Ta Co-Al-W
Co-Cr Co-Cr-Fe Co-Cr-Mo Co-Cr-Ni Co-Cr-Ta Co-Cr-W
Co-Fe Co-Fe-Mo Co-Fe-Ni Co-Fe-Ta Co-Fe-W
Co-Ni Co-Ni-Mo Co-Ni-Ta Co-Ni-W
2.5 Database Validation
The current thermodynamic database for cobalt alloys has been extensively
tested and validated using the published experimental data [2008Ish,
2008Shi]. Some sub-quaternary systems of this database have been critically
assessed: Co-Al-Ni-W, Co-Al-Cr-Ni, but not published yet.
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Figure 2.1 and Figure 2.2 show two calculated isopleth in the Co-Al-Ni-W
quaternary system compared with the experimental data [2008Ish, 2008Shi].
The isopleth in Figure 2.1 is a vertical section at 10 at% of Al and 7.5 at% of
W and that in Figure 2.2 is at 10 at.% of Al and 10 at.% of W. In both
figures, the calculated phase boundaries are in good agreement with the
experimental data. Figure 2.3 and 2.4 show two calculated isothermal
sections with Ni content at 60 at% at 1100oC and 1000oC, respectively. The
calculated results agree well with the experimental observations from anneal
alloy samples [2006Bur]. Figure 2.5 show the comparison between the
calculated liquidus, solidus and ˊ solvus temperatures and the
experimentally measured ones.
Figure 2.1: Calculated ˊ solvus and solidus temperatures of Co-xNi-10Al-7.5W alloys
compared with experiments
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Figure 2.2: Calculated ˊ solvus and solidus temperatures of Co-xNi-10Al-10W alloys
compared with experiments
Figure 2.3: Calculated 1100oC isothermal section of Ni-Al-Cr-Co system with fixed Ni
content at 60 at.% compared with experimental observations
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Figure 2.4: Calculated 1000oC isothermal section of Ni-Al-Cr-Co system with fixed Ni
content at 60 at.% compared with experimental observations
900 1000 1100 1200 1300 1400 1500 1600
900
1000
1100
1200
1300
1400
1500
1600
Ca
lcu
late
d T
em
pe
ratu
re (
oC
)
Experimental Temperature (oC)
Liquidus
solidus
' solvus
Figure 2.5: Comparison between calculated results and experimental data for Liquidus,
solidus and ˊ solvus temperatures.
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2.6 References
[2006Bur] J. Bursik, P. Broz, J. Popovic, "Microstructure and phase equilibria in Ni-Al-Cr-Co alloys", Intermetallics, 2006, 14, 1257-
1261.
[2008Ish] K. Ishida, "Intermetallic Compounds in Co-base alloys - Phase
Stability and Application to Superalloys", MRS proceedings, 2008, vol. 1128.
[2008Shi] K. Shinagawa et al., "Phase Equilibria and Microstructure on g'
Phase in Co-Ni-Al-W System", Materials Transactions, 2008, 49(6), 1474-1479.
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3. PanIron
Thermodynamic database for multi-component Fe-rich alloys
Copyright © CompuTherm LLC
Fe
Al B C
Co
Cr
Cu
Mg
Mn
Mo N Nb Ni
P
S
Si
Sn
Ti
V
W Zr
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3.1 Components
Total of 21 components are included in the database as listed here:
Major alloy elements: Co, Cr, Fe, Mo, Ni, V and W
Minor alloy elements: Al, B, C, Cu, Mg, Mn, N, Nb, P, S, Si, Sn, Ti and Zr
3.2 Suggested Composition Range
The suggested composition range for each element is listed in Table 3.1. It
should be noted that this comosition range is based on the validation we
performed on commercial alloys. For perticular subsystems, the application
range may be wider. Some subsystems can be applied to the entire
composition range as given in section 3.4.
Table 3.1: Suggested composition range
Elements Composition Range (wt.%)
Fe 50 ~ 100
Ni 0 ~ 31
Cr 0 ~ 27
Co, Mo 0 ~ 10
V, W 0 ~ 7
B, C, Cu, Mn, Nb, Si, Ti 0 ~ 4
Al, Mg, N 0 ~ 0.5
P, S, Sn, Zr 0 ~ 0.05
3.3 Phases
Total of 318 phases are included in the database and a few key phases are
listed in Table 3.2. Information on all the other phases can be found at
www.computherm.com .
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Table 3.2: Phase name and related information
Name Lattice Size Constituent
Bcc (ferrite)
(1)(3) (Al,B,Co,Cr,Cu,Fe,Mg,Mn,Mo,Nb,Ni,P,S,Si,Sn,Ti, V,W,Zr)(B,C,N,Va)
Cementite (3)(1) (Co,Cr,Fe,Mn,Mo,Nb,Ni,V,W)(B,C,N)
Fcc (austenite)
(1)(1) (Al,B,Co,Cr,Cu,Fe,Mg,Mn,Mo,Nb,Ni,P,S,Si,Sn,Ti, V,W,Zr)(B,C,N,Va)
Fcc_MC (1)(1) (Al,B,Co,Cr,Cu,Fe,Mg,Mn,Mo,Nb,Ni,P,S,Si,Sn,Ti, V,W,Zr)(B,C,N,Va)
Graphite (1) (B,C)
Hcp (1)(0.5) (Al,B,Co,Cr,Cu,Fe,Mg,Mn,Mo,Nb,Ni,Si,Sn,Ti,V, W,Zr)(B,C,N,Va)
Laves_C14 (2)(1) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Ti,W,Zr) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Ti,W,Zr)
Liquid (1) (Al,B,C,Co,Cr,Cu,Fe,Fe1Si1,Mg,Mn,Mn1Si1,Mo, N,Nb,Ni,P,S,Si,Sn,Ti,V,W,Zr)
M23C6 (20)(3)(6) (Co,Cr,Fe,Mn,Ni,V)(Co,Cr,Fe,Mn,Mo,Ni,V,W) (B,C)
M3C2 (3)(2) (Cr,Mo,V,W)(C)
M5C2 (5)(2) (Fe,Mn,V)(C)
M5Si3 (0.625)(0.375) (Cr,Fe,Mn,Mo,W)(Si)
M6C (2)(2)(2)(1) (Co,Fe,Ni)(Mo,Nb,W)(Co,Cr,Fe,Mo,Nb,Ni,V,W) (C)
M7C3 (7)(3) (Co,Cr,Fe,Mn,Mo,Ni,V,W)(C)
Mu_PHASE (7)(2)(4) (Al,Co,Cr,Fe,Mo,Mn,Nb,Ni)(Mo,Nb,W)(Al,Co,Cr, Fe,Mo,Nb,Ni,W)
P_PHASE (24)(20)(12) (Cr,Fe,Ni)(Cr,Fe,Mo,Ni)(Mo)
R_PHASE (27)(14)(12) (Co,Cr,Fe,Mn,Ni)(Mo,W)(Co,Cr,Fe,Mn,Mo,Ni,W)
Sigma (8)(4)(18) (Al,Co,Fe,Mn,Ni,Si)(Cr,Mo,Nb,V,W)(Al,Co,Cr,Fe, Mn,Mo,Nb,Ni,Si,V,W)
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3.4 Key Elements and Subsystems
Key elements of the system are listed as: Co-Cr-Fe-Mo-Ni-V-W. The modeling
status for the constituent binaries and ternaries of these key elements are
given in Tables 3.3-3.4. The color represents the following meaning:
: Full description
: Full description for major phases
: Extrapolation
Table 3.3: Key binary systems for the Co-Cr-Fe-Mo-Ni-V-W
Cr Fe Mo Ni V W
Co Co-Cr Co-Fe Co-Mo Co-Ni Co-V Co-W
Cr Cr-Fe Cr-Mo Cr-Ni Cr-V Cr-W
Fe Fe-Mo Fe-Ni Fe-V Fe-W
Mo Mo-Ni Mo-V Mo-W
Ni Ni-V Ni-W
V V-W
Table 3.4: Key ternary systems for the major components
3.5 Database Validation
The current thermodynamic database for iron-based alloy systems has been
extensively tested and validated using the published experimental data.
Co Cr Mo Ni W
Fe-B Fe-B-Co Fe-B-Cr Fe-B-Mo Fe-B-Ni Fe-B-W
Fe-C Fe-C-Co Fe-C-Cr Fe-C-Mo Fe-C-Ni Fe-C-W
Fe-Co Fe-Co-Cr Fe-Co-Mo Fe-Co-Ni Fe-Co-W
Fe-Cr Fe-Cr-Mo Fe-Cr-Ni Fe-Cr-W
Fe-Mo Fe-Mo-Ni Fe-Mo-W
Fe-Ni Fe-Ni-W
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Phase Diagram
This database can be used to calculate phase equilibria for multi-component
iron alloys, such as the equilibrium between Bcc (ferrite) and Fcc (austenite).
It can be used to predict phase transformation temperatures, such as
liquidus, solidus, and so on. The fraction of each phase as a function of
temperature, partitioning of components in different phases can also be
calculated. In addition to equilibrium calculations, Scheil simulations can
also be carried out using this database. Some validation results are
presented in Figures 3.1 to 3.4.
Figure 3.1 shows comparison between the calculated and experimentally
measured liquidus and solidus temperatures for variety of steels. Figure 3.2
shows comparison between the calculated and experimentally observed
amounts of austenite in duplex stainless steels. Figure 3.3 is a comparison
between the calculated and experimentally measured partitioning of Fe, Cr,
Mo, and Ni in ferrite and austenite. Figures 3.4a to 3.4e are comparisons
between the calculated and experimentally observed equilibrium
compositions for Fe, C, Cr, Mo, Si, V and W in austenite, ferrite and M6C,
respectively. These figures show reasonable agreement between the
calculated values using PanIron and the experimental determined ones.
CompuTherm LLC Thermodynamic Databases
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Figure 3.1: Comparison between the calculated and experimentally measured liquidus and
solidus temperatures for iron-based alloys with experimental data from [1977Jer]
Figure 3.2: Comparison between the calculated and experimentally measured amounts of
austenite (Fcc)
1200
1300
1400
1500
1600
1200 1300 1400 1500 1600
Measured (oC)
Calc
ula
ted
(oC
)
liquidus
solidus
Diagonal
0
20
40
60
80
100
0 20 40 60 80 100
Measured %
Ca
lcu
late
d %
83Mae
85Hay
85Tho
91Lon
94Lon
94Bon
94Nys
Diagonal
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Figure 3.3: Comparison between the calculated and experimentally measured partitioning of
Fe, Cr, Mo and Ni in ferrite and austenite
Figure 3.4(a): Comparison between the calculated and measured equilibrium composition of
Fe in the Fcc (austenite) phase
0
0.4
0.8
1.2
1.6
2
0 0.4 0.8 1.2 1.6 2
Measured
Ca
lcu
late
d
85Hay
91Cor
90Hay
91Mer
94Ham
Diagonal
88
89
90
91
92
93
94
88 89 90 91 92 93 94
Measured
Calc
ula
ted
diagonal
Fe
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Figure 3.4(b): Comparison between the calculated and measured equilibrium compositions
of C, Cr, and Mo in the Fcc (austenite) phase
Figure 3.4(c): Comparison between the calculated and measured equilibrium compositions
of Si, V and W in the Fcc (austenite) phase
0
1
2
3
4
5
6
0 1 2 3 4 5 6Measured
Calc
ula
ted
diagonal
C
Cr
Mo
0
0.5
1
1.5
2
0 0.5 1 1.5 2Measured
Calc
ula
ted
diagonal
Si
V
W
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Figure 3.4(d): Comparison between the calculated and measured equilibrium compositions
of Cr, Mo, Si, V and W in the Bcc (ferrite) phase
Figure 3.4(e): Comparison between the calculated and measured equilibrium compositions
of Cr, Mo, Fe, V and W in the M6C phase
0
1
2
3
4
5
6
0 1 2 3 4 5 6Measured
Calc
ula
ted
diagonal
Cr
Mo
Si
V
W
0
10
20
30
40
50
60
0 10 20 30 40 50 60
Measured
Calc
ula
ted
diagonal
Cr
V
W
Fe
Mo
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Molar Volume
The molar volume data for the Bcc and Fcc crystal structure of each
elements within the PanFe database are modeled. Figure 3.1 shown the
calculated molar volume of pure iron vs. temperature comparing with
experimental data [1957Gol, 1995Bas]
Figure 3.5: Comparison between the calculated and experimental measured molar volume of
pure iron vs. temperature
The molar volumes of Bcc and Fcc phases in the Fe-X binaries were also
obtained. Figure 3.6 shows the calculated molar volume of both Bcc and Fcc
phases within the Fe-Ni binary system vs. temperature. Comparisons
between calculated and experimental data [1972Mas, 1973Gup and
2005Mis] show good agreement.
One of the most important applications of the molar volume database is to
calculate the relative length change of iron-based alloys during casing
and/or heat-treatment processing. The comparison between the calculated
7.0e-06
7.1e-06
7.2e-06
7.3e-06
7.4e-06
0 200 400 600 800 1000 1200
Temperature [oC]
Vm
[m
3
/mole
_ato
m
s]
austenite
ferrite
Calculated Vm for pure Fe of this workExperimental data [55Bas,57Gol]
Transformation temperature is 910oC
0 200 400 600 800 1000 12007.05e-006
7.15e-006
7.25e-006
7.35e-006
7.45e-006
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and experimentally measured relative length change of SAE5120 alloy is
shown in figures 3.7 and good agreements are obtained.
Figure 3.6: Comparison between the calculated and experimental measured molar volume of
both BCC and Fcc phases of the Fe-Al binary system vs. Temperature
Figure 3.7: Comparison between the calculated and experimentally measured relative length
change of SAE5120 alloy
6.3e-06
6.4e-06
6.5e-06
6.6e-06
6.7e-06
6.8e-06
6.9e-06
7.0e-06
7.1e-06
7.2e-06
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
fcc-Fe
This work at 873KThis work at 673KThis work at 473KThis work at 298K1972Mas1972Mas1972Mas2005Mis
Fe NiMol. Fracn. Ni
Vm
[m
3
/mo
le_ato
m
s]
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 16.3e-006
6.4e-006
6.5e-006
6.6e-006
6.7e-006
6.8e-006
6.9e-006
7e-006
7.1e-006
7.2e-006
6.6e-06
6.7e-06
6.8e-06
6.9e-06
7.0e-06
7.1e-06
7.2e-06
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
bcc-Fe
This work at 298KThis work at 673K2005Mis1973Gup
Fe NiMol. Fracn. Ni
Vm
[m
3
/mole
_ato
m
s]
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 16.6e-006
6.7e-006
6.8e-006
6.9e-006
7e-006
7.1e-006
7.2e-006
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
100 200 300 400 500 600 700 800 900 1000 1100
Temperature [oC]
L/L
Calculation of this workSAE 5120 heating dilatation curve
100 200 300 400 500 600 700 800 900 1000 11000
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
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3.6 References
[1957Gol] H.J. Goldschmidt, JISI, 186 (1957), 68-78
[1973Gup] A. Sen Gupta, Technology, 9(4) (1973), pp: 280
[1977Jer] Jernkontoret, A Guide to the Solidification of Steels. Jernkontoret, Stockholm, (1977).
