Segregation and partitioning phenomena at phase boundaries of complex steels are important for their microstructural, mechanical, and kinetic properties. We present nanoscopic atom probe tomography results across martensite/austenite phase boundaries in a precipitation-hardened maraging TRIP steel after aging at 450°C for 48 hours (12.2 at.% Mn, 1.9 at.% Ni, 0.6 at.% Mo, 1.2 at.% Ti, 0.1 at.% Si, 0.3 at.% Al, 0.05 at.% C). The system reveals compositional changes at the phase boundaries: Mn and Ni are enriched ~2.1 and 1.2 times, respectively, relative to the average matrix content. In contrast, Ti is depleted ~6.9 times relative to the average content, Al ~6.6 times, Mo ~2.0 times, and Fe ~1.2 times. The strong accumulation of Mn at the interfaces is of particular interest as it strongly affects the transformation equilibrium and kinetics in steels. We observe up to 27 at. % Mn in a 20 nm thick layer at the martensite/austenite phase boundary. This can be explained by a large difference in diffusivity between martensite and austenite. The high diffusivity in martensite leads to a Mn-flux towards austenite. The low diffusivity in austenite does not allow accommodation of this flux within the matrix. Consequently, the phase boundary moves towards martensite with a Mn-composition given by the local equilibrium condition. This interpretation relies on diffusion calculations performed with the method DICTRA. A mixed-mode approach involving finite interface mobility was also applied to refine the agreement with the experiments. In order to achieve a good agreement the diffusivity in martensite had to be increased compared to ferrite. This can be attributed to a high defect density.
3. 2
Motivation: Combine TRIP and maraging effects
Mn is among the most important alloying elements for the design
of advanced high strength steels
It affects the stabilization of the austenite, the stacking fault
energy, and the transformation kinetics
Mn has very low diffusion rates in the austenite and a high
segregation or respectively partitioning tendency at interfaces
This context makes Mn a very interesting candidate for an
atomic-scale study of compositional changes across
austenite/martensite interfaces.
Dierk Raabe (d.raabe@mpie.de)
5. 4
Motivation: Combine TRIP and maraging effects
The material studied here is a precipitation-hardened alloy that is referred
to as maraging TRIP steel
It combines the TRIP mechanism with the maraging effect (maraging:
martensite aging)
The TRIP effect exploits the deformation-stimulated transformation of
metastable austenite into martensite and the resulting plasticity required to
accommodate the transformation misfit
The maraging effect uses the hardening of the heavily strained martensite
through the formation of nano-sized intermetallic precipitates during aging
heat treatment
The maraging TRIP steels used in this work reveal the surprising property
that both strength and total elongation increase upon aging reaching an
ultimate tensile strength of nearly 1.3 GPa at an elongation above 20%
Dierk Raabe (d.raabe@mpie.de)
Raabe, Ponge, Dmitrieva, Sander: Scripta Mater. 60 (2009) 1141
6. 5
Fe-Mn based maraging TRIP steel development
TRIP: deformation-stimulated transformation of instable austenite
into martensite and accommodation plasticity (e.g. Mn, Ni, low C)
Maraging effect: hardening of heavily strained martensite via nano-
sized (intermetallic) precipitates (Ni, Al, Ti, Mo)
(see also conventional Maraging steels)
* TRIP: transformation-induced plasticity
* Maraging: martensite aging
Raabe, Ponge, Dmitrieva, Sander: Adv. Eng. Mat. 11 (2009) 547
Quenched austenite: ductile low carbon martensite
Retained austenite (TRIP)
Controlled precipitation hardening
What is maraging-TRIP ?
Dierk Raabe (d.raabe@mpie.de)
7. 6
Low carbon: ductile martensite
Steel C Ni Co Mo Ti Al Mn Fe
Maraging 0.01 18 12 4 1.6 0.15 0.05 Balance
09MnPH 0.01 2 - 1 1.0 0.15 9 Balance
12MnPH 0.01 2 - 1 1.0 0.15 12 Balance
15MnPH 0.01 2 - 1 1.0 0.15 15 Balance
Precipitation Hardenable
Mn (+Ni): austenite (TRIP)
Compositions in mass%
PH
PH
PH
D. Raabe et al. Scripta Materialia 60 (2009) 1141
Martensite aging after quenching at 450°C
Dierk Raabe (d.raabe@mpie.de)
15. 14
R. Kainuma, M. Ise, K. Ishikawa, I. Ohnuma, and K. Ishida, Phase Equilibria and Stability of the B2
Phase in the Ni-Mn-Al and Co-Mn-Al Systems, J. Alloys Compd., 1998, 269, p 173-180
Ni-Mn-Al isothermal section at 850 °C
Ni Mn
Al
Dierk Raabe (d.raabe@mpie.de)
16. Mn atoms
Ni atoms
Mn iso-concentration surfaces at 18 at.%
APT results: Atomic map (12MnPH aged 450°C/48h)
70 million ions
Laser mode
(0.4nJ, 54K)
Dmitrieva et al., Acta Mater, in press 2010
Martensite decorated by precipitations
Austenite
?
?
