1. Yuri Gornostyrev Institute of quantum materials science Institute of metal physics UB RAS Ekaterinburg, http://www.iqms.ru IQMS MISiS, 20-10-2013 In collaboration with O.I.Gorbatov, I.K. Razumov, S.V. Okatov, A.R. Kuznetsov (IQMS), P.V. Korzhavyi, A.V. Ruban (KTH), A.I. Lichtenstein (Hamburg Uni), M.I. Katsnelson (Radboud Uni) V.N. Urtsev, A.V. Shmakov (RTC Ausferr)

2. Problem of Fe. Effect of magnetism on fundamental properties IQMS C. Zener (1952): the start temperature of martensitic transformation M s ~ T C Experiment: M s = 1020K (C. Liu et al, J Mater. Proc. Tech., 2001) Fragment of phase diagram Fe-C H. Hasegava, D.G. Pettifor, PRL, 50, 130 (1983) L. Kaufman, E.V. Clougherty, R.J. Weiss, Acta Metall., 11, 323 (1963) Free energy of Fe with taking into account magnetic fluctuations Magnetism play crucial role in phase equilibrium and transformation kinetic C. Zener, 1952 T C ~ T  -  2 MISiS, 20-10-2013 L. Kaufman, et. al., 1963 M. Hillert, et. al., 1967 G. Inden, 1976 M. Hillert, et. al., 1978 T. Nishizawa, et. al., 1979 G. Inden, 1981 B. Jonsson, 1992, 1994, 1995 Y. Liu, et. al., 2009 Wei Xiong, et. al., 201 2

3. IQMS Selected problems initiated by the metallurgical needs 3 Mechanism polymorphous  –  transformation in steel Transformation kinetic and microstructure formation Effect of alloying elements on phase equilibrium and transformation Precipitation of alloying elements and carbonitride in steels Clustering of foreign atoms in maraging steels Grain boundaries segregations and more … Scheme of controlled rolling low alloying pipe steel MISiS, 20-10-2013 Thus, there is close relation between quantum mechanics and technology

4. The purpose and methods of calculations Motivation: elucidate the effect of magnetism on thermodynamic of iron-based alloy We employed the following methods and approximations 1. P. Hohenberg and W. Kohn, Phys. Rev. 136, B864 (1964); W. Kohn and L.J. Sham, Phys. Rev. 140, A1133 (1965) 2. P. Soven, Phys. Rev. 156, 809 (1967) 3. J. Korringa. Physica 13, 392 (1947); W. Kohn and N. Rostoker. Phys. Rev. 94, 1111 (1954) 4. J.P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996) 5. I.A. Abrikosov, A.M.N. Niklasson, S.I. Simak, B. Johansson, A.V. Ruban, H.L. Skriver. Phys. Rev. Lett. 76, 22, 4203 (1996); I.A. Abrikosov, S.I. Simak, B. Johansson, A.V. Ruban, H.L. Skriver. Phys. Rev. B 56, 15, 9319 (1997) 6. B.L. Gyorffy, A.J. Pindor, J.B. Stauton, G.M. Stocks, H. Winter, J Phys. F 15, 1337 (1985); J.B. Stauton, B.L. Gyorffy, Phys. Rev. Lett. 69, 371 (1992) 7. G. Kresse and J. Furthmuller, Phys. Rev. B 54, P.11169 (1996); G. Kresse and J. Hafner, Journal Phys. Condensed Matter, 6, 8245 (1994); G. Kresse and J. Joubert, Phys. Rev. B 59, 1758 (1999). 4 MISiS, 20-10-2013

5. Play important role in pipe steels and maraging steels and use to control phase stability, transformation and strengthening MISiS, 20-10-2013 IQMS

6. Precipitation in steel. Important cases Distribution of copper atoms in steel with 1.2 at.% Cu after annealing [1]. Strength, plasticity and toughness. This steel proposed in prof. M. Fine group at NWU [1] D. Isheim, M. S. Gagliano, M. E. Fine, D. N. Seidman, Acta Materialia V. 54 p. 841 (2006). IQMS 1. Nb carbonitride precipitation Nb(CN) at T < 1100 C to prevent austenite grain growth 2. Cu-reach nano-size precipitate at T < 700 C 3. Complex precipitation Ti-Al-Mn in maraging steels T < 500 C High strength and plasticity 6KTH, 15-05-2013

7. IQMS 7 Thermodynamics and structure of alloys from first principles Experiment (HREM, 3D AP) properties V (2) Electronic structure and chemical bonding CVS alloy energy Microstructure formation Interaction with dislocation, hardening Effective cluster interactions energy MISiS, 20-10-2013

8. 8 Ab-initio interaction energies between alloying elements Interatomic interactions follow to the number of element in the periodic table The strongest effect of magnetism is for Cr, Mn, Ni, Cu, V The tendency to decomposition for Cu and Zn O.I. Gorbatov, S.V. Okatov, Yu.N. Gornostyrev, P.A. Korzhavyi, A.V. Ruban, PMM, 2013 « + » is repulsion « - » is attraction local ordering decomposition MISiS, 20-10-2013