[1983Mae] Y. Maehara, Y. Ohmori, J. murayama, N. Fujino and T. Kunitake, Metal Science, 17 (1983), 541-547.
[1984Tho] T. Thorvaldsson, H. Eriksson, J. Kutka and A. Salwen, in Proceedings of the Conference for Stainless Steels, Goteborg, Sweden, (1984) 101-105.
[1985Hay] F. H. Hayes, J. Less Common Metals, 14 (1985) 89-96.
[1991Cor] M. B. Cortie and J. H. Potgieter, Met. Trans., 22A (1991) 2173-
2179.
[1991Lon] R. D. Longbottom and F. H. Hayes, in User Aspects of Phase Diagram, The Institute of Metals, London, (1991) 32-39.
[1991Wis] H. Wisell, Met. Trans., 22A (1991) 1391-1405.
[1994Nys] M. Nystrom and B. Karlsson, in Proceedings of the Conference for Duplex Stainless Steels’94, Welding Institute, Cambridge, (1994) 104.
[1995Bas] Z.S. Basinski et al., Proc. Roy. Soc. A229, (1995), pp: 459-467
[2005Mis] Y. Mishin, M.J. Mehl, D.A. Papaconstantopoulos, Acta Materialia, 53(2005), pp: 4029
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4. PanMagnesium
Thermodynamic database for multi-component magnesium-rich casting and wrought alloys
Copyright © CompuTherm LLC
CompuTherm LLC Thermodynamic Databases
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4.1 Components
Total of 21 components are included in the database as listed here:
Major components: Al, Ca, Ce, Cu, Gd, La, Li, Mg, Mn, Nd, Si, Sn, Sr, Y, Zn
Minor components: Ag, Fe, Ni, Sc, and Zr
Trace component: C
4.2 Suggested Composition Range
The suggested composition range for each element is listed in Table 4.1. It
should be noted that this composition range is based on the validation we
performed on commercial alloys. For particular subsystems, the application
range may be wider. Many subsystems can be applied to the entire
composition range as given in section 4.5.
Table 4.1: Suggested composition range
Element Composition Range (wt%)
Mg 75~100
Al, Ca, Ce, Cu, Gd, La, Li, Mn, Nd, Si, Sn, Sr, Y, Zn 0~10
Ag, Fe, Ni, Sc, Zr 0~2
C 0~0.5
4.3 What's new in PanMg2013
Improvements in PanMg2013 compared to the previous version PanMg2012
focused on extended modeling depth in descriptions concerning mutual
interactions of components in multicomponent alloys, without adding new
components.
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Key improvements include:
Gas phase description is added with thermodynamic descriptions of
atomic and molecular species formed from all the 21 components,
enabling pressure dependent phase equilibrium calculations.
Thorough revision of all phase names in the database following strict
and consistent rules set for stoichiometric and solution phases. A
complete list of phase names in PanMg2013 compared to PanMg2012
is provided on demand. In addition, chemical symbols are converted
from all upper case to intuitive case sensitive spelling (MG Mg), also
in all the phase names (AL18MG3MN2 Al18Mg3Mn2). Together with
the new assignment of "phase category" the readability and recognition
of the actual phases in Pandat labeling and legends is significantly
enhanced.
Four substantially improved binary system descriptions
Four substantially improved ternary system descriptions
A large number of solid solution phases with ternary and higher
composition are unified from separate phase descriptions to a unique
phase description comprising phases with the same crystal structure.
That has resulted in a decrease (!) of the number of assessed phases
from 445 to 442 phases, whereas the modeling depth was significantly
improved. That enables more realistic calculations involving
multicomponent alloy systems.
4.4 Phases
Total of 442 phases are included in the database. The phase names are
selected according to the following strict rules in Table 4.2 for consistent and
intuitive phase identification in different categories. Information on all the
other phases can be found at www.computherm.com .
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Table 4.2: Selected Phase names and related information
Name Lattice Size Constituent
Liquid (1) (Ag,Al,C,Ca,Ca2Sn,Ce,Cu,Fe,Gd,La,Li,Mg,Mg2Sn,Mn,Nd,Ni,Sc,Si
,Sn,Sr,Y,Zn,Zr)
AgMg4 (0.2)(0.8) (Ag,Cu)(Al,Mg)
Al12Mg17 (10)(24)(24) (Mg)(Al,Ca,Cu,Li,Mg,Zn)(Al,Cu,Mg,Zn)
Bcc (1) (Ag,Al,Ca,Ce,Cu,Fe,Gd,La,Li,Mg,Mn,Nd,Ni,Sc,Si,Sn,Sr,Y,Zn,Zr)
CuMg2 (1)(2) (Cu,Ni)(Mg)
Fcc (1) (Ag,Al,Ca,Ce,Cu,Fe,Gd,La,Li,Mg,Mn,Nd,Ni,Sc,Si,Sn,Sr,Y,Zn,Zr)
Hcp (1) (Ag,Al,Ca,Ce,Cu,Fe,Gd,La,Li,Mg,Mn,Nd,Ni,Sc,Si,Sn,Sr,Y,Zn,Zr)
Mg17Sr2 (17)(2) (Al,Mg)(Ca,Sr)
Mg23Sr6 (23)(6) (Al,Mg)(Sr)
Mg24Y5 (24)(5) (Mg)(Ce,Gd,Mg,Y)
Mg2M (0.5)(0.25)(0.25) (Mg)(Sn,Si)(VA,Li)
Mg2Ni (2)(1) (Mg)(Cu,Ni)
Mg2Y_C14 (2)(1) (Mg)(Ce,Gd,Nd,Y)
Mg2Zn11 (5)(6)(2) (Al,Zn)(Cu,Zn)(Mg)
Mg2Zn3 (2)(3) (Mg)(Al,Cu,Zn)
Mg38Sr9 (38)(9) (Al,Mg)(Ca,Sr)
Mg3YZn6_I (3)(1)(6) (Mg)(Y)(Mg,Zn)
MgYZn2_W (0.25)(0.25)(0.5) (Mg)(Y)(Mg,Zn)
MgZn (12)(13) (Mg)(Al,Cu,Zn)
MgZn2_C14 (1)(2) (Al,Cu,Mg,Ni,Si,Zn)(Al,Cu,Li,Mg,Ni,Si,Zn)
MgZn2_C36 (1)(2) (Al,Cu,Mg,Ni,Si,Zn)(Al,Cu,Mg,Ni,Si,Zn)
RMg12 (1)(12) (Ce,La,Nd,Y)(Al,Mg,Zn)
RMg12Zn_14
H (12)(1)(1) (Mg)(Gd,Y)(Zn)
RMg2_C15 (0.666667)(0.333333) (Al,Cu,Mg,Zn)(Ce,Gd,La,Nd,Y)
RMg3 (1)(3) (Ce,Gd,La,Nd,Y)(Li,Mg,Zn)
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4.5 Key Elements and Subsystems
The modeling status for the constituent binaries and ternaries is given in
Tables 4.3-4.6. All binary systems for the 20 component-subset, excluding
carbon, are listed in Table 4.3. Thermodynamic descriptions for ternary
systems containing Mg are listed in Tables 4.4-4.5. Additionally, ternary
non-Mg-containing systems are listed in Table 4.6.
The color represents the following meaning:
: Full description
: Full description for major phases
: Extrapolation
Table 4.3: Binary Systems of the PanMg database components (no C)
Al Ca Ce Cu Fe Gd La Li Mg Mn Nd Ni Sc Si Sn Sr Y Zn Zr
Ag Ag-Al Ag-Ca Ag-Ce Ag-Cu Ag-Fe Ag-Gd Ag-La Ag-Li Ag-Mg Ag-Mn Ag-Nd Ag-Ni Ag-Sc Ag-Si Ag-Sn Ag-Sr Ag-Y Ag-Zn Ag-Zr
Al Al-Ca Al-Ce Al-Cu Al-Fe Al-Gd Al-La Al-Li Al-Mg Al-Mn Al-Nd Al-Ni Al-Sc Al-Si Al-Sn Al-Sr Al-Y Al-Zn Al-Zr
Ca Ca-Ce Ca-Cu Ca-Fe Ca-Gd Ca-La Ca-Li Ca-Mg Ca-Mn Ca-Nd Ca-Ni Ca-Sc Ca-Si Ca-Sn Ca-Sr Ca-Y Ca-Zn Ca-Zr
Ce Ce-Cu Ce-Fe Ce-Gd Ce-La Ce-Li Ce-Mg Ce-Mn Ce-Nd Ce-Ni Ce-Sc Ce-Si Ce-Sn Ce-Sr Ce-Y Ce-Zn Ce-Zr
Cu Cu-Fe Cu-Gd Cu-La Cu-Li Cu-Mg Cu-Mn Cu-Nd Cu-Ni Cu-Sc Cu-Si Cu-Sn Cu-Sr Cu-Y Cu-Zn Cu-Zr
Fe Fe-Gd Fe-La Fe-Li Fe-Mg Fe-Mn Fe-Nd Fe-Ni Fe-Sc Fe-Si Fe-Sn Fe-Sr Fe-Y Fe-Zn Fe-Zr
Gd Gd-La Gd-Li Gd-Mg Gd-Mn Gd-Nd Gd-Ni Gd-Sc Gd-Si Gd-Sn Gd-Sr Gd-Y Gd-Zn Gd-Zr
La La-Li La-Mg La-Mn La-Nd La-Ni La-Sc La-Si La-Sn La-Sr La-Y La-Zn La-Zr
Li Li-Mg Li-Mn Li-Nd Li-Ni Li-Sc Li-Si Li-Sn Li-Sr Li-Y Li-Zn Li-Zr
Mg Mg-Mn Mg-Nd Mg-Ni Mg-Sc Mg-Si Mg-Sn Mg-Sr Mg-Y Mg-Zn Mg-Zr
Mn Mn-Nd Mn-Ni Mn-Sc Mn-Si Mn-Sn Mn-Sr Mn-Y Mn-Zn Mn-Zr
Nd Nd-Ni Nd-Sc Nd-Si Nd-Sn Nd-Sr Nd-Y Nd-Zn Nd-Zr
Ni Ni-Sc Ni-Si Ni-Sn Ni-Sr Ni-Y Ni-Zn Ni-Zr
Sc Sc-Si Sc-Sn Sc-Sr Sc-Y Sc-Zn Sc-Zr
Si Si-Sn Si-Sr Si-Y Si-Zn Si-Zr
Sn Sn-Sr Sn-Y Sn-Zn Sn-Zr
Sr Sr-Y Sr-Zn Sr-Zr
Y Y-Zn Y-Zr
Zn Zn-Zr
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Table 4.4: All Ternary Systems for the Mg-Al-Ca-Ce-Li-Mn-Si-Zn subset
Ca Ce Li Mn Si Zn
Mg-Al Mg-Al-Ca Mg-Al-Ce Mg-Al-Li Mg-Al-Mn Mg-Al-Si Mg-Al-Zn
Mg-Ca Mg-Ca-Ce Mg-Ca-Li Mg-Ca-Mn Mg-Ca-Si Mg-Ca-Zn
Mg-Ce Mg-Ce-Li Mg-Ce-Mn Mg-Ce-Si Mg-Ce-Zn
Mg-Li Mg-Li-Mn Mg-Li-Si Mg-Li-Zn
Mg-Mn Mg-Mn-Si Mg-Mn-Zn
Mg-Si Mg-Si-Zn
Table 4.5: Additional selected ternary Mg-Systems
Mg-Ag-Al Mg-Ag-Cu Mg-Al-Cu Mg-Al-Gd Mg-Al-Sc Mg-Al-Sn Mg-Al-Sr
Mg-Ca-Ce Mg-Ca-Sn Mg-Ca-Sr Mg-Cu-Li Mg-Cu-Si Mg-Cu-Y Mg-Cu-Zn
Mg-Li-Gd Mg-Mn-Gd Mg-Mn-Sc Mg-Mn-Y Mg-Mn-Zr Mg-Si-Sn Mg-Y-Zn
Mg-Y-Zr Mg-Al-Y Mg-Ce-Zn Mg-Ce-Nd Mg-Ce-Sn Mg-Gd-Zn Mg-Nd-Zn
Table 4.6: Additional selected ternary non-Mg-Systems
Ag-Al-Cu Al-Ca-Ce Al-Ca-Fe Al-Ca-Li Al-Ca-Si Al-Ca-Sr Al-Ce-Gd Al-Ce-Nd
Al-Ce-Si Al-Ce-Y Al-Cu-Li Al-Cu-Mn Al-Cu-Nd Al-Cu-Si Al-Cu-Sn Al-Cu-Zn
Al-Fe-Mn Al-Fe-Si Al-Gd-Nd Al-Gd-Y Al-Li-Mn Al-Li-Si Al-Mn-Sc Al-Cu-Gd
Al-Mn-Si Al-Nd-Y Al-Si-Y Al-Si-Zn Al-Sn-Zn Ca-Fe-Si Ca-Li-Si
Ca-Sr-Zn Cu-Fe-Si Cu-Sn-Zn Fe-Mg-Si Fe-Mn-Si Mn-Y-Zr
4.6 Database Validation
The early development of the Mg-database, starting in 1995, is described in
[2001Sch] and aspects of quality assurance were first given by [2005Sch].
Progress in systematic development of the current thermodynamic database
for Mg alloys is reported in [2012Sch]. Models for multicomponent alloys are
built in a methodical approach from quantitative descriptions of unary,
binary and ternary subsystems. For a large number of ternary—and some
CompuTherm LLC Thermodynamic Databases
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higher—alloy systems, an evaluation of the modeling depth is made with
concise reference to experimental work validating these thermodynamic
descriptions. A special focus is on ternary intermetallic phase compositions.
These comprise solutions of the third component in a binary compound as
well as truly ternary solid solution phases, in addition to the simple ternary
stoichiometric phases. Concise information on the stability ranges is given.
That evaluation is extended to selected quaternary and even higher alloy
systems. Thermodynamic descriptions of intermetallic solution phases
guided by their crystal structure are also elaborated and the diversity of
such unified phases is emphasized [2012Sch].
Key issues in this large thermodynamic Mg alloy database are consistency,
coherency and quality assurance. These issues and the basic concept are
elaborated in [2013Gro]. The structurally supported modeling, especially of
pertinent solid phases, requires proper consideration of multicomponent
solid solutions of intermetallic phases which are abundant in magnesium
alloys. Moreover, evidence on the database application by predicting phase
formation during solidification or heat treatment in advanced
multicomponent magnesium alloys from thermodynamic calculations is
given in detail in [2013Gro].
