材料热力学与动力学计算技术应用研讨会

Thermo-Calc (TCW+TCC) Training Course

Xiamen, April 19-21st, 2008

HANDOUTS

Contents

1.Program

2.Handouts (copies of slides).

3.TCC File Types and Relations.

Thermo-Calc (TCW)

Training Course

Xiamen, April 19, 2008

Program

Morning

Introduction.

general.

in

Thermo-Calc

functionality.

TCW

Break

Binary phase diagram calculations (Fe-Cr).

Databases.

Plotting thermodynamic functions in unary, binary & ternary systems.

Lunch

Afternoon

Single equilibrium calculations in low alloyed steels.

Property diagrams calculations of multi-component alloys.

Phase diagram calculations in multi-component systems.

?Isopleth section;

?Isothermal section;

?Liquidus surface projection.

Break

Using the Materials module in TCW4.

Calculation of PRE for a duplex stainless steel.

Scheil solidification simulation of steel (with/without back diffusion).

Exercises:

?Liquidus/solidus temperature of a tool steel;

?Ms temperature of M7 steel.

End of the TCW Training Course.

Thermo-Calc (TCC)

Training Course

Xiamen, April 20th, 2008

Program

Morning

Introduction.

general.

in

Thermo-Calc

Thermo-Calc Classic, structure and modules.

Break

Getting started. Binary phase diagram calculation (Fe-C). Lunch

Afternoon

Single equilibrium calculations for multicomponent alloys.

calculations for multicomponent alloys.

diagram

Property

Phase diagram calculations in multicomponent systems.

?Isopleth section;

?Isothermal section;

?Liquidus surface projection.

Exercise: liquidus/solidus temperatures for a tool steel. Break

Scheil solidification simulation of steel (with/without back diffusion).

A3-temperarure and effects of alloying elements in a low-carbon steel.

Simulation of steel refining.

Calculation of a T0-line and para-equilibria in Fe-Mn-C.

Exercises:

?Calculations of a duplex steel;

?Using functions as conditions.

End of the TCC Training Course.

DICTRA

Training Course Xiamen, April 21st, 2008

HANDOUTS

Contents

1.Program

2.Handouts (copies of slides).

DICTRA

Training Course

Xiamen, April 21st, 2008

Program

Morning

Introduction

DICTRA Software, Databases and Applications:

History; Software structure

Overview of mobility databases

Concepts: cell, region, grid types, geometry

Models and Applications

simulation:

One-phase

Theory: One-Phase Model

Example 1: Carburization of a Binary Fe-C Alloy

Break

Moving phase boundary simulation:

Theory: Moving Boundary Model

Example 2: Solidification for a multicomponent

steel AerMet100

Particle coarsening simulation:

Theory: Coarsening Model

Example 3: Coarsening of a M6C in a Fe–Mo-C alloy Para-equilibrium approach in DICTRA simulation:

Theory: Local equilibrium vs para-equilibrium

Example 4: Ferrite growth into Austenite

End of the DICTRA Training Course.

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008Outline

)Computational Thermodynamics and Kinetics

?CHLPHAD Approach ?SGTE Community

?TCS (Thermo-Calc Software)

)Applications of Thermo-Calc Software/Databases )Applications of DICTRA Software/Databases )Applications of TC-PI Programming Interfaces

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Materials Solutions through Computations

The research and development linking materials science and engineering with computer calculations and simulations in the last decade have given birth to a revolutionary approach for quantitative conceptual design of various materials.

A comprehensive combination of thermodynamic and kinetic models makes it possible to predict material compositions, structures and properties resulting from various materials processing.

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008Materials Solutions through Computations

The increased importance of mathematical modeling for product development and process control has proven the high need for thermodynamic calculations and kinetic simulations.

Modern quantitative conceptual design of advanced materials has tremendously benefited from computational thermodynamics and kinetics over the last decades.

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Computational Thermodynamics and Kinetics

9CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry)

9first-principles calculations (e.g.,ab initio , DFT-Density Function Theory)

9MD (Molecular-Dynamics simulations) 9MC (Monte-Carlo simulations) 9PFM (Phase-Field Methods)

9CFD (Computational Fluid Dynamics)

9FEM/FDM (Finite Element Methods & Finite Difference Methods) 9……

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008Extended CALPHAD Method

Fundamental Empirical Experimental Theories

Rules

Information

Models for thermodynamic properties of each phase G(T, P, y, ...)Models for kinetic quantities of each process k(T, P, y, v, t, s, ...)