9. 9 Total effective pair interaction in bcc-Fe with 1 at.% Cu for different global magnetization Dependence of the effective pair interactions in the nn positions on square of global magnetization O.I. Gorbatov, I.K. Razumov, Yu.N. Gornostyrev, V.I. Razumovskiy, P.A. Korzhavyi, A.V. Ruban, PRB in press Effective pair Cu-Cu interactions Interactions depend on the temperature and the concentration of the alloy Dependence on the concentration is more pronounced in the ferromagnetic state chemical contribution relaxation contribution IQMS MISiS, 20-10-2013

10. 10 Increase of copper concentration results in smoothing magnetic effect Concentration dependent Cu-Cu interactions with strained-induce interactions give agreement with the experiment 1% Cu – isolated Cu atoms in pair 12.5% Cu – the nearest neighbor in first coordination shell. Solubility Cu in bcc Fe: results of Monte Carlo modeling ● - G. Salje and M. Feller-Knipmeier, J. Appl.Phys. 48, 1833 (1977) ■ - M. Perez et. al, Philos. Mag. 85, 2197 (2005) IQMS MISiS, 20-10-2013

11. 11 O.I. Gorbatov, I.K. Razumov, Yu.N. Gornostyrev, V.I. Razumovskiy, P.A. Korzhavyi, A.V. Ruban, PRB, in press TTT diagram of decomposition of dilute Fe-Cu alloy showed the time needed to attain the precipitation fraction equal 0.2 from maximal value at given temperature. Accounting of changes in magnetic state is necessary for correct description of the transformation Time-Temperature-Transformation (TTT) diagram of decomposition of dilute Fe-Cu alloy It is in a good agreement with experimental kinetics MISiS, 20-10-2013 PDLM FM IQMS

12. SRO is responsible for induced magnetic anisotropy in Fe-Si, Fe-Al and for large magnetostriction in Fe-Ga MISiS, 20-10-2013 IQMS

13. Profiles of superstructure peak (300) and (003) of single crystal Fe (1-x) Si x (x = 0.08) diffuse scattering [N.V. Ershov et al. 2008, 2009] After cooling from 850°C SRO B2 type is dominate Relative volume of D0 3 regions increases after annealing at 450°C. B2 D0 3 B2 D0 3 Effect of temperature on SRO in Fe-Si 850°C 450°C Different SRO appear in T > T C and T < T C regions What is mechanism of SRO formation in Fe-Si alloys? Why SRO change nearby Curie temperature? MISiS, 20-10-2013 13

14. Effective Si-Si interaction energies for Fe – 8% Si alloy Energy of effective pair interactions 1.The interactions are mostly repulsion and short-ranged 2.Sensitive to magnetic state of iron 3.Interaction energy of 2-th neighbors significant decrease in PM state Chemical interactions Total interactions MISiS, 20-10-2013 14 IQMS

15. - Metropolis Monte Carlo predicts B2 type SRO for T > T C and C Si  8%. - D0 3 type SRO corresponds to T < T C. B2 D0 3 Monte Carlo simulation of short-range order in Fe-Si Τ = 900 o C Τ = 300 o C – the probability of finding an atom Β in the n-th coordination sphere of another atom Β MISiS, 20-10-2013 15 IQMS

16. 1.Short-ranged order formation in Fe-Si and Fe-Al has been investigated by Monte Carlo with ab-initio calculated of interatomic interaction energies. 2.We found essential effect of magnetism on SRO formation - B2 type SRO form at T > T C, and It inherits during cooling down; - D0 3 type SRO is preferable for temperatures T < T C and appears after annealing of quenches samples; 3. The results support the model of the induced magnetic anisotropy based on ordering Si-Si pairs. However, these pairs do not appear during annealing below T C and rather quenched from paramagnetic state MISiS, 20-10-2013 16

17. Give main contribution to microstructure formation The microscopic mechanism is still not clear MISiS, 20-10-2013 IQMS

18. 18 What mechanism of martensitic transformation? Martensitic transformation appear at T < Ms as results of lattice instability What reasons for lattice instability in fcc Fe ? MISiS, 20-10-2013 But there is not soft modes in phonon spectra of fcc Fe Leonov, I., Poteryaev, A.I., Anisimov, V.I. & Vollhardt, D., PRB, 2012

19. Bain path energetics. Importance of magnetic short range order (MSRO). The energy of Fe in dependence on tetragonal distortions for different magnetic states Ferromagnetic FCC Fe is unstable. Paramagnetic (DLM) FCC Fe is stable, however  transition do not lead to energy gain. Paramagnetic BCC Fe stabilize by MSRO Energy barrier connected with magnetic structure SS – FM transition. There is magnetic instability in FM FCC Fe. Cooling down to T T C – nucleation and grows. S.V. Okatov et al, PRB 2009 19 IQMS MISiS, 20-10-2013