Dierk Raabe (d.raabe@mpie.de)
15
17. M A
Mn layer 1
Mn layer 2
Mn layer2
Mn layer 1
Mn iso-concentration surfaces at 18 at.%
Thermo-Calc
Phase equilibrium Mn-contents:
27 at. % Mn in austenite (A)
3 at. % Mn in ferrite (martensite) (M)
1D profile: step size 0.5 nm
M A M
depletion zone
nominal 12 at.% Mn
APT results: chemical profiles
Dmitrieva et al., Acta Mater, in press 2010 16
Dierk Raabe (d.raabe@mpie.de)
18. 17
precipitates in a`
no precipitates in
12MnPH after aging (48h 450°C)
nmDtxDiff 302
nmxDiff 2
Raabe, Ponge, Dmitrieva, Sander: Adv. Eng. Mat. 11 (2009) 547
19. Mean diffusion path of Mn in austenite
(aging 450°C/48h) 2 nm
M A
Mn layer 1
Mn layer 2
nominal 12 at.%
Thermo-Calc
Phase equilibrium Mn content:
27 at. % in austenite
3 at. % in ferrite (martensite)
10 nm
Ti, Si,
Mo
Mn-rich
layer
AM
PB migration
Mn diffusion
phase boundary
aging
New
austenite
(formed
during
aging)
DICTRA
AM
original position
phase boundary
final position
phase boundary
APT results and simulation: DICTRA/ThermoCalc
Dmitrieva et al., Acta Mater, in press 2010 18
Dierk Raabe (d.raabe@mpie.de)
26. Conclusions
25
Mn atoms
Ni atoms
Mn iso-concentration surfaces at 18
at.%
martensite
with
precipitates
martensite with
precipitates
70 million ions
Laser mode
(0.4nJ, 54K)
martensite
with
precipitates
austenit
e
Raabe, Ponge, Dmitrieva, Sander: Adv. Eng. Mat. 11 (2009) 547
Dierk Raabe (d.raabe@mpie.de)
Notes de l'éditeur
Quantitative analysis of the chemical interfaces between austenite and martensite was performed using 1D concentration profiles computed over the region of interest (cylindrical units). We calculated the content of manganese averaged over the 0.5 nm thick cross sections of the cylinders (profile step size 0.5 nm). For both interfaces, strong increase of Mn content up to 26 at. % was observed. The content of the Mn on the austenitic side is about 12 at. %, whereas on the martensitic side a slight depletion of Mn down to 6 at. % can be observed. In order to avoid the contribution of the precipitates to the chemical profile within the martensitic area, we separately measured the 1D concentration profiles within the martensitic matrix after exclusion of the precipitates. These profiles are also plotted.
In order to understand the reasons for the Mn accumulation on the phase boundary, we consider the measured Mn contents. Since the phase equilibrium concentration of Mn in the austenite is much higher than in the ferrite (martensite) as was calculated by using Thermo-Calc (26.7 vs. 3.3 at. %), we expect a redistribution of Mn atoms during aging: enrichment in the austenite and depletion in the martensite. However, the Mn content measured in the austenite remains the same as in the nominal alloy composition (about 12.2 at. %, see Table1). In the martensitic matrix, a slight Mn depletion down to 10.3 at. % was detected. The diffusion in the FCC lattice of austenite is widely suppressed. The martensitic matrix is depleted to 10.3 at. % which is mostly due to the enrichment of Mn in the precipitates. However, Mn content decreases continuously in the martensite toward the phase boundary and, just some nanometers before the Mn-rich layer starts, drops to about 5-6 at. %. The formation of such depletion zone indicates an enhanced diffusion behavior of Mn atoms from the martensite to the austenite. Due to the low diffusion in the austenite, Mn atoms accumulate in the phase boundary and built up a Mn-enriched layer.
The Mn gradient obtained from the thermodynamic calculation using DICTRA provides nearly the same distribution of the Mn content on the austenite/martensite phase boundary (Fig. 4). Enrichment of Mn up to the content of 27 at. % is observed in the interface between austenite and ferrite. For the simulation of the diffusion of Mn in the martensite, we enhanced the mobility of the atoms given for ferrite by a factor of 45.
(During time of annealing at given temperature in (α+γ) range, Mn moves from ferrite to austenite across interface surface between austenite and ferrite until
equilibrium state of the chemical potentials of Mn in austenite and ferrite will be reached. The balance depends on temperature and time of annealing.)
In order to understand the dynamics of the formation of the Mn-enriched layers on the phase boundaries, we consider the phase equilibrium contents of Mn. The averaged content of Mn measured for the Mn-enriched layers is about 26 at. %. This content corresponds to the phase equilibrium content of this element in the austenite which is 26.7 at. %. As known, local phase equilibrium can be easily reached on the grain/phase boundaries. Thus, right on the phase boundary, the equilibrium composition in austenite is reached, and a local phase transformation from martensite to austenite within the Mn-enriched layer can be expected.
However, the
With the growth of the Mn-enriched layer towards the martensitic grain, the material within the layer becomes austenitic and, thus, the phase boundary moves. The final thickness of the Mn-enriched layer is about 20 nm, thus, the phase boundary moved 20 nm during the aging treatment.
The layer-to-austenite interface provides the information about the position of the original phase boundary between the retained austenite and the martensite before aging. Further diffusion of Mn into austenite during aging was suppressed just beyond the crystallographic BCC/FCC boundary. The martensite-to-layer interface, however, indicates the position of the final phase boundary when the Mn diffusion was stopped by the water quenching after the aging treatment. The Mn enriched area in-between these two layers therefore can be addressed as additional austenite formed during the aging.
The growth of the austenite leads to an enhancement of austenite volume fraction during aging. This can be correlated to the growth of the existing austenite grains where the phase boundaries serve as nucleation seeds. We assumed an epitaxial formation of reverted austenite on the phase boundary of the retained austenite.