TCNI8 www.thermocalc.com 1 of 46 TCNI8: TCS Ni-based Superalloys Database (Extended Information) Database name: TCS Ni-based Superalloys Database Database acronym: TCNI Database owner: Thermo-Calc Software AB Database version: 8.1 TCNI is a thermodynamic database for different kinds of Ni-based superalloys for use with Thermo-Calc and the add-on Diffusion Module (DICTRA) and/or Precipitation Module (TC-PRISMA). TCNI contains all the important Ni-based superalloy phases within a 25-element framework + Ar and H for the gas phase only. Developed using the CALPHAD approach with industry input and support, TCNI is based on the critical evaluation of binary, ternary and in some cases higher order systems which enables predictions to be made for multicomponent systems and alloys of industrial importance. The database has also been validated where possible against higher order systems as well. All the necessary volume data (including molar volume and thermal expansion) for various alloy phases is incorporated, which allows for the calculation of volume fraction of phases, as well as density, thermal expansivity and lattice parameters, e.g. misfits between γ and γ’, using Thermo-Calc. However, it should be noted that the molar volume data only provides rough estimations and has no pressure dependence. The TCNI database also contains an extensive GAS mixture phase for the main purpose of considering oxygen/nitrogen-gas controls in alloy making processes, and different gas atmospheres under e.g. heat treatments. Note that argon, Ar, and hydrogen, H, are included in the gas phase only, and there is no solid solubility or condensed phase compounds with these elements included in the TCNI8 database. TCNI includes critically assessed thermodynamic descriptions for 27 elements and 534 phases. Most of the binary systems in this database have been assessed and can be calculated with the BINARY module in Thermo-Calc. TCNI also contains many assessed ternary systems, at least those being in equilibrium with γ and γ’ phase, and can be calculated with the TERNARY Module in Thermo-Calc. These 27 elements are included: Al Ar B C Co Cr Cu Fe H Hf Mn Mo N Nb Ni O Pd Pt Re Ru Si Ta Ti V W Y Zr Ordered and disordered bcc (A2 and B2/β) and fcc (A1 and L12/γ´) phases are modeled with a two sub- lattice model using a single Gibbs energy curve which enables order/disorder transformations to be modeled. All possible binary systems and most Ni-containing ternary systems have been assessed to the full range of composition. TCP phases are modeled using more complex and physically correct models, which gives the ability to correctly predict site-fractions etc. Oxygen has been implemented in an ambitious way using the Compound Energy Formalism (CEF) [1] for the solution phases, e.g. spinel, halite, corundum etc., and the ionic two-sublattice model [2][3] for the metallic and ionized liquid. Molar volume data critically assessed for most phases of importance to Ni-based Superalloys.
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Database owner: Thermo-Calc Software AB Database version: 8.1
TCNI is a thermodynamic database for different kinds of Ni-based superalloys for use with Thermo-Calc and the add-on Diffusion Module (DICTRA) and/or Precipitation Module (TC-PRISMA). TCNI contains all the important Ni-based superalloy phases within a 25-element framework + Ar and H for the gas phase only.
Developed using the CALPHAD approach with industry input and support, TCNI is based on the critical evaluation of binary, ternary and in some cases higher order systems which enables predictions to be made for multicomponent systems and alloys of industrial importance. The database has also been validated where possible against higher order systems as well.
All the necessary volume data (including molar volume and thermal expansion) for various alloy phases is incorporated, which allows for the calculation of volume fraction of phases, as well as density, thermal expansivity and lattice parameters, e.g. misfits between γ and γ’, using Thermo-Calc. However, it should be noted that the molar volume data only provides rough estimations and has no pressure dependence.
The TCNI database also contains an extensive GAS mixture phase for the main purpose of considering oxygen/nitrogen-gas controls in alloy making processes, and different gas atmospheres under e.g. heat treatments. Note that argon, Ar, and hydrogen, H, are included in the gas phase only, and there is no solid solubility or condensed phase compounds with these elements included in the TCNI8 database.