20. IQMS 20 Bain path in dependence on temperature For description of BP at intermediate temperature the exchange interactions in dependence on deformation are nesessary From Fe FM 0K calculation (PM) (FM) Fe From Fe DLM calculation Intermidiate T?Martensitic transformation Nucleation and grows MISiS, 20-10-2013

21. Spin lattice coupling in  - Fe. Exchange energy appear big and comparable with T in distorted FCC Fe Follow expect strong spin lattice coupling Exchange parameters from spin-spiral calculations (VASP) IQMS S.V. Okatov et al, PRB 2012 21 MISiS, 20-10-2013

22. IQMS 22 Simple model of Bain path in dependence on temperature Energy Free energy magnetic contribution (Hellmann-Feynman) Bain path energetics from ab-initio for FM and PM(DLM) states MISiS, 20-10-2013

23. Kinetic equations of model For displacements The solution this equation is determined thee new phase nucleation (with taking into account thermal fluctuations and microstructure formation and composition evolution where 23 IQMS MISiS, 20-10-2013

24. IQMS 24 Results of modeling Martensitic transformation after fast (a)/slow(b) cooling at T < M S MISiS, 20-10-2013

25. ИКМ Towards of consistent model of polymorphic transformation in steel 25 1. Effective Hamiltonian (free energy) parameterization from ab-inito 2. Taking into account effect of carbon on BP energetics and phase equilibrium 3. Taking into account mechanism of plastic relaxation of internal stress associated with transformation What we need to be happy ? MISiS, 20-10-2013

26. IQMS 26 Effect carbon on Bain path and critical points Description of plastic relaxation is still open MISiS, 20-10-2013 C=0% C=1%

27. 27 Thank you for attention MISiS, 20-10-2013

28. 28 Backup MISiS, 20-10-2013

29. IQMS 29 Transformation in Fe-c. Results of modeling Ferrite transformation in Fe-2%C at T=1100K with taking into account carbon distribution (2-nd row) and plastic relaxation (black and white – ferrite two orientations, gray – austenite) MISiS, 20-10-2013 5E+04 7.5E+04 1E+05 6E+05 2E+06 1 1.37 1.5 15 7.5E+05 Bainite transformation in Fe-2%C at T=900K with taking into account carbon distribution (2-nd row) and plastic relaxation (black and white – ferrite two orientations, gray – austenite) Proposed model catch main observed features of polymorphic transformation

30. Effect of magnetism on solubility Magnetic state of the host (iron) exerts an influence Solubility anomaly in Fe-Cu and Fe-Zn at the Curie temperature is the most pronounced effect A.P. Miodownik, Bulletin of Alloy Phase Diagrams, Volume 2, Issue 4, March 1982, Pages 406-412 30 KTH, 15-05-2013

31. 31 Solubility of 3d elements in bcc iron The strongest effect of magnetism is for Cr, Ni, Cu, V, Ti Sc has the largest relaxation contribution O.I. Gorbatov, S.V. Okatov, Yu.N. Gornostyrev, P.A. Korzhavyi, A.V. Ruban, 2008 mRy

32. Multiscale approach: Application to decomposition and hardening in Fe-Cu alloy IQMS ( I ) Ab-initio calculation of the interaction energy between Cu atoms in bcc Fe ( II ) Monte-Carlo simulations of the alloys decomposition with ab- initio parameters Prediction solubility Cu in Fe and phase diagram Precipitate size and morphology vs. time and temperature annealing ( III ) Molecular dynamic modeling of the interaction between dislocation and Cu particles ( IV ) Determination of the shear resistance in dependence on composition and size Cu particles Assessment strengthening Fe due to embedded Cu nano particles Prediction of treatment regimes to obtain high strength and plasticity d=4.5nm Dislocation energy Dislocation locking  cr MISiS, 20-10-2013 32

33. IQMS 33 Effective cluster interactions from SGPM calculations Precipitation kinetics in Fe-Cu-Nb Monte-Carlo modeling with first-principle parameterization KTH, 15-05-2013

34. IQMS 34 Effect carbon on Bain path and critical points Description of plastic relaxation is still open 0 0.05 0.1 0.15 0.2 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 a 1 /a 2 0 0.05 0.1 0.15 0.2 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 a 1 /a 2 0 0.05 0.1 0.15 0.2 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 a 1 /a 2 C=1% C=0% C=3% T,KT,K 1184 840 373 FSFS BSBS MSMS 0 3.4 c, at.% 1000 bcc+fcc fcc+Cem fcc MISiS, 20-10-2013

35. ИКМ Towards of consistent model of polymorphic transformation in steel deformation magnetism carbon (FM) (PM) 1300К 1200К 1100К 1000К (FM) Fe Bain path energetics for FM and PM states Finite T from effective Hamiltonian 35MPIE, 2-10-2012 The construction of effective Hamiltonian for finite T is nesessary