The growing modeling depth of the PanMagnesium database enhances
predictive type calculations of phase formation during solidification, heat
treatment or other processing steps of Mg alloys. Evidence is given by
comparing the results of such calculations with the phase formation
reported in studies of advanced magnesium alloys, such as Mg—Zn--
Y/Zr/Gd/Ce/Nd, Mg—Al—Ca/Mn/Sr/Sn, Mg—Sn—Ca and higher order
Mg—Al—Sn—Ca/Sr and Mg—Sn—Ca--Ce/Gd/Zr alloys [2013Gro].
Reference is made to the extensive material provided in that most current
publication which is not repeated here.
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The current thermodynamic database for magnesium alloys has also been
extensively tested and validated using published experimental data [1998Lia,
1999Gro, 2001Gro4, 2001Gro6, 2001Kev1, 2001Kev2, 2001Kev3, 2002Gro1,
2002Gro2, 2003Gro1, 2003Gro2, 2004Bru, 2004Kev, 2004Gro, 2006Ohn4].
Some sub-quaternary systems of this database have been critically assessed:
Mg-Al-Ca-Ce, Mg-Al-Ca-Li, Mg-Al-Ce-Li, Mg-Al-Cu-Zn, Mg-Mn-Y-Zr. The
quaternary systems Mg-Al-Li-Si [2001Kev4] and Mg-Ce-Mn-Sc, Mg-Gd-Mn-
Sc, Mg-Mn-Sc-Y [2000Pis2, 2001Gro2] were thermodynamically modeled and
used for technical applications.
Figure 4.1: Invariant temperatures for various ternary alloys included in PanMagnesium:
Comparison between calculated and experimental data.
For the reliability of the calculated phase diagrams the fitting of the invariant
temperatures are of paramount importance. Since the measured
temperatures of the invariant reactions are not affected by super-cooling
related problems, these nonvariant data are perfect criteria for comparison of
experimental with calculated data (Figure 4.1).
400 600 800 1000 1200 1400
400
600
800
1000
1200
1400
MgLiGd MgLiSi AlCaSi AlLiSi
MgAlCa MgAlCe MgAlGd MgAlMn MgAlSc MgAlZn MgCaSi
Calc
ula
ted invariant
Tem
pera
ture
(°C
)
Experimental invariant Temperature (°C)
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For the Mg-Al-Mn system the reliability is checked in detail [2005Ohn]. The
liquidus surface of the Mg-rich corner is shown in Figure 4.2. The same
experimental data are plotted in Figures 3a and 3b as comparison between
calculated results and experimental data.
Figure 4.2: Calculated partial liquidus surface, the thick lines indicate monovariant reaction
lines and the thin lines represents the isotherms. Superimposed are the compositions of
experimental alloys further compared to calculated data of the liquidus surface. The primary
solid phase is specified in some experimental data.
This comparison in Figure 4.3 enables easy identification of those groups of
experimental data that are not consistent with the bulk of experimental
work. There is a reasonable agreement with this bulk of experimental data
and the calculated values. Moreover, there is a reasonable agreement with
the primary solidifying phases as shown in Figure 4.2.
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550 600 650 700 750 800 850 900550
600
650
700
750
800
850
900(a)
[10] [9] [8] [6] [5] [4] [3]
Calc
. T
em
pera
ture
(°C
)
Exp. Temperature (°C)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.50.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5(b)
[10] [9] [8] [6] [5] [4] [3]
Calc
. solu
bili
ty o
f M
n in liq
uid
(w
t.%
)
Exp. solubility of Mn in liquid (wt.%)
Figure 4.3: Comparison between calculated results and experimental data for all alloy
samples in the Mg-Al-Mn system. (a) Liquidus temperature at a given composition, (b)
Solubility of Mn in liquid at a given temperature and Al composition. The straight line in
Figs. (a) and (b) is a visual aid corresponding to perfect agreement between experimental
values and the calculated results from the present thermodynamic model.
The experimental data for the commercially very important Mg-Al-Zn alloys
are shown in Figures 4.4a and 4.4b [2006Ohn1]. The liquidus surface of the
Mg-rich corner is given in Figure 4.4a. The same experimental data is plotted
in Figure 4.4b as comparison between calculated results and experimental
data. A similar comparison was done for the Mg-rich phase equilibria of the
Mg-Mn-Zn system [2006Ohn2]. Technical important liquidus and Solidus
CompuTherm LLC Thermodynamic Databases
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temperatures of Mg-rich Mg-Al-Mn-Zn Alloys (AZ series) were investigated
by [2006Ohn3].
Figure 4.4a: Calculated partial Mg−Al−Zn liquidus surface and experimental alloy
compositions. The thick lines indicate monovariant reaction lines and the dashed lines
represent isotherms at an interval of 50°C.
Figure 4.4b: Comparison between calculated and experimental liquidus temperature for all
alloy samples in the Mg-Al-Zn system. The straight line is a visual aid corresponding to
perfect agreement between experimental and calculated results.
350 400 450 500 550 600 650350
400
450
500
550
600
650
[5]
[6]
[7]
[8]
[13]
[this work]
DSC1
DSC2
DTA
exp
. liq
uid
us t
em
pe
ratu
re,
°C
calc. liquidus temperature, °C
0 5 10 15 20 25 300
5
10
15
20
25
30
>>
>>
400°C
500°C
Mg
-Mg17
Al12
(Mg)
550°C
600°C
[5], [6], [7]
[8], [13], [this work]
wt.
% Z
n
wt.% Al
CompuTherm LLC Thermodynamic Databases
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Measured liquidus temperatures for other ternary Mg-alloy systems are
compared in Figure 4.5 with calculations from the magnesium database.
These miscellaneous Mg-X1-X2 systems include the alloying elements Al, Ca,
Ce, Gd, Li, Sc, and Si.
Additionally a selected comparison of experimental data and calculated
phase equilibria is given below. This demonstrates the feasibility to perform
reasonable calculations with PanMagnesium even in some very high alloyed
regions with vanishing Mg-content as outlined in Table 4.6. For the Al-Li-Si
system a comparison between calculated and experimentally measured DTA
data is given in Figure 6 [2001Gro6]. Figure 4.7 shows a calculated vertical
section in the Al-Ce-Si system at constant 90at%Al including the DSC/DTA
signals measured [2004Gro].
Figure 4.5: Liquidus temperatures for various ternary magnesium alloys outside the Mg-
Al-Mn-Zn system, with alloying elements Al, Ca, Ce, Gd, Li, Sc, Si: Comparison between
calculated and experimental data.
400 600 800 1000 1200 1400
400
600
800
1000
1200
1400
Ca
lcu
late
d liq
uid
us T
em
pe
ratu
re (
°C)
Experimental liquidus Temperature (°C)
CompuTherm LLC Thermodynamic Databases
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Figure 4.6: Comparison between calculated and experimentally measured DTA data for
the Al-Li-Si system [2001Gro6].
Figure 4.7: Calculated vertical section Al90Ce10 - Al90Si10 at constant 90at%Al
including the DSC/DTA signals measured in [2004Gro].
Me
as
ure
d t
em
pe
ratu
re, °C
500500
700
700
900
900
Calculated temperature, °C
DTA signal
2 4 6 8
400
600
800
1000
1200
Al 90Ce 0Si 10
Al 90Ce 10Si 0
U11
E1
E2
1 +
(Al)
1 +
2
+ (Al)
L + 2 + (Al)
L + (Al)
Al11
Ce3 (l)
+ 1 + (Al)
2 + (Al) + (Si)
L + 1 +
Al11
Ce3(l)
L + Al
11Ce
3(l)
L + 1
cooling; strong peak heating; strong peak cooling; weak peak heating; weak peak
Te
mp
era
ture
[°C
]
at.% Si
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The good agreement between experimental and calculated results, as
shown in above figures indicates the reliability of the current PanMagnesium
thermodynamic database. Additional validation is given in recent
comprehensive studies [2012Sch, 2013Gro].
4.7 References
[1998Lia] Liang, P., Tarfa, T., Robinson, J.A., Wagner, S., Ochin, P.,
Harmelin, M.G., Seifert, H.J., Lukas, H.L., Aldinger, F., Experimental investigation and thermodynamic calculation of
the Al-Mg-Zn system, Thermochim. Acta 314, 87-110 (1998).
[1999Gro] Gröbner, J., Schmid-Fetzer, R., Pisch, A., Cacciamani, G., Riani, P., Ferro, R.: Experimental Investigations and Thermodynamic
Calculation in the Al-Mg-Sc System. Z. Metallkd. 90(11), (1999), S. 872-880.
[2000Pis2] Pisch, A., Gröbner, J., Schmid-Fetzer, R.: Application of
Computational Thermochemistry to Al- and Mg-alloy processing with Sc additions. Mat. Sci. Eng. A 289, (2000), S. 123-129.
[2001Gro2] Gröbner, J., Pisch, A., Schmid-Fetzer, R.: Selection of Promising Quaternary Candidates from Mg-Mn-(Sc, Gd, Y, Zr) for Development of Creep-resistant Magnesium Alloys. J. Alloys
Comp. 320/2, (2001) 296-301.
[2001Gro4] Gröbner, J., Kevorkov, D., Schmid-Fetzer, R.: Thermodynamic
Calculation of Al-Gd and Al-Gd-Mg Phase Equilibria Checked by Key Experiments. Z. Metallkd. 92 (2001) S. 22-27.
[2001Gro6] Gröbner, J., Kevorkov, D., Schmid-Fetzer, R.: The Al-Li-Si
System, Part 2: Experimental study and Thermodynamic Calculation of the polythermal equilibria. J. Solid State Chem. 156 (2001) S. 506-511.
[2001Kev1] Kevorkov, D., Gröbner, J., Schmid-Fetzer, R.: The Al-Li-Si system, Part 1: A new structure type Li8Al3Si5 and the ternary
solid state phase equilibria. J. Solid State Chem. 156 (2001) S. 500-505.
[2001Kev2] Kevorkov, D.G., Pavlyuk, V.V., Dmytriv, G.S., Bodak, O.I.,
Gröbner, J., Schmid-Fetzer, R.: The ternary Gd-Li-Mg system:
CompuTherm LLC Thermodynamic Databases
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Phase diagram study and computational evaluation. J. Phase Equilibria 22 (1) (2001) S. 34-42.
[2001Kev3] Kevorkov, D., Schmid-Fetzer, R.: The Al-Ca System Part 1: Experimental Investigation of Phase Equilibria and Crystal Structures. Z. Metallkd. 92 (2001) S. 946-952.
[2001Kev4] Kevorkov, D.: Thermodynamics and Phase Equilibria of the Mg-Al-Li-Si System, Ph. D. Thesis TU Clausthal 2001.
[2001Sch] Schmid-Fetzer, R., Gröbner, J.: Focused Development of Magnesium Alloys Using the Calphad Approach. Advanced Engineering Materials 3 (12) (2001) 947-961.
[2002Gro1] Gröbner, J., Schmid-Fetzer, R., Pisch, A., Colinet, C., Pavlyuk, V.V., Dmytriv, G.S., Kevorkov, D.G., Bodak, O.I: Phase equilibria, calorimetric study and thermodynamic modelling of
Mg-Li-Ca alloys, Thermochimica Acta 389 (2002) 85-94.
[2002Gro2] Gröbner, J., Schmid-Fetzer, R.:Thermodynamic Modeling of Al-
Ce-Mg Phase Equilibria Coupled with Key Experiments, Intermetallics 10 (2002) 415-422.
[2003Gro1] Gröbner, J., Kevorkov, D., Chumak, I. and Schmid-Fetzer, R.:
Experimental Investigation and Thermodynamic Calculation of Ternary Al-Ca-Mg Phase Equilibria, Z. Metallkd. 94 (2003) 976-982.
[2003Gro2] Gröbner, J., Kevorkov, D.and Schmid-Fetzer, R.: A new Thermodynamic data set for the binary System Ca-Si and
Experimental Investigation in the ternary System Ca-Mg-Si, Intermetallics 11 (2003) 1065-1074.
[2004Bru] Brubaker, C.O., Liu, Z.-K., A computational thermodynamic
model of the Ca–Mg–Zn system, J. Alloys Comp. 370, 114-122 (2004).
[2004Gro] J. Gröbner, D. Mirkovic, Rainer Schmid-Fetzer: Thermodynamic Aspects of Constitution, Grain Refining and Solidification Enthalpies of Al-Ce-Si Alloys. Metall. Mater. Trans. A 35A, 3349-
3362 (2004).
[2004Kev] Kevorkov, D., Schmid-Fetzer, R. and Zhang F.: Phase Equilibria and Thermodynamics of the Mg-Si-Li System and Remodeling of
the Mg-Si System, J. Phase Equil. Diff. 25 (2004) 140-151.
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[2005Ohn] M. Ohno, R. Schmid-Fetzer: Thermodynamic assessment of Mg-Al-Mn phase equilibria, focusing Mg-rich alloys. Z.
Metallkde. 96, 857-869 (2005).
[2005Sch] R. Schmid-Fetzer, A. Janz, J. Gröbner and M. Ohno: Aspects of quality assurance in a thermodynamic Mg alloy database.
Advanced Engineering Materials 7 , 1142-1149 (2005).
[2006Ohn1] M. Ohno, D. Mirkovic and R. Schmid-Fetzer: Phase equilibria
and solidification of Mg-rich Mg-Al-Zn alloys. Materials Science & Engineering A, 421, 328-337 (2006).
[2006Ohn2] M. Ohno and R. Schmid-Fetzer: Mg-rich phase equilibria of Mg-
Mn-Zn alloys analyzed by computational thermochemistry. Int. J. Materials Research (Z. Metallkunde) 97, 526-532 (2006).
[2006Ohn3] M. Ohno, D. Mirkovic and R. Schmid-Fetzer: Liquidus and
Solidus Temperatures of Mg-rich Mg-Al-Mn-Zn Alloys. Acta Materialia, 54, 3883–3891 (2006).
[2006Ohn4] M. Ohno, A. Kozlov, R. Arroyave, Z.K. Liu, and R. Schmid-Fetzer: Thermodynamic modeling of the Ca-Sn system based on finite temperature quantities from first-principles and experiment.
Acta Materialia, 54, 4939-4951 (2006).