TCNI includes critically assessed thermodynamic descriptions for 27 elements and 534 phases. Most of the binary systems in this database have been assessed and can be calculated with the BINARY module in Thermo-Calc. TCNI also contains many assessed ternary systems, at least those being in equilibrium with γ and γ’ phase, and can be calculated with the TERNARY Module in Thermo-Calc.
These 27 elements are included:
Al Ar B C Co Cr Cu Fe H Hf
Mn Mo N Nb Ni O Pd Pt Re Ru
Si Ta Ti V W Y Zr
Ordered and disordered bcc (A2 and B2/β) and fcc (A1 and L12/γ´) phases are modeled with a two sub-lattice model using a single Gibbs energy curve which enables order/disorder transformations to be modeled.
All possible binary systems and most Ni-containing ternary systems have been assessed to the full range of composition.
TCP phases are modeled using more complex and physically correct models, which gives the ability to correctly predict site-fractions etc.
Oxygen has been implemented in an ambitious way using the Compound Energy Formalism (CEF) [1] for the solution phases, e.g. spinel, halite, corundum etc., and the ionic two-sublattice model [2][3] for the metallic and ionized liquid.
Molar volume data critically assessed for most phases of importance to Ni-based Superalloys.
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Only the phases of interest for superalloys are defined by default, which means that when retrieving the data from the database other phases will automatically be rejected and would need to be manually restored by the user if these are required for a calculation. The complete description of all the binary systems and many ternary systems are available using the BINARY and TERNARY modules in Thermo-Calc. Note that there are several possible composition sets for the phases named FCC_L12 and BCC_B2; they are either disordered (A1/carbonitride and A2) or ordered (L12 (γ’) and B2 (β)).
The complete list of phases is given at the end of this document. First there is a list of all phases defined by default and then a detailed description of all phases, e.g. number of sub lattices and elements on each sub lattice and if available also structure, Pearson symbol and Structur Bericht.
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Assessed Binary Systems in Full Range of Composition and Temperature