Databases for modeling parameters

thermodynamic properties

kinetic quantities

Predictive Calculations:equilibrium states, metastable states phase diagrams, property diagrams Predictive Simulations:tempo-spatial structures compositional profiles microstructure evolutions

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Extended CALPHAD Method

?Models ?Software ?Databases

?

Programming Interfaces

Thermodynamic Calculations

9Thermo-Calc 9TC-iSLAG Kinetic Simulations

9DICTRA 9TC-PRISMA

Application Programming Interfaces

9TQ 9TCAPI

9TC-MATLAB Toolbox

SGTE CommunityScientific Group Thermodata EuropeContributing to the developments and applications of the CALPHAD approach since 1979 Associated with some software available within the CALPHAD community, several high-quality databases have been developed by SGTE and its members through various international/national research projects, and by some other related organizations.
TCS (Thermo-Calc Software)Based on long-historic and sophistic R&D activities in the field of Computational Thermodynamics and Kinetcs at MSE of KTH (Royal Institute of Technology, Sweden), the Thermo-Calc and DICTRA software/database packages had been developed. In 1997, TCS (Thermo-Calc Software) was created by FCT (Foundation of Computational Thermodynamics, Sweden), for the purposes of further developments and applications of Thermo-Calc/DICTRA. Ultimate goals: Assisting in materials design, engineering and applications.
Thermo-Calc Software
XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008
Thermo-Calc Software
XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008
Thermo-Calc and DICTRAThe Thermo-Calc and DICTRA software/database/interface packages have been developed over the past 35 years, aimed at providing materials scientists and engineers with engineering tools in their daily work of research and development. Thermo-Calc is one of the most used software packages in the field of Computational Thermodynamics. It can be used to calculate complicated heterogeneous phase equilibria, multicomponent phase diagrams and many types of property diagrams. DICTRA is probably the only software available in the market today which can precisely simulate Diffusion Controlled phase TRAnsformations in various materials. DICTRA uses ThermoCalc as its engine for thermodynamic calculations, but is extended to handle the kinetics pertaining to diffusion and transformation.Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008
Thermo-Calc:
Thermodynamic Calculations
Thermo-Calc software features a wide spectrum of models and modules, making it possible to perform calculations on most complex problems involving thermodynamics. Thermo-Calc databases cover many different materials, such as steels, alloys, superalloys, melts, slag, salts, solders, ceramics, semi-/super-conductors, polymers, nuclear materials, minerals, gases/fluids, aqueous solutions, organic substances, etc. Thermo-Calc software/database package is suitable for R&D in materials chemistry, thermodynamics, complex heterogeneous equilibria, metastable equilibria, para-equilibria, phase diagrams, property diagrams, solidification simulations, and so forth. Thermo-Calc can also be utilized to establish your own databases through critical assessment based on experimental information.Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008
Thermo-Calc:
Thermodynamic Calculations1500 1400 TEMPERATURE_CELSIUS 1300 1200 11009 7 1 2 3 7 10 2 5 1 8 7 3 3 1 8 2 3 71:FCC_A1 2:FCC_A1#2 3:BCC_A2 4:MC_SHP 5:M23C6 6:M7C3 7:M6C 8:LIQUID 9:MU 10:LAVES 5
Thermo-Calc:
Thermodynamic CalculationsA few clicks in a couple of windows ensures you to reliably obtain the desired multicomponent phase equilibria, phase diagrams and property diagrams.
Phase diagram for a M42 high speed steel.The lines represent where a phase appears or disappears, numbers show on which side of the line that phase is present. The alloy is Fe-4Cr5Mo-8W-2V-0.3Mn-0.3Si-C (wt-%).
1 8
2
1000 900 800 700 0
6 5
1 3 4
3
4
0.5 1.0 WEIGHT_PERCENT C
1.5
Isothermal section in Al-Fe-Mn at 1273 K.Note the dotted line between ordered and disordered states in the bcc one-phase field.
TCW: Thermo-Calc WindowsThermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008 Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008
2

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Thermo-Calc:

Applied to numerous problems

9Calculating stable and meta-stable heterogeneous phase

equilibrium 9Amount and composition of phases

9Transformation temperatures, e.g. liquidus and solidus

temperature 9Predicting driving forces for phase transformations 9Phase diagrams (binary, ternary, isothermal, isoplethal, etc.)9Molar volume, density and thermal expansion

9Scheil-Gulliver (non-equilibrium) solidification simulations 9Thermochemical data such as;

9enthalpies 9heat capacity, 9activities, etc.