[2012Sch] R. Schmid-Fetzer, J. Gröbner: Thermodynamic database for Mg alloys — progress in multicomponent modeling. Metals, 2, 377-
398 (2012). (Special Issue "Magnesium Technology"), Open Access, www.mdpi.com/2075-4701/2/3/377,
dx.doi.org/10.3390/met2030377
[2013Gro] J. Gröbner, R. Schmid-Fetzer: Key issues in a thermodynamic Mg alloy database. Metall. Mater. Trans. A, A44, 2918-2934
(2013) dx.doi.org/10.1007/s11661-012-1483-z
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5. PanMolybdenum
Thermodynamic database for multi-component Mo-rich alloys
Copyright © CompuTherm LLC
Mo
Al B
Cr
Fe
Hf
Mn O
Re
Si
Ti
Zr
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5.1 Components
Total of 12 components are included in the database as listed here:
Major alloying elements Al, B, Cr, Hf, Mn, Mo, Re, Si, Ti
Minor alloying elements: Fe, O and Zr
5.2 Suggested Composition Range
The suggested composition range for each element is listed in Table 5.1. It
should be noted that this comosition range is based on the validation we
performed on commercial alloys. For perticular subsystems, the application
range may be wider. Some subsystems can be applied to the entire
composition arnge as given in section 5.4.
Table 5.1: Suggested composition range
Element Composition range (at.%)
Mo 50 ~ 100
Si, Ti 0 ~ 30
B, Cr 0 ~ 20
Al, Hf, Mn, Re 0 ~ 10
Fe, O, Zr 0 ~ 5
5.3 Phases
Total of 162 phases are included in the database and a few key phases are
listed in Table 5.2. Information on all the other phases can be found at
www.computherm.com.
CompuTherm LLC Thermodynamic Databases
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Table 5.2: Phase name and related information
Name Lattice Size Constituent
Al4Mo3Ti3 (4)(3)(3) (Al)(Mo)(Ti)
Al63Mo37 (0.63)(0.37) (Al)(Mo)
Al8FeMo3 (8)(1)(3) (Al)(Al,Fe)(Mo)
B4Mo (0.8)(0.2) (B)(Mo)
B5Mo2 (2)(5) (Mo)(B,Va)
Bcc (1)(3) (Al,B,Cr,Fe,Hf,Mn,Mo,O,Re,Si,Ti,Zr)(B,O,Va)
CBCC_A12 (1)(1) (Al,Cr,Fe,Mn,Mo,Re,Si,Ti,Zr)(Va)
Delta (3)(1) (Al,Cr,Fe,Mo,Re,Ti)(Al,Cr,Fe,Hf,Mo,Ti)
Eta (0.75)(0.25) (Fe,Ti)(Al,Cr,Hf,Mo,Ti)
Fcc (1)(1) (Al,B,Cr,Fe,Hf,Mn,Mo,Re,Si,Ti,Zr)(B,O,Va)
Laves_C14 (2)(1) (Al,Cr,Fe,Hf,Mo,Ti,Zr)(Al,Cr,Fe,Hf,Mo,Ti,Zr)
Laves_C15 (2)(1) (Al,Cr,Fe,Hf,Mo,Ti,Zr,Si)(Al,Cr,Fe,Hf,Mo,Ti,Zr)
Liquid (1) (Al,B,Cr,Fe,Hf,Mn,Mo,O,Re,Si,Ti,Zr)
Mo1O2_S (1)(2) (Mo)(O)
Mo1O3_S (1)(3) (Mo)(O)
Mo3Si (0.75)(0.25) (Cr,Fe,Hf,Mo,Re,Si,Ti,Zr)(Al,Cr,Fe,Re,Si)
Mo5Si3 (0.625)(0.375) (Cr,Mo,Re,Si,Ti,Zr)(Al,B,Mo,Si)
Mo5SiB2 (0.625)(0.125)(0.25) (Fe,Hf,Mn,Mo,Re,Ti,Zr)(B,Si)(B)
MoSi6Ti2 (1)(2) (Mo,Ti)(Si)
MoSiZr (1)(1)(1) (Mo)(Si)(Hf,Mo,Zr)
Mu_Phase (7)(2)(4) (Al,Cr,Fe,Mn,Mo,Re,Si)(Cr,Mo,Re,Ti) (Cr,Fe,Mo,Re,Ti)
Sigma (10)(4)(16) (Al,Fe,Mn,Re,Si)(Cr,Mo,Re) (Al,Cr,Fe,Mn,Mo,Re,Si)
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5.4 Key Elements and Subsystems
Key elements of the system are listed as: Mo-B-Cr-Hf-Mn-Re-Si-Ti. The
modeling status for the constituent binaries and ternaries of these key
elements are given in Tables 5.3-5.4. The color represents the following
meaning:
: Full description
: Full description for major phases
: Extrapolation
Table 5.3: Key Binary Systems for the PanMolybdenum
B Cr Hf Mn Mo Re Si Ti
Al Al-B Al-Cr Al-Hf Al-Mn Al-Mo Al-Re Al-Si Al-Ti
B B-Cr B-Hf B-Mn B-Mo B-Re B-Si B-Ti
Cr Cr-Hf Cr-Mn Cr-Mo Cr-Re Cr-Si Cr-Ti
Hf Hf-Mn Hf-Mo Hf-Re Hf-Si Hf-Ti
Mn Mn-Mo Mn-Re Mn-Si Mn-Ti
Mo Mo-Re Mo-Si Mo-Ti
Re Re-Si Re-Ti
Si Si-Ti
Table 5.4: Key Ternary Systems for the Major Components Mo-B-Hf-Si-Ti
Hf Si Ti
Mo-B Mo-B-Hf Mo-B-Si Mo-B-Ti
Mo-Hf Mo-Hf-Si Mo-Hf-Ti
Mo-Si Mo-Si-Ti
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5.5 Database Validation
Phase Diagrams
Figure 5.1 shows the calculated liquidus projection of the Mo-Si-B ternary
system. The calculated isothermal lines are also shown in the same figure.
Figure 5.1: Calculated liquidus projection of the Mo-Si-B ternary system superimposed with
the isothermal lines.
Figure 5.2 shows the calculated isothermal section of the Mo-Si-B ternary
system at 1600oC, which demonstrates the equilibrium between the ternary
T2 phase and the binary phases.
Figure 5.3 and 5.4 show the calculated isothermal sections of the Mo-Si-Ti
ternary system with the experimental data of [2003Yan] at 1425oC and
1600oC, respectively. Blue lines are the calculated phase boundaries.
Symbols are the phase equilibrium data measured using EPMA. It can be
seen that the experimentally measured phase equilibrium data are in good
x(B
)
x(Si)
0.0
0.2
0.3
0.5
0.7
0.9
0.0 0.2 0.4 0.6 0.8 1.00 0.2 0.4 0.6 0.8 10
0.2
0.4
0.6
0.8
1
x(Si)
x(B
)
Mo
B
Si
(Mo)
Liquidus Projection
2500oC
2400oC
2300oC
MoSi2
MoB
T2
T1
Mo2B
MoB2
Mo2B5
(B)
BnSi
B6Si
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agreement with the thermodynamic calculations using PanMo
thermodynamic database.
Figure 5.2: Calculated isothermal section of the Mo-Si-B ternary system
Figure 5.3: Calculated isothermal section of the Mo-Si-Ti ternary system at 1600oC
comparing with experimental data of [2003Yan].
x(B
)
x(SI)
0.0
0.2
0.3
0.5
0.7
0.9
0.0 0.2 0.4 0.6 0.8 1.00 0.2 0.4 0.6 0.8 10
0.2
0.4
0.6
0.8
1
x(SI)
x(B
)
MO
B
SI
T=1600oC
Mo2B
MoB
MoB2
Mo2B5
T2
BnSi
B6Si
L
Mo3Si T1 MoSi2
x(S
i)
x(Ti)
0.0
0.2
0.3
0.5
0.7
0.9
0.0 0.2 0.4 0.6 0.8 1.00 0.2 0.4 0.6 0.8 10
0.2
0.4
0.6
0.8
1
x(Ti)
x(S
i)
Mo
Si
Ti
T=1600oC Calculationtie-linetie-triangle
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Figure 5.4: Calculated isothermal section of the Mo-Si-Ti ternary system at 1425oC
comparing with experimental data of [2003Yan]
Solidification
In addition to the validation of phase equilibria, the current database has
also been subjected to extensive validation of solidification data of
commercial aluminum alloys. Figure 5.5 presents the calculated fraction of
solid vs. temperature of the Mo-Si-Ti alloys as well as the solidification
sequence using the Scheil model. The back scattered images of the as-cast
microstructure of these Mo-Si-Ti alloys from [2003Yan] are also shown in the
same figure. The predicated microstructures of the Mo-Si-Ti alloys using the
Scheil model agree well with expeimental observations.
x(S
i)
x(Ti)
0.0
0.2
0.3
0.5
0.7
0.9
0.0 0.2 0.4 0.6 0.8 1.00 0.2 0.4 0.6 0.8 10
0.2
0.4
0.6
0.8
1
x(Ti)
x(S
i)
Mo
Si
Ti
T=1425oCCalculationTie-lineTie-triangle
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Figure 5.5(a) The Scheil simulation of the solidification path of the Mo40Si20Ti40 alloy
Figure 5.5(b) A back scattered image of the as-cast microstructure of the Mo40Si20Ti40
alloy
(b)
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Figure 5.5(c) The Scheil simulation of the solidification path of the Mo40Si25Ti35 alloy
Figure 5.5(d) A back scattered image of the as-cast microstructure of the Mo40Si25Ti35
alloy
(d)
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Figure 5.5(e) The Scheil simulation of the solidification path of the Mo5Si25Ti75 alloy
Figure 5.5(f) A back scattered image of the as-cast microstructure of the Mo5Si25Ti70
alloy
5.6 Reference
[2003Yan] Y. Yang, Y.A. Chang, L. Tan, Y. Du, Materials Science and Engineering A361 (2003), p.281–293
(f)
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6. PanNickel
Thermodynamic Database for Nickel-Based Superalloys
Copyright © CompuTherm LLC
Ni
Al B C
Co
Cr
Cu
Fe
Hf
Ir
Mn Mo N
Nb
Pt
Re
Ru
Si
Ta
Ti
W Zr
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6.1 Components
Total of 22 components are included in the database.
Major alloying elements: Al, Co, Cr, Fe, Ir, Mo, Ni, Pt, Re, Ru and W
Minor alloying elements: B, C, Cu, Hf, Mn, N, Nb, Si, Ta, Ti and Zr
6.2 Suggested Composition Range
The suggested composition range for each element is listed in Table 6.1. It
should be noted that this comosition range is based on the validation we
performed on commercial alloys. For perticular subsystems, the application
range may be wider. Some subsystems can be applied to the entire
composition range as given in Table 6.4.
Table 6.1: Suggested composition range
Element Composition range (wt%)
Ni 50-100
Al,Co,Cr,Fe 0-22
Ir,Mo,Re,Ru,W 0-12
Hf,Nb,Ta,Ti 0-5
B,C,Cu,Mn,N,Si,Zr 0-0.5
Pt 0-40
6.3 Phases
Total of 99 phases are included in the current database. The names and
thermodynamic models of the major phases are given in Table 6.2.
Information on all the other phases can be found at www.computherm.com.
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Table 6.2: Phase name and related information
Name Lattice Size Constituent
B2 (1)(1) (Al,Co,Cr,Fe,Hf,Ir,Mn,Mo,Nb,Ni,Pt,Re,Ru,Si,Ta,Ti,W) (Al,Co,Cr,Fe,Hf,Ir,Mn,Mo,Nb,Ni,Pt,Re,Ru,Si,Ta,Ti,W,Va)
Bcc (1)(3) (Al,Co,Cr,Cu,Fe,Hf,Ir,Mn,Mo,Nb, Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr)(B,C,N,Va)
Delta (3)(1) (Al,Co,Cr,Fe,Mo,Nb,Ni,Re,Ta,Ti) (Al,Co,Cr,Fe,Hf,Mo,Nb,Ni,Ta,Ti,W)
Eta (0.75)(0.25) (Co,Fe,Ni,Ti)(Al,Cr,Hf,Mo,Nb,Ni,Ta,Ti)
Fcc (1)(1) (Al,Co,Cr,Cu,Fe,Hf,Ir,Mn,Mo,Nb, Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr) (B,C,N,Va)
Hcp (1)(0.5) (Al,Co,Cr,Cu,Fe,Hf,Ir,Mo,Nb, Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr)(B,C,N,Va)
L12_FCC (0.75)(0.25)(1) (Al,Co,Cr,Fe,Hf,Ir,Mn,Mo,Nb,Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr) (Al,Co,Cr,Fe,Hf,Ir,Mn,Mo,Nb,Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr)(Va)
Laves_C14 (2)(1) (Al,Co,Cr,Fe,Hf,Mo,Nb,Ni,Ta,Ti,W,Zr) (Al,Co,Cr,Fe,Hf,Mo,Nb,Ni,Ta,Ti,W,Zr)
Laves_C15 (2)(1) (Al,Co,Cr,Fe,Hf,Mo,Nb,Ni,Ta,Ti,W,Zr) (Al,Co,Cr,Fe,Hf,Mo,Nb,Ni,Ta,Ti,W,Zr)
Liquid (1) (Al,B,C,Co,Cr,Cu,Fe,Hf,Ir,Mn,Mo, N,Nb,Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr)
M23C6 (20)(3)(6) (Co,Cr,Fe,Ni,Re)(Co,Cr,Fe,Mo,Nb,Ni,Re,Ta,Ti,W)(B,C)
M3Si (3)(1) (Co,Cr,Fe,Mo,Nb,Ni,Ta,Ti,Zr)(Si)
M5Si3 (0.625)(0.375) (Cr,Fe,Mo,Nb,Ta,Ti,W,Zr)(Si)
M6C (2)(2)(2)(1) (Co,Fe,Ni)(Cr,Mo,Nb,W) (Co,Cr,Fe,Mo,Nb,Ni,W)(C)
M7C3 (7)(3) (Co,Cr,Fe,Mo,Nb,Ni,Re,W)(B,C)
MSi (0.5)(0.5) (Co,Cr,Fe,Hf,Nb,Ni,Ti,Zr)(Si)
Mu_Phase (7)(2)(4) (Co,Cr,Fe,Mo,Nb,Ni,Re,Ta) (Co,Cr,Mo,Nb,Ni,Re,Ta,Ti,W) (Co,Cr,Fe,Mo,Nb,Ni,Re,Ta,Ti,W)
Sigma (8)(4)(18) (Al,Co,Fe,Mn,Ni,Re,Ru,Si) (Co,Cr,Mo,Nb,Ni,Ta,W) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Re,Ru,Si,Ta,W)
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6.4 Key Elements and Subsystems
Key elements of the system are listed as: Ni-Al-Co-Cr-Fe-Pt-Ir-Mo-Re-Ru-W .
The modeling status for the constituent binaries and ternaries of these key
elements are given in Tables 6.3-6.4. The color represents the following
meaning:
: Full description
: Full description for major phases
: Extrapolation
Table 6.3 lists the binaries in the system. Thermodynamic descriptions are
fully developed for the binaries in green color, which means that there is no
composition and temperature limits if calculations are carried out for these
binary systems. Only major phases are considered for the binaries in yellow
color.
