La Constitución

The importance of Mn as a major component in these two-stage TRIP steels can be demonstrated by first principle calculations of both the unstable stacking fault and intrinsic stacking fault energies as discussed by Medvedeva et al. [29], and Limmer et al. [30]. A generalized stacking fault energy curve is shown in Figure 1. A stacking fault is produced by shearing the fcc crystal on {111}γ in the direction of <112>. An unstable

dislocation. The resultant deformed crystal is typically at a higher energy and represents an unstable configuration. The unstable stacking fault energy represents the barrier to the nucleation of a Shockley partial dislocation. Displacing the crystal by a full partial dislocation leads to the formation of an intrinsic stacking fault. Stacking in the {111}γ

changes the ABCABC stacking to an AB[CA|CA]BC where the stacking fault is seen as the break line, |, and the portion within the brackets represents four layers of {0001}ϵ hcp

crystal. Quite often the resultant intrinsic stacking fault energy (ISFE) at room

temperature is negative (more stable than the fcc crystal structure), but is still unstable with respect to either the bcc crystal structure or α-martensite Medvedeva et al. [29] demonstrated a parabolic minimum at 12 atomic percent manganese for the ISFE provided the manganese resides at the stacking fault, whereas there is a continuous decrease in the USFE with manganese addition. Limmer et al. [30] showed that Mn is the only element to both lower the USFE and the ISFE making the ε-martensite both easier to form and more stable. Aluminum and silicon both lower the USFE making ε- martensite, and dislocation nucleation easier however they increase the ISFE [30A]. Medvedeva et al. [29] also calculated that carbon increases the ISFE when placed at the fault plane; however, Mn can help mitigate this effect by segregating to the fault plane to form a Mn-C dipole.

Fig. 1. Generalized stacking fault energy curve for pure Fe calculated by first-principles simulation. Unstable stacking fault energy (USFE) and intrinsic stacking fault energy (ISFE) are shown in the plot at 0.5 and 1.0. Graph redrawn from Medvedeva et al. [29].

1.3. Effect of Chemistry

The complex effect of Mn has also been presented in the works of Pisarik and Van Aken [31] and Field et al. [32]. Thermodynamic calculations by Pisarik and Van Aken [31] determined that the ε-martensite start temperature is related to Mn in a

parabolic fashion, with a minimum occurring at roughly 12-13 wt. pct. Mn. Similar work by Field et al. on the start temperature for α-martensite [32] yielded two distinct

behaviors in the thermodynamic driving force for α-martensite formation. Alloys that contained greater than 12 wt. pct. manganese exhibited a greater temperature dependence for the driving force of transformation and alloys having less than 12 wt. pct. manganese exhibited a thermodynamic relation similar to what had been reported for lath martensitic steels. However, the proposed model was limited Mn contents less than 16 wt. pct. for the prediction of α-martensite start temperatures.

Automotive steels are typically produced as a hot band product with a gauge thickness between 1.8 and 3.3 mm [33] and recrystallization behavior of the hot band steel is of significant concern for subsequent cold rolling. Hot band properties reported by Field and Van Aken [1] for a two-stage TRIP steel with 2.4 wt. pct. Si exhibited a high ultimate tensile strength of 1840 MPa and elongations of 13 pct. whereas the same steel after cold working and batch annealing produced a ultimate tensile strength of 1400 MPa and an elongation to failure of 34 pct. It has been reported in literature that

substitutional alloying elements like silicon and aluminum will influence the dynamic and static recrystallization of TRIP steels [34-36]. Suikkanen et al. [34] found that the rate of static recrystallization linearly decreased with increasing Si up to 1.5 wt. pct. This effect has also been observed in the works by Somani et al. [37], Medina and Mancilla [38], and Medina and Quispe [39]. Silicon’s effect on recrystallization has been rationalized assuming a solute drag effect on grain boundaries. Li-Juan et al. [35] investigated the effect of Si and Mn on the dynamic recrystallization of conventional TRIP steel and showed that Mn had little effect on the dynamic recrystallization; however, they observed that silicon was effective in slowing the dynamic

recrystallization and increased the static recrystallization temperature. It was also shown by Zhu et al. [36] that the dynamic recrystallization response is greatly impeded when the silicon content is increased to 1.5 wt. pct. silicon.

Little has been reported on the influence of Al on the recrystallization of TRIP steel. Somani et al. [34] found that Al had a negligible effect on static recrystallization. Aluminum’s effect on the properties of first generation advanced high strength TRIP steels is considered to be very complicated. Aluminum has been shown to affect the

work hardening behavior and the dynamic strain aging (DSA) response of TWIP and TRIP steels [1, 19, 40]. It has been shown in the high-Mn TWIP steels that Al additions will reduce the work hardening rate by reducing the deformation twin density [40]. Lee et al. [40] investigated the dynamic strain aging of two TWIP steels, one containing aluminum, 0.6C-18Mn-1.5Al-BalFe (wt. pct.), and the second being an Al-free 0.6C- 18Mn-balFe (wt. pct.) steel, and it was observed that the work hardening rate and

ultimate tensile strength were reduced with the addition of aluminum. Lee et al. showed that Al was effective in suppressing the dynamic strain aging of the TWIP steel. Work by Grässel et al. [19] shows that the ultimate tensile strength of 15Mn-xSi-yAl (in wt. pct.) exhibited a decrease in ultimate tensile strength with increasing aluminum content and that the ductility increased with increasing aluminum content. The effects silicon and aluminum on recrystallization are of great concern for potential two-stage TRIP steels because both Al and Si reduce the USFE [30] and are considered favorable alloying elements for ε-martensite formation.

Nitrogen and carbon are also expected to affect the strength of the newly designed two-stage TRIP steels. Field and Van Aken [1] found that nitrogen in α-ferrite was a potential cause for both static and dynamic strain aging in an intercritically annealed 10 wt. pct. Mn steel. It is well established that DSA leads to increased ultimate tensile strengths and reduced elongations. Two additional DSA mechanisms were identified: in microstructures containing ε-martensite trapping of Mn atoms at stacking faults and Mn- C defect pairs in γ-austenite also contribute to dynamic strain aging.

The purpose of this work is to attempt to understand and empirically model the effect of chemistry and microstructure on the measured properties of recently developed

medium-Mn two-stage TRIP steels and to show how stacking fault energy calculations can be used to formulate two-stage TRIP alloys.