9Thermodynamic properties of chemical reactions 9And much, much more….

Designing and

optimization of alloys Design and optimization of processes

Photo: Stig-G?ran Nilsson (2002)

Example of calculations

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

DICTRA:Kinetics (Diffusion) Simulations

DICTRA is the software for simulations of DIffusion Controlled phase TRAnsformation processes in complex multicomponent systems. DICTRA, coupled with Thermo-Calc, is a powerful engineering tool for simulating a wide variety of scientific and industrial applications.

Successful application examples are homogenization of alloys, carburizing/decarburizing of steels and alloys/superalloys, nitriding/nitrocarburizing of steels, solidification, austenite-ferrite transformations, growth/dissolution of carbides in steels and alloys, growth/dissolution of intermediary phases, interdiffusion in composite materials, gradient sintering of cemented carbides, dissolution/distribution and coarsening of particles, growth of pearlite in alloyed steels, and so on.

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

DICTRA:Kinetics (Diffusion) Simulations

200

10203040

E-3010

E-4Penetration Depth [meter]

Quadakkers et al. (1987)

O v e r a l l M a s s -f r a c t i o n C a r b o n

Ni-30Cr Alloy

850o C, 1000h, αC =1

0.100.200.300.4001020

E-4Penetration depth [meter]

M 3C 2

M 7C 3

M 23C 6

M o l e -f r a c t i o n C a r b i d e s

Ni-30Cr Alloy

850o C, 1000h, αC =1

Composition profiles of carburization process of a Ni-30Cr alloy after 1000 hours at 850o C and αC =1. Total mass-fraction of carbon and mole-fraction of precipitated carbides are illustrated.

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

DICTRA:Applied to numerous problems

2.60 m

Ball screw for the Airbus A380 aircraft: a martensitic as carburized stainless steel

0,0

0,40,81,21,62,02,42,83,23,64,04,4

4,8

100

200

300400500600700800900

祄%C profil carbone calcul?en fin d'enrichissement

profil carbone calcul?apr 鑣 3h de diffusion Fe-12Cr-2Ni-2Mo-0.12C at 955°C :Calculated carbon profile at the end of the enrichment step

Calculated carbon profile after 3h of diffusion

Example:Simulation of carbon evolution in high alloyed steels by Aubert & Duval, France.

Turpin et al., Met. Trans. A 36(2005), pp. 2751-60

Distance from surface (μm)

C a r b o n c o n t e n t (%)

9Carburizing and decarburization

9Microsegregation during solidification 9Precipitate growth and dissolution 9Precipitate coarsening

9Interdiffusion in coating/substrate 9TLP bonding of alloys 9

and much more ……

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Thermodynamic Databases: Extended CALPHAD

Fundamental Theory

Empirical Rules

Experimental

Data

Models

Parameter Optimization Database

Thermodynamic Properties

Equilibrium States Phase Diagrams

A b I n i t i o C a l c u l a t i o n

E x p e r i m e n t a l D e t e r m i n a t i o n

()

φ

φ

i m x P T G ,,

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Kinetic (Mobility) Databases: Extended CALPHAD

Diffusion without a chemical gradient:-Tracer diffusion coefficients

Logarithm of the Atomic Mobility for

Individual Elements

Applications

()

)

,,(ln P T x f RTM B =α

-ab-initio -Correlation

E x p e r i m e n t s

T h e o r y Data

Data

Diffusion under a chemical gradient:-Chemical interdiffusion coefficients -Intrinsic diffusion coefficients

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Thermo-Calc/DICTRA Databases

Generally these databases are specialised and each covers one class of materials. There are databases for steels (including stainless steels, HS steels, HSLA steels, cast irons,etc .), Ni-based super-alloys,Ti-/Al-/Mg-/Cu-/Zr-based alloys, hard materials, ceramics, molten salts, slag, semi-/super-conductors, solders, nuclear materials, earth materials, inorganic compounds, aqueous solutions, polymers, organic substances.

Two widely used databases, which cover many different metallic alloys, are the SGTE Alloy Solutions Database (SSOL4) and TCS Alloy Mobility Database (MOB2).

Upon request, special subsets of some databases can be provided.Thermo-Calc Software and its partners are devoted to further develop more industry-oriented databases for new applications.