Table 6.3: Key Binary Systems for the Ni-Al-Co-Cr-Fe-Ir-Mo-Pt-Re-Ru-W
Subset
Co Cr Fe Ir Mo Ni Pt Re Ru W
Al Al-Co Al-Cr Al-Fe Al-Ir Al-Mo Al-Ni Al-Pt Al-Re Al-Ru Al-W
Co Co-Cr Co-Fe Co-Ir Co-Mo Co-Ni Co-Pt Co-Re Co-Ru Co-W
Cr Cr-Fe Cr-Ir Cr-Mo Cr-Ni Cr-Pt Cr-Re Cr-Ru Cr-W
Fe Fe-Ir Fe-Mo Fe-Ni Fe-Pt Fe-Re Fe-Ru Fe-W
Ir Ir-Mo Ir-Ni Ir-Pt Ir-Re Ir-Ru Ir-W
Mo Mo-Ni Mo-Pt Mo-Re Mo-Ru Mo-W
Ni Ni-Pt Ni-Re Ni-Ru Ni-W
Pt Pt-Re Pt-Ru Pt-W
Re Re-Ru Re-W
Ru Ru-W
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Table 6.4: Key Ternary Systems for the Ni-Al-Co-Cr-Fe-Pt-Ir-Mo-Re-Ru-W
Subset
Co Cr Fe Pt Ir Mo Re Ru W
Ni-Al Ni-Al-Co Ni-Al-Cr Ni-Al-Fe Ni-Al-Pt Ni-Al-Ir Ni-Al-Mo Ni-Al-Re Ni-Al-Ru Ni-Al-W
Ni-Co Ni-Co-Cr Ni-Co-Fe Ni-Co-Pt Ni-Co-Ir Ni-Co-Mo Ni-Co-Re Ni-Co-Ru Ni-Co-W
Ni-Cr Ni-Cr-Fe Ni-Cr-Pt Ni-Cr-Ir Ni-Cr-Mo Ni-Cr-Re Ni-Cr-Ru Ni-Cr-W
Ni-Fe Ni-Fe-Pt Ni-Fe-Ir Ni-Fe-Mo Ni-Fe-Re Ni-Fe-Ru Ni-Fe-W
6.5 Database Validation
This database focuses on the nickel-rich corner of multicomponent nickel
alloys, and has been extensively tested and validated by a large number of
commercial nickel alloys. Table 6.5 lists the alloys and references used for
testing the current database. In the table, fT ,
s
fT , and '
fT represent liquidus,
solidus ( starts to form from liquid), and solvus ( starts to precipitate in
the phase matrix) temperatures, respectively. 'f represents the volume
fraction of the phase, and )( inXx , ' )( inXx represent the equilibrium
compositions of component X in the and phases, respectively. The
recommended composition ranges given in Table 6.1 are the ones that have
been extensively tested. Users need to be careful when using the database
beyond the suggested ranges.
This database can be used to calculate phase equilibria for multi-component
alloys, such as the equilibrium between and . It can be used to predict
phase transformation temperatures, such as liquidus, solidus and solvus.
The fraction of each phase as a function of temperature and partitioning of
components in different phases can also be calculated. In addition to
equilibrium calculations, Scheil simulations can also be carried out using
this database. Some calculation results are presented in Figures 6.1 to 6.10.
Figure 6.1 shows comparison between calculated and experimentally
measured liquidus and solidus temperatures for nickel-based superalloys,
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while Figure 6.2 is for that of the solvus temperatures of the phase.
Figure 6.3 shows comparison between calculated and experimentally
determined amounts of the phase. Figures 6.4 to 6.10 are comparisons
between the calculated and experimentally measured equilibrium
compositions for Al, Co, Cr, Mo, Re, Ti, and W in and phases,
respectively. These figures show reasonable agreement between the
calculated values using the current nickel database and the experimentally
determined ones.
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Table 6.5: Experimental Data Used for Testing the Current Nickel Database
Alloy Experimental Information References
Udimet-700 'fT , Tvsf . ' ,
TvsinWMoTiCrAlx . ' ),,,,(
[1971Mol]
Ni-14Cr-6.5~12Al-4Ti-1~5Mo '
fT [1972Loo]
Ni-4~13Al-6.5~20.5Cr-0.25~4.5Ti-0~6Mo-0~4W
Catf o850 ' ,
' ),,,,( andinWMoTiCrAlx
[1974Dre]
IN-939 ' ),,,,,( andinWTaTiCrCoAlx [1983Del]
Udimet-520 ' ),,,,,( andinWMoTiCrCoAlx [1983Mag]
Udimet-710 ' ),,,,,( andinWMoTiCrCoAlx [1983Mag]
Udimet-100 ' ),,,,,( andinWMoTiCrCoAlx [1983Mag]
N-18 'fT [1988Duc]
IN-100 'fT [1988Duc]
MERL-76 'fT [1988Duc]
RENE-95 'fT [1988Duc]
ASTROLOY 'fT [1988Duc]
Nimonic-105 ' ),,,,( andinMoTiCrCoAlx [1991Tri]
BJH, BJJ, BJK, BJL, BJM, BJP
fT ,
s
fT , '
fT [1992Dha]
2D8625, 2D8638, 2D8639, 2D8640
fT ,
s
fT , '
fT [1992Dha]
MA6000 fT ,
s
fT , '
fT [1992Dha]
CMSX-2 fT ,
s
fT , '
fT [1992Dha]
SRR-99 ' ),,,,,( andinWTaTiCrCoAlx [1992Sch]
Modified IN738LC ' ),,,,,( andinMoWTaCrCoAlx [1993Zha]
MC2 ' ),,,,,,( andinMoWTiTaCrCoAlx [1994Duv]
Ni-Al-Re-X(X: Cr, Mo, W, Ti, Ta, Nb, Co)
' ),,( andinXREAlx [1994Miy]
Rene N6 fT ,
s
fT , '
fT , 'f ,
' ),,,,,,( andinMoWRETaCrCoAlx
[1998Rit] [1999Rit] [2001Cop]
CompuTherm LLC Thermodynamic Databases
62
Figure 6.1: Comparison between the calculated and experimentally measured liquidus
and solidus temperatures
Figure 6.2: Comparison between the calculated and experimentally measured solvus
temperatures of the phase
1600
1620
1640
1660
1680
1700
1720
1740
1600 1620 1640 1660 1680 1700 1720 1740
Measured (K)
Ca
lcu
late
d (
K)
01Cop-Liquidus
01Cop-Solidus
92Dha-Liquidus
92Dha-Solidus
Diagonal
1100
1200
1300
1400
1500
1600
1700
1100 1200 1300 1400 1500 1600 1700
Measured (K)
Calc
ula
ted
(K
)
01Cop
92Dha
88Duc
71Mol
Diagonal
CompuTherm LLC Thermodynamic Databases
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Figure 6.3: Comparison between the calculated and experimentally measured amounts of
the phase
Figure 6.4: Comparison between the calculated and experimentally measured equilibrium
compositions of Al in and phase
0
20
40
60
80
100
0 20 40 60 80 100Measured
Ca
lcu
late
d
01Cop
84Kha
74Dre
72Loo
Diagonal
0
5
10
15
20
25
0 5 10 15 20 25
Measured (Al at%)
Ca
lcu
late
d (
Al
at%
)
01Cop -g
94Miy -g
93Zha -g
92Sch -g
01Cop -g_p
94Miy -g_p
93Zha -g_p
92Sch -g_p
84Kha -g_p
74Dre -g_p
Diagonal
'
'
'
'
'
'
CompuTherm LLC Thermodynamic Databases
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Figure 6.5: Comparison between the calculated and experimentally measured equilibrium
compositions of Co in and phases
Figure 6.6: Comparison between the calculated and experimentally measured equilibrium
compositions of Cr in and phases
0
5
10
15
20
25
30
0 5 10 15 20 25 30
Measured (Co at%)
Ca
lcu
late
d (
Co
at%
)
01Cop -g
94Miy -g
93Zha -g
92Sch -g
91Tri -g
01Cop -g_p
94Miy -g_p
93Zha -g_p
92Sch -g_p
91Tri -g_p
Diagonal
'
'
'
'
'
0
5
10
15
20
25
30
35
40
0 5 10 15 20 25 30 35 40
Measured (Cr at%)
Ca
lcu
late
d (
Cr
at%
)
01Cop -g
94Miy -g
92Sch -g
91Tri -g
74Dre -g
01Cop -g_p
94Miy -g_p
92Sch -g_p
74Dre -g-p
Diagonal
'
'
'
'
CompuTherm LLC Thermodynamic Databases
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Figure 6.7: Comparison between the calculated and experimentally measured equilibrium
compositions of Mo in and phases
Figure 6.8: Comparison between the calculated and experimentally measured equilibrium
compositions of Re in and phases
0
2
4
6
8
10
0 2 4 6 8 10
Measured (Mo at%)
Ca
lcu
late
d (
Mo
at%
)
01Cop -g
94Duv -g
93Zha -g
74Dre -g
01Cop -g-p
94Duv -g-p
93Zha -g-p
Diagonal
'
'
'
0
1
2
3
4
5
6
0 1 2 3 4 5 6
Measured (Re at%)
Ca
lcu
late
d (
Re a
t%)
01Cop-g
94Miy-g
01Cop-g_p
94Miy-g_p
Diagonal
t
()
()
'
'
CompuTherm LLC Thermodynamic Databases
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Figure 6.9: Comparison between the calculated and experimentally measured equilibrium
compositions of Ti in and phases
Figure 6.10: Comparison between the calculated and experimentally measured equilibrium
compositions of W in and phases
0
3
6
9
12
15
0 3 6 9 12 15
Measured (Ti at%)
Ca
lcu
late
d (
Ti
at%
)
94Miy -g
94Duv -g
92Sch -g
94Miy -g-p
94Duv -g-p
93Zha -g-p
92Sch -g-p
74Dre -g-p
Diagonal
'
'
'
'
'
0
1
2
3
4
5
6
0 1 2 3 4 5 6Measured (W at%)
Ca
lcu
late
d (
W a
t%)
01Cop-g
93Zha-g
92Sch-g
83Del-g
74Dre
01Cop-g_p
92Sch-g_p
83Del-g_p
94Miy-g-p
Diagonal
()
()
()
()
'
'
'
'
CompuTherm LLC Thermodynamic Databases
67
6.6 References
[1971Mol] E. H. van der Molen, J. M. Oblak and O. H. Kriege, Metal. Trans., 2 (1971) 1627-1633.
[1972Loo] W. T. Loomis, J. W. Freeman and D. L. Sponseller, Metal. Trans., 3 (1972) 989-1000.
[1974Dre] R. L. Dreshfield and J. F. Wallace, Metal. Trans., 5 (1974) 71-78.
[1983Del] K. M. Delargy and G. D. W. Smith, Metal. Trans., 14A (1983)
1771-1783.
[1983Mag] M. Magrini, B. Badan and E. Ramous, Z. Metallkde., 74 (1983)
314-316.
[1988Duc] C. Ducrocq, A. Lasalmonie and Y. Honnorat, in Superalloys 1988, Ed. S. Reichman, D. N. Duhl, G. Maurer, S. Antolovich and C. Lund, (The Metallurgical Society, 1988) 63-72.
[1991Tri] K. Trinckauf and E. Nembach, Acta Metall. Mater., 39(12) (1991)
3057-3061.
[1992Dha] S.-R. Dharwadkar, K. Hilpert, F. Schubert and V. Venugopal, Z. Metallkde., 83 (1992) 744-749.
[1992Sch] R. Schmidt and M. Feller-Kniepmeier, Scripta Metal. Mater., 26
(1992) 1919-1924.
[1993Zha] J. S. Zhang, Z.Q. Hu, Y. Murata, M. Morinaga and N. Yukawa, Metal. Trans., 24A (1993) 2443-2450.
[1994Duv] S. Duval, S. Chambreland, P. Caron and D. Blavette, Acta Metall. Mater., 42(1) (1994) 185-194.
[1994Miy] S. Miyazaki, Y. Murata and M. Morinaga,, Iron and Steel (Japan) 80(2) (1994) 78-83.
[1998Rit] F. J. Ritzert, D. Arenas, D. Keller and V. Vasudevan, NASA/TM 1998-206622.
[1999Rit] F. J. Ritzert, D. Keller and V. Vasudevan, NASA/TM 1999-209277.
[2001Cop] E. H. Copland, N. S. Jacobson and F. J. Ritzert, NASA/TM
2001-210897.
CompuTherm LLC Thermodynamic Databases
68
7. PanTitanium
Thermodynamic Database for Titanium-Based Alloys
Copyright © CompuTherm LLC
Ti
Al B
C
Cr
Cu
Fe
H
Mo N Nb
Ni
O
Si
Sn
Ta
V
Zr
CompuTherm LLC Thermodynamic Databases
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7.1 Components
Total of 18 components are included in the database as listed here:
Major alloying elements: Al, Cr, Cu, Fe, Mo, Nb, Ni, Sn, Ta, Ti, V and Zr
Minor alloying elements: B, C, H, N, O and Si
7.2 Suggested Composition Range
The suggested composition range for each element is listed in Table 7.1. It
should be noted that this comosition range is based on the validation we
performed on commercial alloys.
Table 7.1: Suggested composition range
Element Composition range (wt%)
Ti 75-100
Al,V 0-11
Mo,Nb,Ta, Zr 0-8
Cr,Sn 0-5
Cu, Fe,Ni 0-3
B, C, H, N, O, Si 0-0.5
7.3 Phases
A total of 126 phases are included in the current database, and Table 7.2
lists those that are important for commercial titanium alloys. Information on
all the other phases can be found at www.computherm.com .