Al B C Co Cr Cu Fe Hf Mn Mo N Nb Ni O Pd Pt Re Ru Si Ta Ti V W Y
B x
C x x
Co x x x
Cr x x x x
Cu x x x x x
Fe x x x x x x
Hf x x x x x x x
Mn x x x x x x x x
Mo x x x x x x x x x
N x x x x x x x x
Nb x x x x x x x x x x x
Ni x x x x x x x x x x x x
O x x x x x x x x x x x x x
Pd x x x x x x x x x x x x x
Pt x x x x x x x x x x x x x x
Re x x x x x x x x x x x x x x x
Ru x x x x x x x x x x x x x x x x
Si x x x x x x x x x x x x x x x x x x
Ta x x x x x x x x x x x x x x x x x x x
Ti x x x x x x x x x x x x x x x x x x x x
V x x x x x x x x x x x x x x x x x x x x x
W x x x x x x x x x x x x x x x x x x x x x
Y x x x x x x x x x x x x x x x x x x x x x x
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Zr x x x x x x x x x x x x x x x x x x x x x x x x
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Assessed Ternary Systems in Full Range of Composition and Temperature
Al-B-Co
Al-B-Cr
Al-B-Hf
Al-B-Mo
Al-B-Ni
Al-B-Re
Al-B-Ti
Al-B-Zr
Al-C-Cr
Al-C-Hf
Al-C-Mo
Al-C-Ni
Al-C-Ta
Al-C-Ti
Al-C-W
Al-C-Zr
Al-Co-Cr
Al-Co-Fe
Al-Co-Hf
Al-Co-Mo
Al-Co-Ni
Al-Co-O
Al-Co-Ta
Al-Co-Ti
Al-Co-W
Al-Co-Zr
Al-Cr-Hf
Al-Cr-Ni
Al-Cr-O
Al-Cr-Pt
Al-Cr-Ta
Al-Cr-Ti
Al-Cr-Zr
Al-Cu-Fe
Al-Cu-Mn
Al-Cu-Ni
Al-Cu-Si
Al-Fe-Mn
Al-Fe-Mo
Al-Fe-Ni
Al-Fe-O
Al-Fe-Ti
Al-Hf-Mo
Al-Hf-Ni
Al-Hf-O
Al-Hf-Re
Al-Hf-Ta
Al-Hf-Ti
Al-Hf-W
Al-Hf-Zr
Al-Mn-Ni
Al-Mn-O
Al-Mn-Si
Al-Mn-Ti
Al-Mo-Ni
Al-Mo-Re
Al-Nb-Ni
Al-Nb-O
Al-Nb-Si
Al-Ni-O
Al-Ni-Pd
Al-Ni-Pt
Al-Ni-Re
Al-Ni-Ru
Al-Ni-Si
Al-Ni-Ta
Al-Ni-Ti
Al-Ni-V
Al-Ni-W
Al-Ni-Zr
Al-O-Si
Al-O-Ti
Al-O-Y
Al-O-Zr
Al-Ru-Ti
Al-Ta-Ti
B-Co-Cr
B-Co-Hf
B-Co-Mo
B-Co-Ni
B-Co-Re
B-Co-Ta
B-Co-Ti
B-Co-W
B-Cr-Ni
B-Cr-Re
B-Fe-Nb
B-Hf-Nb
B-Hf-Ni
B-Hf-Re
B-Hf-Ta
B-Mo-Nb
B-Mo-Ni
B-Mo-Re
B-Nb-Re
B-Ni-Re
B-Ni-Ta
B-Re-Ta
B-Re-Ti
B-Re-W
B-Re-Zr
C-Co-Cr
C-Co-Mo
C-Co-Ti
C-Co-W
C-Co-Zr
C-Cr-Hf
C-Cr-Mo
C-Cr-Ni
C-Cr-Re
C-Cr-Ta
C-Cr-Ti
C-Cr-W
C-Cr-Zr
C-Cu-Fe
C-Fe-Mn
C-Fe-O
C-Hf-Mo
C-Hf-Ni
C-Hf-Re
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C-Hf-Ta
C-Hf-Ti
C-Hf-W
C-Hf-Zr
C-Mo-Ni
C-Mo-Ta
C-Mo-Ti
C-Mo-W
C-Mo-Zr
C-N-Ta
C-Nb-Re
C-Nb-W
C-Ni-Ti
C-Ni-W
C-Ni-Zr
C-Re-Ta
C-Re-W
C-Ta-Ti
C-Ta-W
C-Ta-Zr
C-Ti-W
C-Ti-Zr
C-W-Zr
Co-Cr-Cu
Co-Cr-Mo
Co-Cr-Nb
Co-Cr-Ni
Co-Cr-O
Co-Cr-Re
Co-Cr-Ti
Co-Cr-W
Co-Cu-Fe
Co-Cu-Mn
Co-Cu-Nb
Co-Cu-Ni
Co-Cu-Ti
Co-Fe-Nb
Co-Fe-O
Co-Fe-Ti
Co-Hf-W
Co-Mn-O
Co-Mo-Ta
Co-Mo-W
Co-Ni-O
Co-Ni-Re