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Thermo-Calc Engine

DICTRA

phase diagrams,composition profiles, & other types of graphs

Thermo-Calc Engine

Literature Data

Experimental

Data

POST

Thermodynamic and Kinetic

Databases

TDB

400

800

1200

T e m p e r a t u r e (o C )

0.20.40.60.

8 1.0

Mole-fraction Cu

PARROT

TC-Toolboxes in MATLAB, etc.

R e s

e a r c h e r N o

r m a l u s e r

For Material Property Calculations and Material Process Simulations

Build up YOUR own Application Programs

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Application Programming Interfaces

Application programming interfaces of the Thermo-Calc and DICTRA software with other programs or third-party software packages for materials property calculations, materials structure simulations and materials process controls, have been rapidly developed over the past several years. There are now different ways of doing this.

Both TQ (Thermodynamic Calculation Interface) and TCAPI (Application Programming Interface) allow the users to write their own applications. TQ (written in FORTRAN) is available for all modern computer platforms, while TCAPI (written in C/C++ and suitable for C/C++,VC, VB, Delphi, Java, VJ, etc.)has been used under Windows and LINUX.

These interfaces also allow the users to program in other third-party software packages. TCAPI was recently used to create a unique TC MATLAB Toolbox in the MATLAB ?software package.

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008TCAPI

Thermo-Calc Engine

Application Programs

TCW ( )

TC Toolboxes in Third-Party Software

TQ DICTRA

Materials Interface (S tructure/P roperty/P rocess )

Application Programming Interfaces

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Outline

)Computational Thermodynamics and Kinetics

?CHLPHAD Approach ?SGTE Community

?TCS (Thermo-Calc Software)

)Applications of Thermo-Calc Software/Databases

)Applications of DICTRA Software/Databases )Applications of TC-PI Programming Interfaces

Thermo-Calc ModelsThermodynamic models handle EOS & all kinds of thermodynamic properties for various materials. Following models are now available in Thermo-Calc:Compound-Energy Model (interaction on up to ten sublattices): Redlich-Kister polynomials (Muggianu or Kohler extrapolation) Stoichiometric constraints Ionic constituents Interstitial solutions Vacancy distributions Magnetic transformations Magnetic ordering Miscibility gaps Chemical ordering (B2, L12, etc.) Two-Sublattice Ionic Liquid Model Associated Model Quasi-chemical Model Kapoor-Frohberg Cell Model General Two-State Model for liquid-amorphous/glass-solid transformations CVM (Cluster Variation Methods) for chemical ordering General PVT Model for solids and liquids Birch-Murnagham Model (pressure-dependency) for solids and liquids SUPERFLUID Model for C-H-O-S-N-Ar fluid & gaseous mixtures DHLL, SIT, HKF and PITZ Models for aqueous solutions Flory-Huggins Model for polymersThermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008
Thermo-Calc Functionality? ? ? ? ? ? ? ? ? ? ? ? ? ? ?Equilibrium calculations Thermodynamic functions Binary phase diagrams Ternary phase diagrams Isothermal phase diagrams Isopleth phase diagram sections Para-equilibrium T0 temperature Miscibility gaps Order-disordering phases Pitting Resistance Equivalence Oxide layers on steels/alloys Simulation of steel refining Scheil-Gulliver solidification Chemical driving forces
? ? ? ? ? ? ? ? ? ? ? ? ? ? ?
CVD calculations CVM calculations Pourbaix diagrams Predominant diagrams Various property diagrams Partial pressures of gas species Interface facility - TQ/TCAPI/Toolbox Diffusion simulations - DICTRA Microstructure simulations Fluid-dynamics simulations CCT & TTT diagram calculations Surface reaction simulations Chemical kinetics simulations and many many more
Thermo-Calc Software
XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008
Thermo-Calc ApplicationsMSE R&D: Other R&D:
Case 1: Carbon in M42 High Speed Steel1 5
? ? ? ? ? ? ? ? ? ?
Steels: SS, HSLA, HSS, CI, … Alloys: Al, Ti, Ni, Cu, Mg, REE, … Hard materials carbides, nitrides, … Ceramics Semi-/Supper-conductors Polymers Composites Powder Metallurgy Hydro-metallurgy Earth materials: diamond, gold, petroleum, ...
? ? ? ? ? ? ? ? ? ? ? ? ? ?
Car industries
Temperature, oC
Aqueous chemistry Materials corrosion CVD depositions Chemical engineering Organic materials Energy conversion Environmental assessment Geochemistry/Geophysics Nuclear waste management Food/medicine production and many many more
1:BCC_A2 2:FCC_A1#2 3:FCC_A1 4:M6C 5:MC_SHP 6:M23C6 7:M7C3 8:LIQUID 9:LAVES
Mole fraction phase
Aerospace industries
1:FCC_A1 2:FCC_A1#2 3:M6C 4:LIQUID 5:BCC_A2 6:M23C6
4
5 3 6 2 6 3 2 4
4
1 5 3 4
Mass percent C
Temperature, oC
Phase diagram for a M42 high speed steel. The lines represent where a phase appears or disappears, numbers show on which side of the line that phase is present. The alloy is Fe4Cr-5Mo-8W-2V-0.3Mn-0.3Si-C(wt%).Thermo-Calc Software
Property diagram for a M42 high speed steel. Shows how the fractions of the phases in the system vary with temperature. The alloy is Fe4Cr- 5Mo-8W-2V-0.3Mn-0.3Si-0.9C.
Thermo-Calc Software
XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008
XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008
Case 2: Nitrogen in HSLA SteelHSLA: Fe-1.5Mn-0.3Si-0.1V-C (wt%)Austenite
Case 3a: Liquidus Surface of Al-Mg-Si AlloyTCC/TCW can automatically calculate and plot liquidus surface projection. The invariant reactions and their types are identified and listed simultaneously.
AusteniteAustenite + V(CN)
Austenite + VC Ferrite + Austenite + VCFerrite + Austenite + V(CN)
V(C,N) particles act as grand refinersFerrite + Aus + V(CN) + Cem
Ferrite + Aus + VC + Cem Ferrite + VC + Cem + Graphite
Ferrite + V(CN) + Cem + Graphite
1. No nitrogen present This isopleth shows that to avoid graphitization at long exposures at 500oC, less than 0.15 wt% C should be used. Heat treatment above 900oC may lead to grain growth.Thermo-Calc Software
2. With the addition of only 0.003 wt-% N. The two phase field of austenite + V(C,N) is much extended, and grain growth can be avoided up to 1000oC. The phase diagram at low T is not much altered compared to 1.XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008 Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008
5