CompuTherm LLC Thermodynamic Databases
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Table 7.2: Phase Name and Related Information
Name Lattice Size Constituent
A15_Nb3Al (3)(1) (Cr,Nb,Si,Ti)(Al,Cr,Nb,Si)
Bcc (1)(3) (Al,Cr,Cu,Fe,Mo,Nb,Ni,Si,Sn,Ta,Ti,V,Zr) (B,C,H,N,O,Va)
Cr3Si_A15 (3)(1)(3) (Cr,Nb,Si,Ti)(Cr,Nb,Si)(Va)
DO19_Ti3Al (0.75)(0.25)(0.5) (Al,Cr,Mo,Nb,Sn,Ta,Ti,V,Zr) (Al,Cr,Mo,Nb,Si,Sn,Ta,Ti,V,Zr)(O,Va)
DO22_TiAl3 (3)(1) (Al,Mo,Ti,V)(Cr,Mo,Nb,Ta,Ti,V)
Diamond_A4 (1) (Al,C,Si,Sn,Ti)
Fcc (1)(1) (Al,Cr,Cu,Fe,Mo,Nb,Ni,Si,Sn,Ta,Ti,V,Zr) (B,C,H,N,O,Va)
Hcp (1)(0.5) (Al,Cr,Cu,Fe,Mo,Nb,Ni,Si,Sn,Ta,Ti,V,Zr) (B,C,H,N,O,Va)
L10_TiAl (1)(1) (Al,Cr,Mo,Nb,Si,Ta,Ti,V) (Al,Cr,Mo,Nb,Ta,Ti,V)
Laves_C14 (2)(1) (Al,Cr,Fe,Mo,Nb,Si,Ta,Ti,Zr) (Al,Cr,Fe,Mo,Nb,Ta,Ti,Zr)
Laves_C15 (2)(1) (Al,Cr,Si,Ti,Zr)(Al,Cr,Si,Ti,Zr)
Laves_C36 (2)(1) (Al,Cr,Ni,Zr)(Al,Cr,Ni,Zr)
Liquid (1) (Al,B,C,Cr,Cu,Fe,H,Mo,N,Nb,Ni,O,Si,Sn,Ta,Ti,V,Zr)
Sigma (8)(4)(18) (Al,Fe,Ni)(Cr,Mo,Nb,Ta,Ti,V) (Al,Cr,Fe,Mo,Nb,Ni,Ta,Ti,V)
7.4 Sub-System Information
The composition limits given in Table 7.1 are for multicomponent
commercial titanium alloys in general. Complete and partial thermodynamic
descriptions are developed for many binary systems as listed in Table 7.3.
CompuTherm LLC Thermodynamic Databases
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This means the current database works in a much wider composition range
in many sub-systems.
Table 7.3 lists all the binaries in the 18-component system. Thermodynamic
descriptions are fully developed for the binaries in green color, which means
that there is no composition limits if calculations are carried out for these
binary systems. Only major phases are considered for the binaries in yellow
color. Partial of the system is modeled for the binaries in red color. The
number in front of one of the elements specifies the valid composition range.
For example, Al-5B indicates that this system is modeled from pure Al to
5wt% of B. No model parameters are developed for those binaries in white
color.
In addition to the binaries, thermodynamic description for the key ternary
Ti-Al-V system is also developed.
: Full description
: Full description for major phases
: Partial description for certain composition range
: Extrapolation
Table 7.3: Current Status of Key Binary Systems
Cr Cu Fe Mo Nb Ni Si Sn Ta Ti V Zr
Al Al-Cr Al-Cu Al-Fe Al-Mo Al-Nb Al-Ni Al-Si Al-Sn Al-Ta Al-Ti Al-V Al-Zr
Cr Cr-Cu Cr-Fe Cr-Mo Cr-Nb Cr-Ni Cr-Si Cr-Sn Cr-Ta Cr-Ti Cr-V Cr-Zr
Cu 2Cu-Fe Cu-Mo Cu-Nb Cu-Ni Cu-Si Cu-Sn Cu-Ta Cu-Ti Cu-V Cu-Zr
Fe Fe-Mo Fe-Nb Fe-Ni Fe-5Si Fe-Sn Fe-Ta Fe-Ti Fe-V Fe-Zr
Mo Mo-Nb Mo-Ni Mo-8Si Mo-Sn Mo-Ta Mo-Ti Mo-V Mo-Zr
N N-Nb N-Ni N-Si N-Sn N-Ta N-Ti N-V N-Zr
Nb Nb-Ni Nb-5Si Nb-Sn Nb-Ta Nb-Ti Nb-V Nb-Zr
Ni Ni-Si Ni-Sn Ni-Ta Ni-Ti Ni-V Ni-Zr
Si Si-Sn 5Si-Ta Si-Ti 25Si-V 3Si-Zr
Sn Sn-Ta Sn-Ti Sn-V Sn-Zr
Ta Ta-Ti Ta-V Ta-Zr
Ti Ti-V Ti-Zr
V V-Zr
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7.5 Database Validation
Since this database has been designed for use with conventional - types of
titanium alloys, it has been focused at the Ti-rich corner. This database has
been tested by a large number of - type of titanium alloys, such as Ti64,
Ti6242 and Ti6246. Table 7.4 lists the alloys and references used for
validating the current database. The suggested composition ranges given in
Table 1 are based on the compositions of these testing alloys. Users need to
be careful while using the database beyond the suggested ranges.
Table 7.4: Experimental Data Used for Testing the Current Titanium
Database
Alloy Experimental Information References
Ti64
transus, approach curve, partitioning
of Al and V in and .
[1966Cas,1979Las, 1986Kah,1986Ro, 1991Lee,2003Fur, 2003Sem,2003Ven]
Ti-144A transus, approach curve, and/or partition coefficient
[2003Ven]
Ti-155A transus, approach curve, and/or partition coefficient
[2003Ven]
Ti-6246 transus [2003Fur]
Ti-6242 transus [2003Fur]
IMI 834 transus [2003Fur]
Ti-17 transus [2003Fur]
Ti-10-2-3 transus [2003Fur]
Ti-6-6-2 transus [2003Fur]
Ti-62222 transus [2003Fur]
Ti-6Al-2Nb-1Ta-0.8Mo
transus [1984Lin]
Corona X approach curve [2003Boy]
Ti-4.5Al-5Mo-1.5Cr(Corona 5)
transus [1984Yod]
Ti-10-2-3 transus, approach curve [1980Due]
IMI 550 transus, approach curve, partitioning
of Al, Mo, Sn and Si in and .
[2001Kha]
, +, and alloys listed in the handbook
transus [1994Boy]
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This database can be used to calculate phase equilibria for multi-
component alloys, such as equilibrium between and . It can be used to
predict phase transformation temperatures, such as -transus. The fraction
of each phase as a function of temperature, partitioning of components in
different phases can also be calculated. In addition to equilibrium
calculations, Scheil simulations can also be carried out using this database.
Some calculated examples are given below.
Beta transus, the temperature at which starts to form from , is an
important reference parameter in the selection of processing conditions,
such as heat treatment process, for the conventional - type of titanium
alloys. This temperature has been calculated for a large number of Ti64 and
other titanium alloys using PanTitanium. Figure 7.1 shows a comparison
between the predicted and observed beta transus temperatures for more
than 150 Ti64 heats, reasonable agreement is obtained. The accuracy of the
prediction depends on the reliability of the database and the accuracy of the
input chemistry of the alloy. The calculated beta transus temperature is
found to be very sensitive to the amount of the interstitial elements, such as
C, H, N, and O. It is seen from Figure 7.1 that the predicted beta transus
temperatures are in general higher than the observed ones. This can be
explained by the fact that the calculated beta transus temperature
corresponds to the temperature at which just starts to form, while its
amount is 0%. It is very difficult to catch this exact temperature by
experiments, and normally the measured temperature may corresponds to
which 1~2% of phase has formed. Taking this factor into consideration, the
transformation temperatures corresponding to 2% of phase are calculated
for the same alloys and are compared with observed values as shown in
Figure 7.2. It is seen that better agreement is obtained.
Figure 7.3 shows a similar comparison for other titanium alloys, including
Ti6222, Ti6242, Ti6246, Ti17 and so on, and reasonable agreement is
CompuTherm LLC Thermodynamic Databases
74
obtained. The agreement can be improved if the transformation
temperatures corresponding to 2% of phase are used for comparison.
Figure 7.1: Comparison between predicted and observed beta transus for more than 150
Ti64 heats. The calculated transformation temperatures correspond to 0% of phase
formed and the experimental data are from [1966Cas, 2003Sem, 2003Fur]
Figure 7.2: Comparison between predicted and observed beta transus for more than 150
Ti64 heats. The calculated transformation temperatures correspond to 2% of phase
formed. The experimental data are from [1966Cas, 2003Sem, 2003Fur]
970
980
990
1000
1010
1020
1030
970 980 990 1000 1010 1020 1030
Measured (oC)
Ca
lcu
late
d (
oC
), 2
%H
CP
66Castro
02Semiatin
Furrer_1
Furrer_2
Furrer_3
Furrer_4
Furrer_5
CompuTherm LLC Thermodynamic Databases
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Figure 7.3: Comparison between predicted and observed beta transus for other titanium
alloys. The calculated transformation temperatures correspond to 0% of phase formed.
Figure 7.4: Beta approach curve for a Ti64 alloy with experimental data from [2003Sem]
The relative amounts of and phases are critical in the determination of
alloy properties for an - alloy. Beta approach curve, the volume fraction of
beta phase as a function of temperature, is therefore important in the
selection of final heat treatment temperature. Beta approach curves for two
Ti64 heats are calculated as plotted in Figures 7.4 and 7.5. The experimental
750 800 850 900 950 1000 1050 1100
750
800
850
900
950
1000
1050
1100
Ca
lcu
late
d (
oC
)
Measured (oC)
6246 Ti
6242 Ti
IMI834
Ti-17
Ti 10-2-3
Ti 6-6-2
720 760 800 840 880 920 960 1000
0.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n o
f B
eta
Ph
ase
Temperature [oC]
Measured [03Sem]
Calculated, mole
Calculated, volume
CompuTherm LLC Thermodynamic Databases
76
data [2003Sem, 1966Cas] are also plotted on the diagrams for comparison;
very good agreements are obtained.
It should point out that the calculated phase fractions are mole fractions,
while the measured values are volume fractions. However, since the molar
volume of the phase is very close to that of the phase, the error induced
due to the direct comparison between them is small. This can be seen in
Figure 7.4 in which both the mole factions and the volume fractions of
phase are plotted.
Figure 7.5: Beta approach curve for a Ti64 alloy with experimental data from [1966Cas].
In addition to Ti64, beta approach curves are also calculated for other
titanium alloys. Figure 7.6 shows the beta approach curve for one Ti6242
alloy, and the experimental data are from Semiatin [2005Sem].
600 650 700 750 800 850 900 950 1000
0.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n o
f B
eta
Ph
ase
Temperature [oC]
Measured [66Cas]
Calculated
CompuTherm LLC Thermodynamic Databases
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Figure 7.6: Beta approach curve for a Ti-6242 alloy with experimental data from
[2005Sem].
Equilibrium phase compositions are useful in understanding the partitioning
of elements in different phases. These are calculated and compared with the
experimental measurements for Ti64 and Ti6242 alloys. Examples are given
in Figures 7.7 to 7.9. Figure 7.7 shows the equilibrium compositions of Al
and V in and for one Ti64 alloy. In general, the calculated equilibrium
compositions agree with the experimental data very well. The calculated V
concentrations in the phase are higher than the measurements at low
temperatures. This is due to the fact that the grains were too small to allow
an accurate analysis [1979Las]. Figures 7.8 and 7.9 show the equilibrium
compositions of Al, Mo, and Ti in and for the Ti6242 alloy.
Figures 7.10 and 7.11 show the calculated fractions for IMI550 and
Corona-X alloys, respectively. Both calculations agree with experimental
data very well.
700 750 800 850 900 950 1000 1050
0.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n o
f B
eta
Ph
ase
Temperature [oC]
Measured [05Sem]
Calculated, mole
CompuTherm LLC Thermodynamic Databases
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Figure 7.7: Equilibrium compositions of Al and V in the alpha and beta phases for a Ti64
alloy with the experimental data from [2003Sem].
Figure 7.8: Equilibrium compositions of Al and Mo in the alpha and beta phases for a
Ti6242 alloy with the experimental data from [2005Sem].
700 750 800 850 900 950 1000
0
5
10
15
20
Co
mp
ositio
ns [
wt%
]
Temperature [oC]
Al, Measured [03Sem]
V, Measured [03Sem]
Al, Calculated
V, Calculated
700 750 800 850 900 950 1000
0
5
10
15
20
25
Co
mp
ositio
ns [
wt%
]
Temperature [oC]
Al Alpha
Mo Alpha
Al Beta
Mo Beta
Pandat Al Alpha
Pandat Mo Alpha
Pandat Al Beta
Pandat Mo Beta
CompuTherm LLC Thermodynamic Databases
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Figure 7.9: Equilibrium compositions of Ti in the alpha and beta phases for a Ti6242
alloy with experimental data from [2005Sem].
Figure 7.10: Alpha Fraction curve for an IMI550 alloy with experimental data [2001Kha].
800 850 900 950 1000
70
75
80
85
90
Co
mp
ositio
ns [
wt%
]
Temperature [oC]
Ti Alpha
Ti Beta
Pandat Ti Alpha
Pandat Ti Beta
750 800 850 900 950 1000
0.0
0.2
0.4
0.6
0.8
1.0
Fra
ctio
n o
f A
lph
a P
ha
se
Temperature [oC]
Ti-IMI550
SEM [01Kha]
Optical [01Kha]
Calculated
CompuTherm LLC Thermodynamic Databases
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Figure 7.11: Alpha Fraction curve for a Corona-X alloy with experimental data [2001Kha].
7.6 References
[1966Cas] R. Castro and L. Seraphin, Mem. Sci. Rev. Met., 63 (1966), 1025-
1058.
[1979Las] A.L. Lasalmonie and M.Loubradou, J. Mat. Sci., 14 (1979), 2589-2595.
[1980Due] T.W. Duerig, G.T. Terlinde and J.C. Williams, Met. Trans. A, 11A (1980), 1987-1998.
[1984Lin] F. S. Lin, E. A. Starke, Jr., S. B. Chakrabortty and A. Gysler, Met. Trans., 15A (1984), 1229-1246.
[1984Yod] G.R. Yoder, F.H. Froes and D. Eylon, Met. Trans., 15A (1984), 183-197.
[1986Kah] A.I. Kahveci and G.E. Welsch, Scripta Met., 20 (1986), 1287-
1290.
[1986Ro] Y. Ro, H. Onodera, and K. Ohno, Trans. Iron Steel Inst. Japan,
26(4) (1986), 322-327.
[1991Lee] Y.T. Lee, M. Peters and G. Welsch, Met. Trans., 22A (1991), 709-
714.
750 800 850 900 950
0.0
0.2
0.4
0.6
0.8
Fra
ctio
n o
f A
lph
a P
ha
se
Temperature [oC]
Ti-Corona-X
Exp [03Boy]
Calculated
CompuTherm LLC Thermodynamic Databases
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[1994Boy] R. Boyer, G. Welsch and E. W. Collings, Materials Properties Handbook: Titanium Alloys, ASM International, Materials Park,
OH, 1994.
[2001Kha] K.K. Kharia and H.J. Rack, Met. Trans., 32A (2001), 671-679.
[2003Boy] R. Boyer, Boeing, private communication, 2003.
[2003Fur] D. Furrer, LADISH, private communication, 2003.
[2003Sem] S.L. Semiatin, S.L. Knisley, P.N. Fagin, F. Zhang and D.R.
Barker, Met. Trans., 34A (2003), 2377-2386.
[2003Ven] V. Venkatesh, TIMET, private communication, 2003.
