Designing martensitic steels: structure & properties Enrique Galindo-Nava and Pedro Rivera

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1 Designing martensitic steels: structure & properties Enrique Galindo-Nava and Pedro Rivera Feng Qian, Mark Rainforth (Sheffield); Wenwen Song (Aachen) 1

2 Outline Aim: Understand the factors controlling mechanical properties in martensitic steels Identify alloy/process design scenarios for resource efficiency Modelling the structure of Fe-C martensite: Lath martensite: Low/Medium-C steels Twinned martensite: High-C steels Modelling the structure of maraging steels: Martensite+austenite+intermetallic evolution Elongation VS reverted austenite 2

3 Fe-C martensite Fe-.18C wt% Hardness (HV3) Fe-1.6C wt% Sherby et al., Mater Trans (28) 3

4 Maraging steels: Fe-1Mn-2Ni-1Al-1Mo-.85Ti (wt%) As-quenched: Low & high-angle GBs+dislocations Tempered: reverted γ+ni 2 TiAl 4

5 Alloy/process design: strengthening in martensite? Microstructural contributions: 1. Solid solution hardening (σ ss ) 2. Hall-Petch of high & low angle GBs (σ HP ) Strength (MPa) Dislocations+twins (σ dis ) 4 4. Precipitation hardening (σ p ) 2 5. Other phases (austenite, ferrite, ) Typical strengthening contribution in Maraging steels As-quenched Tempered σ Y = σ ss +σ HP +σ dis +σ p Precipitation Dislocations Hall-Petch Solid solution 5

6 Low/Med C steels: Lath martensite Hierarchical structure formed by diffusionless transformation Packets and blocks (HAGBs) form to compensate crystallographic distortions and ensure that the overall strain is a pure dilatation (*) Laths (LAGBs) form to minimise the strain energy produced by the lattice distortions around carbon atoms: Lattice strains are accommodated by dislocations at & within lath boundaries (**) (*) Kinney et al., Acta Mater. (214), (**) Olson & Cohen, Metall. Trans. (1975) 6

7 Packet and block arrangements σ ss +σ HP +σ dis +σ p All 24 variants of the Kurdjumov-Sachs orientation are used within a prior austenite grain (*) Prior-austenite grain: 4 packets Packet: 6 blocks with each variant sharing the same {111}FCC plane Fe-9Ni (*) Kinney et al., Acta Mater. (214) 7

8 Packet and block arrangements ( 1) FCC ( 1) (a) BCC 111 (b) ( ) FCC ( 11) BCC [ 1] FCC [ 11] BCC!11 " # $! FCC " 111# $ BCC ε Bain 8

9 Martensite structure: model σ ss +σ HP +σ dis +σ p A prior-austenite grain is subdivided into 4 packets that contain all Kurdjumov-Sachs variants (*) A packet contains 6 blocks with each variant sharing the same {111} FCC plane Prior-austenite grain Packet V PAG = N packets V packet V packet = N blocks V block Block Laths (*) Kinney et al., Acta Mater. (214) 9

10 Results: PAGS effects in Fe-C steels Packet size (µm) Exp - Hoseiny et al. (212) Exp - Morito et al. (26) Exp - Morito et al. (26) Exp - Maki et al. (26) Exp - Zhang et al. (212) Model Block size (µm) Exp - Yan et al. (214) Exp - Morito et al. (26) Exp - Morito et al. (26) Exp - Zhang et al. (212) Model Austenite grain size (µm) Austenite grain size (µm) No effects of chemical composition! Galindo-Nava & Rivera-Díaz-del-Castillo, Acta Mater. (215) 1

11 Laths: Dislocations & C effects σ ss +σ HP +σ dis +σ p There is less understanding on lath formation: Experimental evidence shows no PAGS effects (*) Olson & Cohen s martensite nucleation mechanism: Dislocation arrangements at the γ\α interface (**) Lath size and dislocation density are linked: Strain energy within a lath: E dis = E lattice ρ ε 2 Bain 2 d lath (*) Morito et al., Mater. Sci. Eng. A (26), (**) Olson & Cohen (1975) 11