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008Case 3b: Liquidus Surface of Sn-Cu-Ag Alloy

Liquidus projections and monovariant

lines in the Sn-Cu-Ag Solder. Primary and secondary solidification projections in the Sn-Cu-Ag Solder.

0123

4

56

78

910W e

g h

t _P

e r c

e n

t o

f A

g

0.5 1.0 1.5 2.0 2.5 3.0

Weight_Percent of Cu

1:*AG3SN_EPSILON LIQUID 2

2:*CU6SN5 LIQUID 2

112

3:*BCT_A5 LIQUID

33

1132

310320

310

300

290

280

270

260

250

240

230226

224222

220218

300

290280270260

250

240230

BCT

Ag3Sn_epsilon

Cu6Sn5

Sn-Cu-Ag: Liquidus Projections + Monovariant Lines

05

10

15

20

25303540

W E I G H T _P E R C E N T A G

1

2

3

4

5

6

7

8

9

10

WEIGHT_PERCENT CU

3:*AG3SN_EPSILON LIQU 3

2

2:*CU3SN LIQUID

3

3

2

4 4:*CU6SN

5 LIQUID

3

4

434450 C

400 C

350 C

300 C

250 C

450 C

400 C

350 C

300 C

250 C

Cu6Sn5

Cu3Sn

Ag3Sn-epsilon

Sn-Cu-Ag: Liquidus Projections + Monovariant Lines

BCT

2

+ Secondary Solidifications

+ BCT/Cu6Sn5/Cu3Sn

+ BCT/Ag3Sn-epsilon/Cu3Sn

HCP

+ Ag3Sn-epsilon/Cu6Sn5

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Case 3c: Liquidus Surface of Fe-Cr-C Alloy

Liquidus surface of the Fe-Cr-C ternary alloy.The liquidus temperature as the 3rd axis variable (Z) is projected on 2D as shown in diagram A (TCC/TCW),and is plotted in 3D as illustrated in diagram B (SIM VRMLView).