[2005Sem] S.L. Semiatin, AFRL, private communication, 2005.
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82
8. PanBMG
Thermodynamic Database for Bulk Metallic Glass
Copyright © CompuTherm LLC
BMG
Al
Cu
Ni
Si
Ti
Zr
CompuTherm LLC Thermodynamic Databases
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8.1 Components
Total of 6 components are included in the database as listed here:
Major alloying elements: Al, Cu, Ni, Ti, Si, and Zr
8.2 Suggested Composition Range
The suggested composition range for each element is listed in Table 8.1. The
PanBMG database is a full description of the six-component system, which
includes 15 binaries and 20 ternaries.
Table 8.1: Suggested composition range
Element Composition range (wt%)
Al 0-100
Cu 0-100
Ni 0-100
Ti 0-100
Zr 0-100
Si 0-100
8.3 Phases
Total of 122 phases are included in the database, which account for all the
stable phases appearing in the alloy system. The name, the structure, and
model type of major phases are given in Table 8.2.
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Table 8.2: Phase name and related information
Name Lattice Size Constituent
Al5CuTi2 (0.75)(0.25) (Al,Cu)(Ti)
Al5CuZr2 (0.625)(0.125)(0.25) (Al)(Cu)(Zr)
Al6Cu3Ni (0.6)(0.3)(0.1) (Al)(Cu)(Ni)
AlCu2Ti (0.75)(0.25) (Al,Cu)(Ti)
AlCu2Zr (0.25)(0.5)(0.25) (Al)(Cu)(Zr)
AlCuTi (0.6667)(0.3333) (Al,Cu)(Ti)
AlCuZr (0.667)(0.333) (Al,Cu)(Zr)
B2 (0.5)(0.5) (Al,Cu,Ni,Ti,Zr)(Cu,Ni,Ti,Zr,VA)
Bcc (1)(3) (Al,Cu,Ni,Si,Ti,Zr)(VA)
Cu2TiZr (0.5)(0.25)(0.25) (Cu)(Ti)(Zr)
Cu3Si4Zr2 (0.3334)(0.4444)(0.2222) (Cu)(Si)(Zr)
Cu4Si2Zr3 (0.4444)(0.2222)(0.3334) (Cu)(Si)(Zr)
Cu4Si4Zr3 (0.3636)(0.3636)(0.2728) (Cu)(Si)(Zr)
Fcc (1)(1) (Al,Cu,Ni,Si,Ti,Zr)(Va)
Gamma_D83 (1)(1) (Al,Cu,Ni,Si)(Va)
Hcp (1)(0.5) (Al,Cu,Ni,Si,Ti,Zr)(Va)
L12 (0.75)(0.25)(1) (Al,Cu,Ni,Si,Ti,Zr)(Al,Cu,Ni,Si,Ti,Zr)(Va)
Laves_C14 (2)(1) (Al,Ni,Ti)(Al,Ni,Ti)
Liquid (1) (Al,Cu,Ni,Si,Ti,Zr)
Ni4Si9Zr7 (0.2)(0.45)(0.35) (Ni)(Si)(Zr)
NiSiZr (0.3333)(0.3333)(0.3334) (Ni)(Si)(Zr)
NiTi (0.5)(0.5) (Cu,Ni)(Al,Ti,Zr)
NiTi2 (0.333333)(0.666667) (Cu,Ni)(Al,Ti)
NiTiZr (1)(1)(1) (Ni)(Ti)(Zr)
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8.4 Sub-System Information
All the binary systems and ternary systems in the PanBMG database were
critically assessed and thermodynamic descriptions were validated
extensively against experimental information. All the equilibrium phases in
each binary system and ternary system were covered in the database.
Complete phase diagrams can be calculated for all binary and ternary
systems in the Zr-Al-Cu-Ni-Ti-Si system. The binary systems and ternary
systems included in the PanBMG database are listed in Tables 8.3 and 8.4.
A calculated Cu-Zr binary phase diagram and a calculated liquidus
projection for the Al-Ni-Zr system are shown in Figures 8.1 and 8.2,
respectively.
Some sub-quaternary systems of this database have been critically assessed
and thermodynamically modeled. Figure 8.3 shows the comparison between
the calculated integral enthalpy of mixing of liquid Al17Ni66Si17—Cu alloys at
1575K and the experimental data from [2000Wit].
: Full description
: Full description for major phases
: Extrapolation
Table 8.3 Binary Systems Included in the PanBMG Database
Cu Ni Si Ti Zr
Al Al-Cu Al-Ni Al-Si Al-Ti Al-Zr
Cu Cu-Ni Cu-Si Cu-Ti Cu-Zr
Ni Ni-Si Ni-Ti Ni-Zr
Si Si-Ti Si-Zr
Ti Ti-Zr
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Table 8.4: Ternary Systems Included in the PanBMG Database
Ni Si Ti Zr
Al-Cu Al-Cu-Ni Al-Cu-Si Al-Cu-Ti Al-Cu-Zr
Al-Ni Al-Ni-Si Al-Ni-Ti Al-Ni-Zr
Al-Si Al-Si-Ti Al-Si-Zr
Al-Ti Al-Ti-Zr
Cu-Ni Cu-Ni-Si Cu-Ni-Ti Cu-Ni-Zr
Cu-Si Cu-Si-Ti Cu-Si-Zr
Cu-Ti Cu-Ti-Zr
Ni-Si Ni-Si-Ti Ni-Si-Zr
Ni-Ti Ni-Ti-Zr
Si-Ti Si-Ti-Zr
Figure 8.1: Calculated Cu-Zr binary phase diagram
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Figure 8.2: Calculated liquidus projection for Al-Ni-Zr ternary system
Figure 8.3: Comparison between the calculated and experimental integral enthalpy of
mixing of liquid Al17Ni66Si17—Cu alloys at 1575K
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8.5 Database Validation
Since the major application of the PanBMG database is to predict the
composition region of low-lying liquidus surfaces of the Zr-Al-Cu-Ni-Si-Ti
system where bulk metallic glass (BMG) tends to form, the database is
validated by comparing the predicted composition region with the low-lying
liquidus surfaces and experimentally identified bulk metallic glass forming
region. The low-lying liquidus surfaces are indicated by the temperatures of
the invariant reactions occurring on the liquidus surface, which can be
automatically calculated by Pandat. Examples of these comparisons for Zr-
Cu-Ni-Ti and Zr-Al-Cu-Ni-Ti are given below.
Zr-Cu-Ni-Ti
Using the PanBMG database, the invariant temperatures for all the five-
phase equilibria in the Cu-Ni-Ti-Zr alloys with one of these phases being a
liquid phase were calculated. Figure 8.4 compares the calculated liquid
composition of the invariant reactions with the lowest temperatures and
experimentally identified regions for BMG formation [2001Yan]. The
calculated liquid compositions of these invariant reactions are denoted as
solid circles and the experimentally identified BMG forming compositions by
Lin and Johnson [1995Lin] are denoted by open squares.
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0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.4
0.6
0.8
1.0
X(Zr)
X(Cu+Ni)X(Ti)
Calculated
Lin, Johnson
Figure 8.4: Comparison of the thermodynamically predicted and experimentally identified
[1995Lin] liquid compositions of the five-phase invariant reactions with one of phases being
liquid in the Zr-Cu-Ni-Ti system
Zr-Al-Cu-Ni-Ti
Figure 8.5 shows that thermodynamically predicted liquid alloy compositions
with low-lying liquidus surface illustrate a region of the quinary composition
space, in which a series of new Zr-rich alloys were subsequently found
experimentally to form bulk metallic glasses with diameters up to 14mm by
using the conventional copper mold dropping casting (or suction casting)
method. Five representative novel glass-forming alloys are denoted as G1-G5
in Figure 8.5 as well. Strikingly, the calculated compositional region is noted
to be in good agreement with those experimental results [1999Joh, 1996Xin,
2000Pel, 1999Xin, 2003Zha, 2005Cao, 2005Ma] (presented as green dots in
Figure 8.5).
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Figure 8.5: Comparison of the thermodynamically predicted and experimentally identified
liquid compositions of the six-phase invariant equilibria with one of phases being liquid in
the Zr-Al-Cu-Ni-Ti system
Figure 8.6 shows a calculated isopleth of the quinary Zr-Al–Cu–Ni–Ti phase
diagram with 8.5%Al, 31.3%Cu, and 4.0%Ni, using the PanBMG database.
The concentration of Ti varies from 0 to 15% with a corresponding
concentration of Zr from 56.2% to 41.2%. In other words, Ti was used to
partially replace Zr in a quaternary base alloy Zr56.2Cu31.3Ni4.0Al8.5. This
quaternary alloy was identified to be a bulk glass-forming alloy (with a
critical casting diameter for glass formation of 6 mm) based on the calculated
low-lying liquidus surface of the quaternary Zr–Al-Cu-Ni system. As shown
in this isopleth, the calculated liquidus at the origin of the compositional
coordinate, i.e., the base alloy Zr56.2Cu31.3Ni4.0Al8.5, decreases rapidly to a
minimum of about 4.9%Ti and then increases again. Thus, the liquidus
depression reaches a maximum of 102K at 4.9%Ti replacement. Accordingly,
a series of alloys of Zr56.2-xTixCu31.3Ni4.0Al8.5 with values of x varying from 0 to
12, were prepared with the expectation that the alloy with 4.9%Ti would
exhibit the highest Glass Forming Ability (GFA).
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Figure 8.6: (a) The critical casting diameter as a function of Ti concentration in a series
of alloys Zr56.2-xTixCu31.3Ni4.0Al8.5(x=0–12), showing A* (containing 4.9%Ti) is the bulkiest
glass-forming alloy; (b) The calculated isopleth with the compositions of Cu, Ni, and Al fixed
at 31.3%, 4.0%, and 8.5%, respectively. The shaded area denotes the experimentally
observed bulk glass-forming range
Figure 8.7: Surface appearance of the glassy alloys rods obtained in a recent study based
on the thermodynamic calculations
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8.6 References
[1995Lin] X. H. Lin and W. L. Johnson, J Appl. Phys., 1995; 78 (11), 6514.
[1996Xin] L. Q. Xing, P. Ochin, M. Harmelin, F. Faudot, J. Bigot and J. P. Chevalier, Mater Sci Eng, 1996, A220(1-2), 155-161.
[1999Joh] W. L. Johnson, MRS Bulletin, 1999, 24(10), 42.
[1999Xin] L. Q. Xing, J. Eckert, W. Loser, L. Schultz, Appl Phys Lett, 1999, 74(5), 664.
[2000Pel] J. M. Pelletier, J. Perez and J. L. Soubeyroux, J Non-Cryst Solids 2000, 274(1-3), 301-306.
[2000Wit] V. T. Witusiewicz, I. Arpshofen, H. J. Seifert, F. Sommer, F. Aldinger, Thermochimica Acta, 356(2000), 39-57.
[2001Yan] X.-Y. Yan, Y. A. Chang, Y. Yang, F.-Y. Xie, S.-L. Chen, F. Zhang,
S. Daniel, M.-H. He, Intermetallics, 2001, 9, 535-538.
[2003Zha] Y. Zhang, D. Q. Zhao, M. X. Pan and W. H. Wang, J Non-Cryst Solids, 2003, 315(1,2), 206.
[2005Cao] H. Cao, D. Ma, K-C Hsieh, L. Ding, W. G. Stratton, P. M. Voyles,
Y. Pan and Y. A. Chang, unpublished.
[2005Ma] D. Ma, H. Cao, L. Ding, Y. A. Chang, K. C. Hsieh and Y. Pan, Applied Physics Letters, 87, 171914 (2005).
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9. ADAMIS
Alloy Database for Micro-Solders
Materials Design Technology Co.,Ltd.
2-5 Odenmacho, Nihonbashi, Chuo-ku
Tokyo 103-0011 JAPAN
Copyright © Materials Design Technology Co.,Ltd.
ADAMIS
Solder
Ag Al
Au
Bi
Cu
In Ni
Pb
Sb
Sn
Zn
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9.1 Components
Total of 11 components are included in the database as listed here:
Major elements: Ag, Al, Au, Bi, Cu, In, Ni, Pb, Sb, Sn, and Zn
9.2 Suggested Composition Range
The suggested composition range for each element is listed in Table 9.1. It
should be noted that the ADAMIS solder database has been tested with
many commercial micro-soldering alloys, such as Sn-Ag-X, Sn-Cu-X, Sn-In-
X, Sn-Zn-X based alloys, and also Cu-X-Y based alloy systems.
Table 9.1: Suggested composition range
9.3 Phases
Total of 122 phases are included in the database, which account for most of
the phases appearing in the commercial micro-soldering alloys. The name,
the structure, and model type of major phases are given in Table 9.2.
Element Composition range (wt%)
Ag 0-100
Al 0-100
Au 0-100
Bi 0-100
Cu 0-100
In 0-100
Ni 0-100
Pb 0-100
Sb 0-100
Sn 0-100
Zr 0-100
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9.4 Sub-System Information
Tohoku University started to carry out research and experiment for the
solder-semiconductor systems since 1980’s, and based on which the
ADAMIS solder database was developed.
Table 9.3 lists all the 55 binary systems. Thermodynamic descriptions for all
these binaries are critically assessed as colored by green. Table 9.4 lists all
the ternary systems that are assessed for this system. Thermodynamic
descriptions for the ternaries in green color are critically assessed; while
those in yellow color are also developed, but are not yet fully validated.
ADAMIS database can be used to predict various thermodynamic properties
for Sn-Ag-X, Sn-Cu-X, Sn-In-X, Sn-Zn-X based alloy, and also Cu-X-Y based
alloy systems.