Co-Ni-Ru
Co-Ni-Ta
Co-Ni-W
Co-O-Si
Co-O-W
Co-Re-W
Co-Ta-W
Co-Ti-W
Co-Ti-Zr
Co-W-Zr
Cr-Cu-Fe
Cr-Cu-Nb
Cr-Cu-Ni
Cr-Cu-Si
Cr-Fe-Mo
Cr-Fe-N
Cr-Fe-Ni
Cr-Fe-O
Cr-Fe-Si
Cr-Fe-W
Cr-Hf-Nb
Cr-Mn-N
Cr-Mn-O
Cr-Mo-Ni
Cr-Nb-Ni
Cr-Nb-Si
Cr-Ni-O
Cr-Ni-Re
Cr-Ni-Ru
Cr-Ni-Si
Cr-Ni-Ta
Cr-Ni-Ti
Cr-Ni-W
Cr-Ni-Zr
Cr-O-Si
Cr-O-Y
Cr-O-Zr
Cr-W-Zr
Cu-Fe-Mn
Cu-Fe-Mo
Cu-Fe-N
Cu-Fe-Nb
Cu-Fe-Ni
Cu-Fe-Si
Cu-Fe-Ti
Cu-Fe-V
Cu-Mn-Ni
Cu-Mn-Si
Cu-Mo-Ni
Cu-Ni-Si
Cu-Ni-Ti
Cu-Ti-Zr
Fe-Mn-N
Fe-Mn-Ni
Fe-Mn-O
Fe-Mn-Si
Fe-Mo-Ni
Fe-Mo-W
Fe-Nb-Ni
Fe-Nb-Zr
Fe-Ni-O
Fe-Ni-W
Fe-O-Si
Fe-O-W
Fe-O-Y
Fe-O-Zr
Hf-Mo-Ni
Hf-Nb-Si
Hf-Ni-Ta
Hf-O-Si
Mn-Ni-O
Mn-O-Si
Mn-O-W
Mn-O-Y
Mn-O-Zr
Mo-Nb-Ni
Mo-Ni-O
Mo-Ni-Re
Mo-Ni-Ta
Mo-Ni-Ti
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Mo-Ni-W
Mo-Re-Ta
Nb-Ni-Ti
Nb-Ni-W
Nb-O-Si
Nb-Re-Ta
Nb-Re-W
Ni-O-Si
Ni-O-W
Ni-O-Y
Ni-O-Zr
Ni-Re-Ta
Ni-Re-Ti
Ni-Re-W
Ni-Re-Zr
Ni-Ru-Ti
Ni-Ta-W
Ni-W-Zr
O-Si-Ti
O-Si-Y
O-Si-Zr
O-Y-Zr
Re-Ta-W
Re-Ta-Zr
Re-W-Zr
Ta-W-Zr
Ti-W-Zr
Example Calculations Using TCNI
Figure 1. Phase diagrams calculated for Al-Fe [4] and Al-Ni [5].
Figure 2. Isothermal sections of Al-Cr-Ni [6] and Ni-Re-W [7] calculated at 1273 K.
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Figure 3. Isothermal sections of Co-Cr-Mo [8] and Mo-Ni-Re [9] calculated at 1273 K.
Figure 4. Section ZrO2-Y2O3 compared with experimental information[10][11][12].
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Figure 5. Predicted amount of phases (metastable calculation) at varying temperatures for a Ni-18Cr-18Fe-3Mo-0.5Al-1Ti-5.3Nb-0.02C (wt. %) alloy. Experimental γ’’ (BCT_D022) solvus temperature [14]is close to 900 ºC and the γ’+ γ’’ fraction is between 15-20 %.
Figure 6. Predicted amount of phases at varying temperatures for a Ni-18Cr-10Fe-9Co-2.8Mo-1.5Al-0.7Ti-5.3Nb-0.02C (wt. %) alloy. Experimental γ’ solvus temperature [15] is close to 950 ºC and delta (NI3TA_D0A) solvus close to 1010 ºC. The delta phase fraction was measured around 8% and γ’ fraction around 20% at 760 ºC after 500 hr heat treatment.
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Figure 7. Predicted amount of phases at varying temperatures for a Ni-11.5Cr-15.5Co-6.5Mo-4.3Al-4.3Ti-0.5Hf (wt. %) alloy. Experimental γ’ solvus temperature [13] is close to 1150 ºC and both σ and µ phases were observed at 760 ºC after 1000 hr heat treatment.