1:*LIQUID FCC_A1 5:*LIQUID GRAPHITE 7

9 10:*LIQUID BCC_A2

16:*BCC_A2 LIQUID F0 FCC_A118

1914500.2

0.4

0.6

0.8

1.0

W e i -F r a c C r

0.020.040.06

0.080.100.120.14W ei-Frac C

Z-AXIS = 1151. + 77.62 * Z

1

1

2 2:*BCC_A2 LIQUID

3 3:*LIQUID M23C64

4:*LIQUID M7C3

5

11

2

2

3

6

6:*M7C3 LIQUID 7 7:*GRAPHITE LIQUID 77

6

8 8:*M23C6 LIQUID

2777

9

9:*M3C2 LIQUID 6

777

6

77

7

77

2

210

222

211 11:*GRAPHITE LIQUID F0 M7C3

12 12:*CEMENTITE LIQUID F0 GRAPHITE 13 13:*CEMENTITE LIQUID F0 FCC_A114 14:*CEMENTITE LIQUID F0 M7C315

15:*FCC_A1 LIQUID F0 M7C31617 17:*BCC_A2 LIQUID F0 M7C3 18:*BCC_A2 LIQUID F0 M23C6 19:*M23C6 LIQUID F0 M7C31920

20:*FCC_A1 LIQUID F0 GRAPHITE

1121 21:*GRAPHITE LIQUID F0 M3C2

22 22:*M3C2 LIQUID F0 M7C3

3

2

1

2

3

4234

23

4

5

4678

67

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Case 4a: Solidification Paths of Al-Alloys Temperature o C

L a t e n t H e a t E v o l u t i o n (J /m o l e )

L →fcc

L →fcc + Mg2Si

L →fcc + Mg2Si + Si

Scheil-Gulliver simulation of

solidification process in a Al-3Mg-2Si alloy.

The square diagrams show, in turn, how the amount of

liquid phase diminishes, how the latent heat evolution varies with temperature and the changing composition of the liquid phase. The Gibbs triangle shows the liquidus surface in Al-Mg-Si with this alloy’s liquid composition dotted.

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Case 4b: Solidification Paths of Steels/Fe-Alloys

Advanced Scheil-Gulliver simulation of the solidification process in Fe-alloys.

Solidification paths and microsegressions for two Fe-based alloys with bulk compositions of Fe-0.3Co-3.9Cr-0.1Cu-0.32Mn-4.9Mo-0.36Ni-0.3Si-6.1W-1.9V-0.88C and Fe-10Cr-1C (wt%), respectively. The simulations are conducted using various approaches, and the experimental data are imposed for comparisons.

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Case 5: Para-Equilibrium State in Steels

500

600

700

800900100011001200T E M P E R A T U R E _K E L V I N

1

2345678910

10

-3

MASS U-FRACTION, C

Steel: Fe-1.92Cr-0.497M n-0.49M o-2.0Ni-0.26Si-[0.0-1.0]C (wt%)

1:*FCC_A 1#1

2

2:*M23C6 3:*BCC_A 233

4:*CEMENTITE 4

5:*M7C3

55

1

1

5

6:*FCC_A 1#2 (MC1-x)

5

7:*MC_SHP 7

5

2 8:*M3C27

2

8

4

6

5

6

25

4

8

6

2

9:*SIGMA 9

10:*MU_PHA SE

1010

11

11:*LAVES_PHA SE_C14

2 12:*M6C

121

12

1

4

3

2

Para-Equilibrium BCC+FCC (with tie-lines)

Isopleth and para-equilibrium state between austenite and ferrite for a Fe-1.92Cr-0.497Mn-0.49Mo-2.00Ni-0.26Si-C (wt%) steel. The para-equilibrium state between austenite and ferrite (with tie-lines) are imposed onto the equilibrium isopleth.

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Case 6: Optimal Conditions for β’-Sialon

10-22

10-2110-2010-19

10-1810-17

10-16

10-15

P a r t i a l p r e s s u r e o f o x y g e n (b a r )

0.10.20.30.40.50.60.70.80.9 1.0

Equivalent fraction Al

SiO 2

AlO 1.5

T ridym ite + M ullite X 1+M ullite

T ridym ite + X 1

M ullite

Mullite

+

Corundum

X 1+Corund um

X 1+O X 1+β'-s ia lon

β'-sia lon +O'

O'

Coru ndu m

+β'-sia lo n

β'-sia lo n

β'-sia lo n + AlN

T =1623 K P N 2=1 b ar

Property diagram of the Si-Al-O-N system at 1623 K and P N2=1 bar.Phase stabilities vary with oxygen partial pressure and equivalent fraction of Al in the system.