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Table 9.2: Phase name and related information
Name Lattice Size Constituent
Liquid (1) (Ag,Al,Au,Bi,Cu,In,Ni,Pb,Sb,Sn,Zn)
BCC (1) (Ag,Al,Au,Bi,Cu,In,Ni,Pb,Sb,Sn,Zn)
BCT_A5 (1) (Ag,Bi,Cu,In,Ni,Pb,Sb,Sn,Zn)
Fcc (1) (Ag,Al,Au,Bi,Cu,In,Ni,Pb,Sb,Sn,Zn)
Hcp (1) (Ag,Al,Au,Bi,Cu,In,Ni,Pb,Sb,Sn,Zn)
RhombohedralA7 (1) (Ag,Au,Bi,Cu,In,Pb,Sb,Sn,Zn)
Tetragonal_A6 (1) (Bi,In,Pb,Sb,Sn,Zn)
AgCuZn_Eps (1) (Ag,Al,Cu,Zn)
AgCuZn_Gamma (0.15385)(0.15385) (0.23077)(0.46154)
(Ag,Cu,Zn)(Ag,Cu,Zn)(Ag,Cu)(Zn)
AgZn_Zeta (1) (Ag,Sn,Zn)
Ag3SnSb (0.75)(0.25) (Ag,Sb)(Ag,Bi,Sb,Sn)
BiInPbSn_Bea (1) (Bi,In,Pb,Sn)
Cu77InSn (0.77)(0.23) (Cu)(In,Sn)
Cu7In3 (0.7)(0.3) (Cu)(In,Sn)
CuInSn_Eta (0.545)(0.122)(0.333) (Cu)(Cu,In,Sn)(In,Sn)
Cu3Sn (0.75)(0.25) (Cu)(In,Sn)
Cu41Sn11 (0.788)(0.212) (Cu)(In,Sn)
Gama (0.654)(0.115)(0.231) (Cu)(Cu,In)(In,Sn)
InSn_Gamma (1) (Bi,In,Sb,Sn)
Sb1Sn1 (1) (Pb,Sb,Sn)
AuIn (0.5)(0.5) (Au)(In,Sb,Sn)
AuIn2 (0.33333)(0.66667) (Au)(In,Sb,Sn)
AlCu_GammaH (0.3077)(0.0769)(0.6154) (Al,Zn)(Al,Cu,Zn)(Ag,Cu)
Sn2Ni3 (0.5)(0.25)(0.25) (Ni,Sn)(Au,Ni)(Au,Ni)
NiZn_Bet1 (1)(1) (Cu,Ni,Zn)(Ni,Zn)
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: Full description
: Full description for major phases
: Extrapolation
Table 9.3: Current Status of Binary Systems of ADAMIS database
Al Au Bi Cu In Ni Pb Sb Sn Zn
Ag Ag-Al Ag-Au Ag-Bi Ag-Cu Ag-In Ag-Ni Ag-Pb Ag-Sb Ag-Sn Ag-Zn
Al Al-Au Al-Bi Al-Cu Al-In Al-Ni Al-Pb Al-Sb Al-Sn Al-Zn
Au Au-Bi Au-Cu Au-In Au-Ni Au-Pb Au-Sb Au-Sn Au-Zn
Bi Bi-Cu Bi-In Bi-Ni Bi-Pb Bi-Sb Bi-Sn Bi-Zn
Cu Cu-In Cu-Ni Cu-Pb Cu-Sb Cu-Sn Cu-Zn
In In-Ni In-Pb In-Sb In-Sn In-Zn
Ni Ni-Pb Ni-Sb Ni-Sn Ni-Zn
Pb Pb-Sb Pb-Sn Pb-Zn
Sb Sb-Sn Sb-Zn
Sn Sn-Zn
Table 9.4: Current Status of Ternary systems of ADAMIS database
Ag-Bi-Cu Ag-Bi-In Ag-Bi-Pb Ag-Bi-Sb Ag-Bi-Sn Ag-Bi-Zn
Ag-Cu-In Ag-Cu-Pb Ag-Cu-Sb Ag-Cu-Sn Ag-Cu-Zn Ag-In-Pb
Ag-In-Sb Ag-In-Sn Ag-In-Zn Ag-Pb-Sb Ag-Pb-Sn Ag-Pb-Zn
Ag-Sb-Sn Ag-Sb-Zn Ag-Sn-Zn
Bi-Cu-In Bi-Cu-Pb Bi-Cu-Sb Bi-Cu-Sn Bi-Cu-Zn Bi-In-Pb
Bi-In-Sb Bi-In-Sn Bi-In-Zn Bi-Pb-Sb Bi-Pb-Sn Bi-Pb-Zn
Bi-Sb-Sn Bi-Sb-Zn Bi-Sn-Zn
Cu-In-Pb Cu-In-Sb Cu-In-Sn Cu-In-Zn Cu-Pb-Sb Cu-Pb-Sn
Cu-Pb-Zn Cu-Sb-Sn Cu-Sb-Zn Cu-Sn-Zn
In-Pb-Sb In-Pb-Sn In-Pb-Zn In-Sb-Sn In-Sb-Zn In-Sn-Zn
Pb-Sb-Sn Pb-Sb-Zn Pb-Sn-Zn
Sb-Sn-Zn
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9.5 Database Validation
Figure 9.1: Ternary Sn-Ag-Cu 400 C Isotherm with the experimental data [2000Ohn]
Figure 9.2: Ternary Sn-Ag-Cu 600 C Isotherm with the experimental data [1959Geb]
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Figure 9.3: Vertical section diagram of the Ag-Cu-Sn ternary with 10mass% Sn, the
experimental data [1959Geb] are plotted for comparison
Figure 9.4: Vertical section diagram of the Ag-Cu-Sn ternary with 25mass% Sn, the
experimental data [1959Geb] are plotted for comparison
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Figure 9.5: Projection of liquidus surface in Sn-rich portion of the Sn-Ag-Cu ternary
9.6 Applications
Alloy design and processing optimization for micro-soldering alloys.
Multi-component phase diagram calculations, such as liquidus
projection, isothermal section and isopleth.
Solidification sequence simulation using the Scheil model to predict the
microstructure of multi-component solder alloys at the as-cast state.
Equilibrium line calculation to predict the microstructure information,
such as equilibrium phases, phase fraction, phase composition and
phase transformation temperature.
Thermodynamic property calculations, such as specific heat and latent
heat.
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9.7 References
[1959Geb] E.Gebhardt and G.Petzow, Z. Metallkd., 50 (1959), 597-605.
[1999Ohn] I.Ohnuma, X.J.Liu, H.Ohtani, and K.Ishida, J. Electron. Mater., 28 (1999), 1164-1171.
[2000Ohn] I.Ohnuma, M.Miyashita, K.Anzai, X.J.Liu, H.Ohtani,
R.Kainuma, and K.Ishida, J. Electron. Mater., 29 (2000), 1137-1144.
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10. MDT Copper
Thermodynamic database for multi-component Cu-rich alloys
Copyright © CompuTherm LLC
Cu
Al B
Bi
C
Cr
Fe
Mn Ni P
Pb
Se
Si
Sn
Ti
Zn
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10.1 Components
Total of 16 components are included in the database as listed here:
Major alloy elements: Cr, Cu, Fe, Ni, Pb, Si, Sn, Zn
Minor alloy elements: Al, B, Bi, C, Mn, P, Se and Ti
10.2 Suggested Composition Range
The suggested composition range for each element is listed in Table 10.1. It
should be noted that this comosition range is based on the validation we
performed on commercial alloys. For perticular subsystems, the application
range may be wider. Some subsystems can be applied to the entire
composition arnge as given in section 10.4.
Table 10.1: Suggested composition range
Elements Composition Range (wt.%)
Cu 50 ~ 100
Al, Mn 0 ~ 3
Cr, Fe 0 ~ 10
Ni 0 ~ 35
Bi, P, Se 0 ~ 2
Pb, Si 0 ~ 5
Sn 0 ~ 14
Zn 0 ~ 45
B, C, Ti 0 ~ 0.5
10.3 Phases
Total of 219 phases are included in the database and a few key phases are
listed in Table 10.2. Information on all the other phases can be found at
www.computherm.com.
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Table 10.2: Phase name and related information
Name Lattice Size Constituent
Al2Cu (0.667)(0.333) (Al)(Al,Cu)
AlCu_Delta (0.4)(0.6) (Al)(Cu)
AlCu_Eps1 (0.4)(0.6) (Al,Cu)(Al,Cu)
AlCu_Eps2 (0.5)(0.5) (Al,Cu)(Cu)
AlCu_Eta (0.5)(0.5) (Al,Cu)(Cu)
AlCu_Zeta (0.45)(0.55) (Al)(Cu)
Bcc (1)(3) (Al,B,Bi,Cr,Cu,Fe,Mn,Ni,P,Pb,Si,Sn,Ti,Zn)(C,Va)
Cu3Se2 (3)(2) (Cu)(Se)
Cu3Ti2 (0.6)(0.4) (Cu)(Ti)
Cu41Sn11_LEE (0.788)(0.212) (Cu)(Sn)
Cu4Ti (0.8)(0.2) (Cu,Ti)(Cu,Ti)
Cu4Ti3 (0.571)(0.429) (Cu)(Ti)
Cu56Si11 (0.835821)(0.164179) (Cu,Zn)(Si)
CuInSn_Eta (0.545)(0.122)(0.333) (Cu)(Cu,Sn)(Sn)
Fcc (1)(1) (Al,B,Bi,Cr,Cu,Fe,Mn,Ni,P,Pb,Si,Sn,Ti,Zn)(C,Va)
Gammabrass (1) (Al,Cu,Fe,Ni,Si,Zn)
Hcp (1)(0.5) (Al,B,Bi,Cr,Cu,Fe,Mn,Ni,Pb,Si,Sn,Ti,Zn) (C,Va)
Laves_C15 (2)(1) (Cr,Cu,Fe,Ni,Ti)(Cr,Cu,Fe,Ni,Ti)
Laves_C36 (2)(1) (Cu,Ni,Ti)(Cu,Ni,Ti)
Liquid (1) (Al,B,Bi,Bi2Se3,C,Cr,CrSe,Cu,Cu2Se,Fe,FeSe,Mn,Ni,P,Pb,Se,MnSe,PbSe,Si,Sn,SeNi,SeSn,Se2Si,SeZn,Ti,Zn)
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10.4 Key Elements and Subsystems
Key elements of the system are listed as: Cu-Cr-Fe-Ni-Pb-Si-Sn-Zn. The
modeling status for the constituent binaries and ternaries of these key
elements are given in Tables 10.3-10.4. The color represents the following
meaning:
: Full description
: Full description for major phases
: Extrapolation
Table 10.3: Key Binary Systems for the MDT Cu Database
Cr Cu Fe Ni Pb Si Sn Zn
Al Al-Cr Al-Cu Al-Fe Al-Ni Al-Pb Al-Si Al-Sn Al-Zn
Cr
Cr-Cu Cr-Fe Cr-Ni Cr-Pb Cr-Si Cr-Sn Cr-Zn
Cu
Cu-Fe Cu-Ni Cu-Pb Cu-Si Cu-Sn Cu-Zn
Fe
Fe-Ni Fe-Pb Fe-Si Fe-Sn Fe-Zn
Ni Ni-Pb Ni-Si Ni-Sn Ni-Zn
Pb Pb-Si Pb-Sn Pb-Zn
Si Si-Sn Si-Zn
Sn Sn-Zn
Table 10.4: Ternary Systems for the Key Cu-Cr-Fe-Ni-Sn-Zn Subset
Fe Ni Sn Zn
Cu-Cr Cu-Cr-Fe Cu-Cr-Ni Cu-Cr-Sn Cu-Cr-Zn
Cu-Fe Cu-Fe-Ni Cu-Fe-Sn Cu-Fe-Zn
Cu-Ni Cu-Ni-Sn Cu-Ni-Zn
Cu-Sn Cu-Sn-Zn
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10.5 Database Validation
Figure 10.1: Calculated isothermal section diagrams of the Fe-Cu-Cr system at (a) 1273K,
(b) 1373K, and (c) 1573K with the experimental data [1997Oht, 2002Wan]
mas
s% C
r
mass% Cu
0.0
17.3
34.6
52.0
69.3
86.6
0 20 40 60 80 1000 20 40 60 80 1000
20
40
60
80
100
mass% Cu
mass
% C
r
FE
CR
CU
FCC_A1+Liq
BCC_A2+Liq
mas
s% C
r
mass% Cu
0.0
17.3
34.6
52.0
69.3
86.6
0 20 40 60 80 1000 20 40 60 80 1000
20
40
60
80
100
mass% Cu
mass
% C
r
FE
CR
CU
FCC_A1+Liq
BCC_A2+Liq
mas
s% C
r
mass% Cu
0.0
17.3
34.6
52.0
69.3
86.6
0 20 40 60 80 1000 20 40 60 80 1000
20
40
60
80
100
mass% Cu
mass
% C
r
FE
CR
CU
FCC_A1+FCC_A1
BCC_A2+FCC_A1
(a) 1273K
(b) 1373K
(c) 1573K
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Figure 10.2: Calculated isothermal section diagrams of the Fe-Cu-Si system at (a) 1173K,
(b) 1573K, and (c) 1723K with the experimental data [1997Oht, 1999Him, 2002Wan]
mas
s% C
r
mass% Cu
0.0
17.3
34.6
52.0
69.3
86.6
0 20 40 60 80 1000 20 40 60 80 1000
20
40
60
80
100
mass% Cu
mass
% C
r
FE
SI
CU
Liq
Liq1Liq2
Liq1+Liq2
BCC
FCC
(c) 1723K
mas
s% S
i
mass% Cu
0.0
17.3
34.6
52.0
69.3
86.6
0 20 40 60 80 1000 20 40 60 80 1000
20
40
60
80
100
mass% Cu
mass
% S
i
FE
SI
CU
(Si)+Liq
Liq2
Liq1
FCC_A1
BCC_A2BCC_A2+LIQUID
Liq1+Liq2
FeSi+Liq2
FeSi+Liq1+Liq2
(b) 1573K
mas
s% S
i
mass% Cu
0.0
17.3
34.6
52.0
69.3
86.6
0 20 40 60 80 1000 20 40 60 80 1000
20
40
60
80
100
mass% Cu
mass
% S
i
FE
SI
CU
FeSi2+(Si)+Liq
BCC_A2+FCC_A1
FeSi2+FeSi+Liq
FeSi+Liq
Fe5Si3+FeSi+FCC_A1Fe5Si3+BCC_A2+FCC_A1
(a) 1173K
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10.6 References
[1997Oht] H.Ohtani, H.Suda, K.Ishida, ISIJ International, 37 (1997), 207-
216.
[1998Kai] R.Kainuma, N.Satoh, X.J.Liu, I.Ohnuma, K.Ishida, J. Alloys Compounds, 266 (1998), 191-200. (Cu-Al-Mn)
[1998Wan] C.P.Wang, X.J.Liu, I.Ohnuma, R.Kainuma, S.M.Hao, and K.Ishida, Z. Metallkunde, 98 (1998), 828-835. ( Cu-Al-Fe)
[1999Him] M.Hino, T.Nagasaka, and T.Washizu, J. Phase Equilibria, 20 (1999), 179-186.
[2000Wan] C.P.Wang, X.J.Liu, I.Ohnuma, R.Kainuma, K.Ishida, CALPHAD, 24 (2000), 149-167.
[2002Wan] C.P.Wang, X.J.Liu, I.Ohnuma, R.Kainuma, K.Ishida, J. Phase Equilibria, 23 (2002), 236-245.
[2004Wan] C.P.Wang, X.J.Liu, I.Ohnuma, R.Kainuma, K.Ishida, J. Phase Equilibria, 25 (2004), 320-328.
[2005Jia] M.Jiang, C.P.Wang, X.J.Liu, I.Ohnuma, R.Kainuma,
G.P.Vassilev, K.Ishida, J. Physics Chem. of Solids, 66 (2005), 246-250. (Cu-Ni-Zn)