12 Carbon segregation at dislocations: as-quenched Fe-.32C-1.6Si (*) At least 9% of C atoms segregate to dislocations (Cottrell atmospheres): d Cottrell 7 nm C dis ~5-7 at% (*) Sherman et al., Metall. Mater Trans A (27) d Cottrell d lath = d Cottrell x C 2/3 12

13 Results: Carbon content effects σ ss +σ HP +σ dis +σ p Lath width (µm) As-quenched lath width 3 Exp - Kim et al. (214) Exp - Hutchinson et al. (211) Model Exp - Swarr & Krauss (1976) Exp - Ghassemi-Armaki et al. (29) C (wt%) Dislocation density (m -2 ) Dislocation density (m -2 ) TEM density measurements Exp - Morito et al. (23) Exp - Kehoe & Kelly (197) Exp - Norstrom (1976) Model C (wt%) ρ ε 2 Bain 2 d lath Galindo-Nava & Rivera-Díaz-del-Castillo, Acta Mater. (215) 13

14 Martensite tempering Carbon migration from lath boundaries promotes lath coarsening and dislocation recovery (*): d lath = d AQ lath + d Cottrell N C! N C = x C 3 π $ # & " 2 % 1/3! AD diff t $ # & " kt % The matrix & yield stress are given by: σ α ' = 3 d block +.25Mµb ρ 2/3 Carbide precipitation is obtained from experiments (σ p ) (*) Cottrell & Bilby, Proc. Phys. Soc. (1948) 14

15 Yield Stress (MPa) 18 (a) (c) x1 15 T ( o C).4C (wt%) 1h tempering Exp - Saeglitz & Krauss (1997) Model Medium C steel:.56c-1.4si (b) Yield stress (MPa) (d) Exp - Kim et al. (214) Model.56C (wt%).5 h tempering D =12 µm T ( o C) ρ (m -2 ) 6x1 15 4x1 15 2x1 15 Exp - Kim et al. (214) Model T ( o C) lath width (nm) T ( o C) Exp - Kim et al. (214) Model 15

16 2 1.25C (wt%) D g =2 µm Alloy/process design: Martensite strength D (c) g =2 µm T ( o C) hour tempering D g =2 µm 1 t (hours) C (wt%) (d) C (wt%) t (hours) o C tempering 9 D g =2 µm C (wt%) t (hours) Grange et al., Metall. Trans (1975) 16

17 Martensite strength (a) 9 8 H f γ Exp - Grange et al. Exp - Litwinchuk et al. Mod Mod - No f γ ( ) ( )( H lath f lath + H twinned 1 f ) lath 7 HV As-quenched C (wt%) Galindo-Nava & Rivera-Díaz-del-Castillo, Scripta Mater. (215) 17

18 MARAGING STEELS 18

19 Maraging steels: elemental optimisation Important family of high-strength steels (high-strength and toughness) Factors controlling strength-elongation: α +intermetallics+γ (reverted) Wide compositional space: Fe-Ni-Mn-Cr-Ti-Al-Mo-Cu Understand their contributions to microstructure (resource efficiency) PH13-8Mo (*): Fe-12Cr-8Ni-1Al-2Mo (*) Schnitzer et al., Mater. Sci. Eng. A (21) 19

20 Alloying contributions to microstructure Fe Ni Mn Ti Cr Al Mo Cu Martensite X X X X Intermetallics X X X X X Reverted austenite X X X X Solid solution X X Galindo-Nava et al., Acta Mater. (216) 2

21 Martensitic structure σ ss +σ HP +σ dis +σ p Prior-austenite grain GB and dislocation density distribution: Packet Nucleation sites for precipitation Reverted austenite distribution Elemental segregation to laths also occurs (*) Block Laths Fe-9Mn (*) Kuzmina et al., Science (215) 21