Property diagram of the Si-Al-O-N system at 1623 K and P O2=10-20bar.Phase stabilities vary with nitrogen partial pressure in the system.

S y n t h e s i s o f β’-s i a l o n f r o m m i x e d S i O 2a n d A l 2O 3p o w d e r b y r e d u c t i o n -n i t r i d a t i o n

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008Case 7a: Aqueous Corrosion of Stainless Steel

F A +

O O +e F iF F +F O +C I For the heterogenous interaction -1.5

-1.0-0.500.5

1.0

1.5E h (V )

1

2

3

4

5

6

7

8

9

10

pH

GAS (Reducing)e C r

2O

4

GAS (Oxiding)

Q U E O U S

Cr 2O 3

Fe 23

C r 23 F 2

O

3

+ N iF

e 2O

4

C r

2O 3+ F e 2O

3 + N iF e 2O 4

e 2O

3+ N

e 2O 4

F e C

r 2O

4+ F e 3O

4 + N iF e 2O

4e C

r

2O 4

F e 3O 4+ F C C FeCr 2O 4+ FCC

e C r

24 F e 2O

3

FeCr 2O 4+ Fe 3O 4

o r

r o s io

n

m m

u n it y

P a s s iv a ti o n

Pourbaix Diagram

between 0.001 m of Fe-alloy (Fe-5Cr-5Ni mole%) and 1 kg of water (and with 3 m NaCl), at 200o C and 100 bar.

.001

Gaseous Mixture Cr2O3G Steel: 0.1 g [Fe-17.00Cr-12.00Ni-2.5Mo (wt%)]

.01

.1

1

10

100

1000

10000

S t a b l e P h a s e s / g r a m s

-1.5

-1.0-0.500.5 1.0 1.5 2.0

Eh (V)

Aqueous Solution

MoO2MoO2.75

G a s e o u s M x t u r e MoO2.889

MoS2

NiS2

Pyrite

M a g n e t t e

F e C r 2O 4

A u s t e n t e

(O 2-d o m n a n t )

(H2O-dominant)

a s e o u s M x t u r e (H 2-d o m n a n t )

Aqueous Solution: 1 kg of water with 0.537 m H2SO4T=85o C, P=1 bar Aqueous Solution

Pourbaix diagrams and property diagrams for the heterogeneous interaction systems between 0.001 m of steel [Fe-5Cr-5Ni mole%] and 1 kg of water (and with 3 m NaCl), at 200o C and 100 bar, and between 0.1 g of steel [Fe-17.00Cr-12.00Ni-2.5Mo (wt%)] and 1 kg of water (and with 0.537 m H2SO4, at 85o C and 1 bar, respectively.

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Case 7b: Aqueous Corrosion of Stainless Steel

G )

a s (H +m +C r A A A FeO +Cu +MnO q +A A m 4:*CU2FE2O4_S 9:*FCC_A 15-0.8

-0.6-0.4-0.200.20.40.6

0.81.01.21.40

51015

1 1:*MN1O2_S

2:*FE2NI1O4_S 3:*H1MN1O2_S 3334

5

5:*CR2O3_S 54

6:*CU1O1_S 6

1111664

7:*CR2FE1O4_S 7

27

7

22

58

8:*GA S

51

9 10:*FE2O3_HEMA TITE 141010 11:*FE2MN1O4_S 1122 12:*BCC_A 21212

13:*H2MN1O2_S 1310 14:*MA GNETITE 9

15:*B1H1O2_S

851412105

10

8

158

7

E h (V )

pH

a s (

H 2+B

O (O

H )

G 2)

A q s H 2O 3A q s +F C C +M t +C r 2F e O 4+M n O (O H )A q s +

C u O q s +H m

Aqs+Cr 2O 3Aqs+Cr 2FeO 4G a s (H 2)+B C C +B O (O H )Aqs+FCC+Cr 2FeO 4

q s +H m +C r 2O 3+F e 2N i O 4q s Aqs+FCC+Cr 2O 3A q s +H m +C

r 2F e O 4A q s +F C C +H m +C r 2F e O 4+F e 2M n O 4+F e 2N i O 4Aqs+FCC+Mt+Cr 24A q s +M t +C r 2F e O 4

Aqs+Hm+Cr 2O

3

2Fe 2O 4 +Fe 2NiO 4

(OH)

