modelling of phases in mg-db - computherm llc · total of 250 phases are included in the database...

Thermodynamic Database

User’s Guide

Copyright © 2000-2013 CompuTherm LLC

CompuTherm LLC Thermodynamic Databases

i

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


3.3 Phases ........................................................................................... 18


ii



3.6 References ..................................................................................... 28

4. PanMagnesium ................................................................................. 29

4.1 Components .................................................................................. 30


4.3 What's new in PanMg2013 ............................................................. 30

4.4 Phases ........................................................................................... 31



4.7 References ..................................................................................... 42

5. PanMolybdenum ............................................................................... 45

5.1 Components .................................................................................. 46


5.3 Phases ........................................................................................... 46



5.6 Reference ..................................................................................... 544

6. PanNickel ......................................................................................... 55

6.1 Components .................................................................................. 56


iii


6.3 Phases ........................................................................................... 56



6.6 References ..................................................................................... 67

7. PanTitanium ..................................................................................... 68

7.1 Components .................................................................................. 69


7.3 Phases ........................................................................................... 69

7.4 Sub-System Information ................................................................ 70


7.6 References ..................................................................................... 80

8. PanBMG ........................................................................................... 82

8.1 Components .................................................................................. 83


8.3 Phases ........................................................................................... 83



8.6 References ..................................................................................... 92

9. ADAMIS ............................................................................................ 93


iv

9.1 Components .................................................................................. 94


9.3 Phases ........................................................................................... 94



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


1

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


2

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 .

http://www.computherm.com/


3

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)


4

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.


5

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)


6

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


7

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


8

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).


9

2. PanCobalt

Thermodynamic Database for Cobalt-Based Superalloys


Co

Al B

C

Cr

Fe

Mo Ni

Pt

Re

Ta

W


10

2.1 Components


Major alloying elements: Al, Co, Cr, Fe, Mo, Ni, Pt, Re, Ta, and W

Minor alloying elements: B and C






composition range as given in Table 2.4.


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 .



11



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)


12


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


: 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


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.


13

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


14

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


15

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.


16

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.


17

3. PanIron

Thermodynamic database for multi-component Fe-rich alloys


Fe

Al B C

Co

Cr

Cu

Mg

Mn

Mo N Nb Ni

P

S

Si

Sn

Ti

V

W Zr


18

3.1 Components


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






composition range as given in section 3.4.


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 .



19



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)


20


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


: 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


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


21

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.


22

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


23

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


24

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


25

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


26

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


27

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


28

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


29

4. PanMagnesium

Thermodynamic database for multi-component magnesium-rich casting and wrought alloys



30

4.1 Components


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



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.


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.


31

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 .



32

Table 4.2: Selected Phase names and related information


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)


33


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


: 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


34

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


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


35

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.


36

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)


37

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.


38

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


39

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


40

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)


41

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


42

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:


43

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.


44

[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


45

5. PanMolybdenum

Thermodynamic database for multi-component Mo-rich alloys


Mo

Al B

Cr

Fe

Hf

Mn O

Re

Si

Ti

Zr


46

5.1 Components


Major alloying elements Al, B, Cr, Hf, Mn, Mo, Re, Si, Ti

Minor alloying elements: Fe, O and Zr








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



www.computherm.com.


47



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)


48


Key elements of the system are listed as: Mo-B-Cr-Hf-Mn-Re-Si-Ti. The



meaning:

: Full description


: 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


49


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


50

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


51

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


52

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)


53

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)


54

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)


55

6. PanNickel

Thermodynamic Database for Nickel-Based Superalloys


Ni

Al B C

Co

Cr

Cu

Fe

Hf

Ir

Mn Mo N

Nb

Pt

Re

Ru

Si

Ta

Ti

W Zr


56

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






composition range as given in Table 6.4.


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.



57



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)


58


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


meaning:

: Full description


: 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


59

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


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,


60

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.


61

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]



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]


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


63

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

'

'

'

'

'

'


64


compositions of Co in and phases


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

'

'

'

'


65


compositions of Mo in and phases


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

()

()

'

'


66


compositions of Ti in and phases


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

()

()

()

()

'

'

'

'


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.


68

7. PanTitanium

Thermodynamic Database for Titanium-Based Alloys


Ti

Al B

C

Cr

Cu

Fe

H

Mo N Nb

Ni

O

Si

Sn

Ta

V

Zr


69

7.1 Components


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




performed on commercial alloys.



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 .



70

Table 7.2: Phase Name and Related Information


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.


71

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


: 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


72


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]


IMI 834 transus [2003Fur]


Ti-10-2-3 transus [2003Fur]

Ti-6-6-2 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]


73

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


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


75

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


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


77

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


78

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


79

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


80

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


81

[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.


82

8. PanBMG

Thermodynamic Database for Bulk Metallic Glass


BMG

Al

Cu

Ni

Si

Ti

Zr


83

8.1 Components


Major alloying elements: Al, Cu, Ni, Ti, Si, and Zr


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.



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.


84



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)


85


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


: 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


86

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


87

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


88


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.


89

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).


90

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).


91

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


92

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).


93

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


94

9.1 Components


Major elements: Ag, Al, Au, Bi, Cu, In, Ni, Pb, Sb, Sn, and Zn



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.


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.


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


95


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.


96



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)


97

: Full description


: 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


98


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]


99

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


100

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.


101

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.


102

10. MDT Copper

Thermodynamic database for multi-component Cu-rich alloys


Cu

Al B

Bi

C

Cr

Fe

Mn Ni P

Pb

Se

Si

Sn

Ti

Zn


103

10.1 Components


Major alloy elements: Cr, Cu, Fe, Ni, Pb, Si, Sn, Zn

Minor alloy elements: Al, B, Bi, C, Mn, P, Se and Ti








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



www.computherm.com.


104



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)


105


Key elements of the system are listed as: Cu-Cr-Fe-Ni-Pb-Si-Sn-Zn. The



meaning:

: Full description


: 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


106


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


107

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


108

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)

modelling of phases in mg-db - computherm llc · total of 250 phases are included in the database...

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