Table 1. Predicted compositions of γ and γ’ as well as the fraction in two Ni-base alloys compared with measurements (in brackets) from Sudbrack et al.[16].
at.% Ni Al Cr W Experimental γ ’ fraction
Predicted γ’ fraction
Ni-9.8Al-8.3Cr γ 82.9 (82.7)
8.51 (8.43)
8.61 (8.86) -
Ni-9.8Al-8.3Cr γ’ 76.7 (76.6)
16.7 (17.4)
6.63 (5.99) - 18.9 15.8
Ni-9.7Al-8.5Cr-2W γ 81.4 (81.8)
6.75 (6.23)
9.51 (10.48) 2.35 (1.54)
Ni-9.7Al-8.5Cr-2W γ’ 76.2 (76.2)
16.4 (16.9)
6.19 (3.94) 1.21 (3.00) 30.8 30.5
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Figure 8. Predicted densities of liquid Ni-Cr-Al-Mo alloys where the molar ratio of Ni:Cr:Al is close to the average value for commercial superalloys INCO713, CM247LC and CMSX-4. Symbols are the experimental values from Fang et al.[17].
Figure 9. Predicted lattice parameters of disordered FCC of Inconel-600 at varying temperatures compared to X-ray diffraction values by Raju et al. [18]. At low temperature the calculation gives, besides the disordered FCC, also an ordered L12 phase, which causes the kink in the curve.
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Figure 10. Predicted γ /γ’ lattice mismatch of a Ni-0.6Mo-0.92Ta-12.5Al-1.83Ti-10.5Cr-3.3W (at. %) compared to an experimental determination by Nathal et al. [19].
Acknowledgement
Dr Nathalie Dupin and Prof Bo Sundman are acknowledged for many valuable discussions and important contributions.
References
[1] Hillert, M. (2001). The compound energy formalism. Journal of Alloys and Compounds, 320(2), 161–176.
[2] Hillert, M., Jansson, B., Sundman, B., & Ågren, J. (1985). A two-sublattice model for molten solutions with different tendency for ionization. Metallurgical Transactions A, 16(1), 261–266.
[3] Sundman, B. (1991). Modification of the two-sublattice model for liquids. Calphad, 15(2), 109–119.
[4] M Seiersten, Sintef report STF28F93051 (1993).
[5] Ansara, I., Dupin, N., Lukas, H. L., & Sundman, B. (1997). Thermodynamic assessment of the Al-Ni system. Journal of Alloys and Compounds, 247(1–2), 20–30.
[6] N. Dupin, Private communication, unpublished work.
[7] N. Dupin, Private communication, unpublished work.
[8] N. Dupin, Private communication, unpublished work.
[9] N. Dupin, Private communication, unpublished work.
[10] Noguchi, T., Mizuno, M., & Yamada, T. (1970). The Liquidus Curve of the ZrO2-Y2O3 System as Measured by a Solar Furnace. Bulletin of the Chemical Society of Japan, 43(8), 2614–2616.
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[11] STUBICAN, V. S., HINK, R. C., & RAY, S. P. (1978). Phase Equilibria and Ordering in the System ZrO2-Y2O3. Journal of the American Ceramic Society, 61(1-2), 17–21.
[12] Rouanet, A. (1968). High-temperature solidification and phase diagrams of the ZrO 2–Er 2 O 3, ZrO 2–Y 2 O 3, and ZrO 2–Yb 2 O 3 systems. CR Acad. Sci. Ser. C, 267(23), 1581–1584.
[13] Cui, C. Y., Gu, Y. F., Ping, D. H., & Harada, H. (2009). Microstructural Evolution and Mechanical Properties of a Ni-Based Superalloy, TMW-4. Metallurgical and Materials Transactions A, 40(2), 282–291.
[14] Experimental Data (various sources).
[15] Experimental Data Superalloys (2007).