A s H m +M n O (O H )Aqs+BCC+Mt+Cr 2FeO 4

A q s +H m +M n O 2q s

+H m

+C r

2O 3+M n O (O H )+F e 2N i O 4Aqs+Hm+Cr 2O 3+Cu 2Fe 2O 4+Fe 2MnO 4+Fe 2NiO 4q s

+H

+C r

2F e O

4+F e

2M n

O 4+

F e

2N i O 4P o u r b a i x d i a g r a m s f o r t h e h e t e r o g e n e o u s i n t e r a c t i o n s y s t e m s b e t w e e n 0.001 m o f s t e e l [F e -7.676C r -5.0N i -2.1887M n -1.0C u m o l e %] a n d 1 k g o f w a t e r (a n d w i t h 1.2 m H 3B O 3, 0.022 m L i a n d 0.001 m N H 3), a t 25o C a n d 1 b a r . T h i s a p p l i c a t i o n i s p a r t i c u l a r u s e f u l f o r s a f e t y a s s e s s m e n t s o f n u c l e a r r e c t o r s a n d n u c l e a r w a s t e r e p o s i t o r i e s .

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Case 8: Salt Corrosion of Alloy Surface

10-4

.001

.01.11S t a b l e p h a s e s (w e i g h t _f r a c t i o n )

200

400600800100012001400TEMPERATURE_CELSIUS Corrosion of Cr2O3 in C-H-O-S-N-Na-Cl environment Gaseous Mixture

Cr2O3Ionic_Liquid

Hexagonal Halite

O r t h o r h o m b i c

10-12

10-1010-810-610

-4

.011

C r i n s t a b l e p h a s e s (m o l e _f r a c t i o n )

200400600800100012001400

TEMPERATURE_CELSIUS

Corrosion of Cr2O3 in C-H-O-S-N-Na-Cl environment G a s

e o u s M i x

t u r e Cr2O3

Ionic_Liquid

Hexagonal O r t h o r h o m b i c

As a typical form in the oxide layer on the surface of stainless steels, Ni-based superalloys, etc, Cr2O3 provides a protection from corrosion attacks by hot or molten salts, high-temperature gases, or aqueous solutions. This calculation illustrates that under certain aggressive conditions, the Cr2O3 layer may be dissolved by the attacking salts , and thus the applied alloy may be exposed to further corrosion attacks from oxidizing and sulphidising environments.

Thermo-Calc Software XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

Outline

)Computational Thermodynamics and Kinetics

?CHLPHAD Approach

?SGTE Community

?TCS (Thermo-Calc Software)

)Applications of Thermo-Calc Software/Databases )Applications of DICTRA Software/Databases

)Applications of TC-PI Programming Interfaces

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

DICTRA:Kinetics (Diffusion) Simulations

Kinetics

Thermodynamics

DATABASES

Gibbs Energy

Mobility Diffusion Coefficients

Local Equilibria

Diffusion Equations Flux Balances

Rates of Interactions

?2G ——?X 2

400

800

1200

T e m p e r a t u r e (o C )

00.20.40.60.8 1.0

Mole-fraction Cu

Phase Diagram of Al-Cu Alloy

510

E-7P a r c e d a m e e r (m e e r )

10-2

Time (seconds)

Experimental points Calculated curve

100102104

Dissolution of Cementite in Alloy

Fe-Cr-C Alloy, 910o C

-15

-14

L o g

D f f u s v y

0.2

0.4

0.6

0.8

1.0

Mole-fraction Ni

Badia&Vignes 1967

Duffusivity of Ni in Ni-Fe Alloy

Evolution in Space and Time

10203040

E-30

10

20

E-4

Penetration depth [meter]

Quadakkers et al.(1987)

0.10

0.200.30

0.40010

20

E-4

Penetration depth [meter]

M C M C M 23C Mass-fraction of C and Mole-fraction of Carbides in Carburization of an Ni-30Cr Alloy

O v e a M a s s a c o n C a b o n

M o e a c o n C a b d e s

Ni-30Cr Alloy

850o C, 1000h, αC =1

Ni-30Cr Alloy

850o C, 1000h, αC =1Interface Positions

Thermo-Calc Engine

Thermo-Calc Software

XMU-CISRI-TCS Seminar/Course, Xiamen, April 18-21, 2008

DICTRA Geometry

Sphere with a certain radius

Infinitely long cylinder of a certain radius Infinitely wide plate of a certain thickness

Infinitely long tube of a certain radius.

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