22 Precipitation hardening: tempering σ ss +σ HP +σ dis +σ p Standard precipitation kinetics modelling (*) Nucleation sites: dislocations in martensite # & I = N Zβ exp% ΔG* ( $ k B T '! N = ρ N $ a # & " % V m 1/3 ( c p c i ) dr p dt = D diff Hardening: Orowan bowing σ p = µbf 1/2 p r p dc dr p! ln r $ p # & " b % r p (nm) (c) Exp - 53 o C Exp - 48 o C Exp - 44 o C Model - 53 o C Model - 48 o C Model - 44 o C Ni 3 Ti Exp - 53 o C Exp - 48 o C Model - 53 o C Model - 48 o C M35 t (h) (*) Kozeschnik, Modeling Solid-State Precipitation C3 22 l p (nm) (d) (H v ) (b) (a)

23 Age hardening in M35: factors controlling hardness 7 6 Fe-18Ni-12.5Co-4Mo-1.7Ti (*) Total Martensite Solid solution Precipitation Exp Hardness (H V ) o C t (h) Ni 3 Ti σ ss +σ HP +σ dis +σ p (*) Viswanathan et al., Metall. Trans. (1993), Zhu et al., Mater. Sci. Tech. (211) 23

24 Elongation VS Reverted austenite: GB embrittlement High segregation of Ni and/or Mn from quenching (underaging) Early formation of intermetallics nearby GBs (NiMn, NiAl, ) Elongation increases during overaging (*): Ni/Mn-rich γ formation Fe-1Ni-7Mn (**) Intermetallic coarsening (*) Heo et al., Phil. Mag. (28), (**) Nasim et al., Mater. Sci. Eng. (2) 24

25 Reverted austenite evolution Fe-12Mn-2Ni-1Al-1Mo-.85Ti γ α d lath γ r γ Interface-controlled diffusion d block γ γ γ h γ γ 25

26 Results: PH13-8Mo Fe Cr Ni Al Mo Bal (a) f γ (%) Exp - PH13-8Mo o C Exp - PH13-8Mo o C Model - PH13-8Mo o C Model - PH13-8Mo o C Exp - 5Mn Mod - 5Mn (b) r γ (nm) Exp - PH13-8Mo o C Model - PH13-8Mo o C Exp - 5 Mn Mod - 5 Mn 1 5 (c) h γ (nm) t (h) Exp - PH13-8Mo o C Model - PH13-8Mo o C t (h) (d) 1 f γ (%) γ t (h) t (h) γ Exp - AISI31-85 o C Exp - AISI31-8 o C Exp - AISI31-75 o C Model - AISI31-85 o C Model - AISI31-8 o C Model - AISI31-75 o C Exp - M35-54 o C α Mod - M35-54 o C Galindo-Nava et al., Acta Mater. (216) 26

27 Reverted austenite VS elongation Ni & Mn enrichment in the austenite aids in increasing elongation: (a) El (%) (c) (at%) 4 PH13-8Mo Lean-1Mn 35 Lean-12Mn 3 7Mn 17-4 SS 25 9Mn Fit El (%) = f γ f γ (%) 25 3 (a) (b) Mn (at%) (c) gation (%) Ni/Mn content VS Elongation (%) o C for 5 h Ni Ni (at%) (at%) 55 Mn o C M35 stronger effect 14.9Ni4Mn1.9Ti3Mo than Ni! PH13-8Mo 17-4 SS (b) Elongation (%)

28 Alloy design for elongation: resource efficiency Composition (wt%) Steel Fe Ni Mn Co Ti Mo M35 Bal Ni4Mn1.9Ti3Mo Bal σ Y (MPa) o C t (h) M35 15Ni4Mn1.9Ti3Mo Austenite fraction (%) Elongation (%) Strength-elongation: overaging σ Y (MPa) M35 15Ni4Mn1.9Ti3Mo 28

29 Summary Fe-C martensitic steels: Hierarchical structure of lath martensite Twinned martensite: Carbon segregation at twins and dislocations Design process routes for high strength (C VS T) Maraging steels: Links between composition and microstructure Ni & Mn: reverted austenite Al, Ti, Cu: precipitation Mo: solid solution Design for resource efficiency considering strength-elongation 29

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