[16] Sudbrack, C. K., Ziebell, T. D., Noebe, R. D., & Seidman, D. N. (2008). Effects of a tungsten addition on the morphological evolution, spatial correlations and temporal evolution of a model Ni–Al–Cr superalloy. Acta Materialia, 56(3), 448–463.
[17] Fang, L., Wang, Y. F., Xiao, F., Tao, Z. N., & MuKai, K. (2006). Density of liquid NiCrAlMo quarternary alloys measured by a modified sessile drop method. Materials Science and Engineering: B, 132(1-2), 164–169.
[18] Raju, S., Sivasubramanian, K., Divakar, R., Panneerselvam, G., Banerjee, A., Mohandas, E., & Antony, M. . (2004). Thermal expansion studies on Inconel-600® by high temperature X-ray diffraction. Journal of Nuclear Materials, 325(1), 18–25.
[19] Nathal, M. V., Mackay, R. A., & Garlick, R. G. (1985). Temperature dependence of γ-γ’ lattice mismatch in Nickel-base superalloys. Materials Science and Engineering, 75(1-2), 195–205.
Suggested Reference for the Citation of this Database
J. Bratberg, H. Mao, L. Kjellqvist, A. Engström, P. Mason and Q. Chen. “ The development and validation of a new thermodynamic database for Ni-based alloys”, (2012), P. 803-812, Superalloys, eds. E.S. Huron, R.C. Reed, M.C. Hardy, M.J. Mills, R.E. Montero, P.D. Portella and J. Telesman. Proceedings of the International Symposium on Superalloys 2012, Seven Springs, PA, US. http://doi.org/10.1002/9781118516430.ch89.
List of Phases Included in TCNI
Table 2. List of phases defined by default.
LIQUID:L FCC_A1 FCC_L12
BCC_A2 BCC_B2 HCP_A3
CBCC_A12 CUB_A13 DIAMOND_A4
BETA_RHOMBO_B GRAPHITE NI3TI_D024
NI3TA_D0A BCT_D022 C14_LAVES
DIS_MU MU_PHASE DIS_SIG
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SIGMA R_PHASE P_PHASE
CHI_A12 MC_ETA MC_SHP
M23C6 CEMENTITE M12C
M3C2 M6C M7C3
TAU MB_B33 MB2_C32
M3B2 M2B_TETR CU2TI
CUTI3 G_PHASE CU3TI2
CU4TI1 CU4TI3 NI3B_D011
D5A_M3B2 Z_PHASE HALITE:I
CORUNDUM:I SPINEL:I GAS:G
Table 3. List of all phases in TCNI and the thermodynamic model used to describe the phase. Prototype, Pearson symbol and Structur Bericht are given if available. Phases in gray are suspended by default.
Name Prototype Pearson S. Bericht. Thermodynamic model
FCC_A1 Cu cF4 A1 (Al,Co,Cr,Cu,Fe,Hf,Mo,Mn,Nb,Ni,Pd,Pt,Re,Ru,Si,Ta,Ti,V,W,Y,Zr) (B,C,N,O,VA)
This phase appears only when FCC_L12 has been rejected by the user.
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FCC_L10 AuCu tP4 L10 (Mn,Ni,Pd)0.5 (Mn,Ni,Pd)0.5
FCC_L12 Cu cF4 A1 (Al,Co,Cr,Cu,Fe,Hf,Mn,Mo,Nb,Ni,Pd,Pt,Re,Ru,Si,Ta,Ti,V,W,Y,Zr)0.75 (Al,Co,Cr,Cu,Fe,Hf,Mn,Mo,Nb,Ni,Pd,Pt,Re,Ru,Si,Ta,Ti,V,W,Y,Zr)0.25 (B,C,N,O,VA)
NOTE: When the global minimisation is used, the number attributed to this phase is given randomly. Only the filling of the different sublattices allow to identify the different crystallographic structures described by this model.