Third-generation advanced high-strength steels (3G AHSS) are being developed to assist in vehicle light weighting so that fuel efficiency may be improved without sacrificing passenger safety. 3G-AHSS have received significant interest from the automotive industry as a critical candidate for their unique combination of high strength and ductility. However, due to selective oxidation of the principal alloying elements such as Mn, Si, Al, and Cr at the steel surface during the annealing stage prior to immersion in the galvanizing Zn(Al, Fe) bath, the process of continuous hot-dip galvanizing of these steel is challenging. This thesis determined the influence of annealing process parameters such as oxygen partial pressure and annealing time, on the selective oxidation and reactive wetting of an Fe-0.15C-5.56Mn-1.17Si-1Al (wt%) prototype 3G AHSS during intercritical annealing as well as continuous galvanizing. Simulated annealing and galvanizing were conducted on the prototype Fe-0.15C-5.56Mn-0117Si-1Al (wt%) 3G steel; Intercritical annealing heat treatments were carried out at 690˚C in a N2-5 vol pct H2 process atmosphere under dew points of 223 K (–50 °C), 243 (–30 °C) and 268 K (–5 °C). MnO was the major oxide formed at the outmost layer of the external oxides on all annealed samples. The experimental parameters, on the other hand, had a substantial impact on the morphology, distribution, thickness, and surface oxide coverage. The greatest Mn surface concentration as well as maximum surface oxide coverage and thickness was obtained by annealing the panels under the 223 K (–50 °C) and 243 (–30 °C) dp process atmospheres. The oxides formed under these process atmospheres largely comprised coarse, compact, and continuous film nodules. In contrast, MnO nodules formed under the 268 K (–5 °C) dewpoint process, exhibited wider spacing between finer and thinner nodules, which was consistent with the internal oxidation mode, while under 223 K (–50 °C) dp process atmosphere, generally external oxidation took place. Poor reactive wetting was obtained for the panels annealed under the 223 K (–50 °C) dp process atmosphere for both the 60 s and 120 s holding times as well as the 243 K (–30 °C) dp process atmosphere for 120 s. This was attributed to the formation of a thick, compact oxide layer on the steel surface, which acted as a barrier between the substrate and Zn bath, preventing Fe dissolution from the substrate surface for the formation of the desired Fe2Al5Znx interfacial layer. However, a well-developed interfacial Fe-Al intermetallic layer was formed under the 268 K (–5 °C) and 243 (–30 °C) dp process atmospheres for intercritical annealing times of 60 s, which is indicative of a good reactive wetting since the thinner and nodule-like oxides on the steel surface after annealing encourage the reactive wetting. External oxides morphology plays a dominant role in facilitating the contact between Zn-alloy bath and the substrate via different mechanisms such as aluminothermic reduction which occurred for the sample annealed under the 268 K (–5 °C) dp process atmosphere. / Thesis / Master of Applied Science (MASc)

Medium Mn (med-Mn) third generation advanced high strength steels (3G AHSSs) are promising candidates for meeting automotive weight reduction requirements without compromising passenger safety. However, the thermal processing of these steels should be compatible with continuous galvanizing line (CGL) processing capabilities as it provides cost-effective, robust corrosion protection for autobody parts. Hence, the main objective of this Ph.D. research is to develop a CGL-compatible thermal processing route for a prototype 0.2C-6Mn-1.5Si-0.5Al-0.5Cr-xSn (wt%) (x = 0 and 0.05 wt%) med-Mn steel that will result in the 3G AHSS target mechanical properties (24,000 MPa%  UTS × TE  40,000 MPa%) and high-quality galvanized coatings via enhanced reactive wetting. It was found that the starting microstructure, intercritical annealing (IA) time/temperature, and Sn micro-alloying had a significant effect on the retained austenite volume fraction and stability and, thereby, the mechanical properties of the prototype med-Mn steel. For the as-received cold-rolled (CR) starting microstructure, the intercritical austenite nucleated and grew on dissolving carbide particles and resulted in blocky retained austenite. However, Sn micro-alloying significantly effected the intercritical austenite chemical stability by segregating to the carbide/matrix interface and retarding C partitioning to the intercritical austenite. This resulted in lower volume fractions of low stability retained austenite which transformed to martensite (via the TRIP effect) at low strains, thereby quickly exhausting the TRIP effect and resulting in a failure to sustain high work hardening rates and delay the onset of necking. Consequently, the Sn micro-alloyed CR starting microstructure was unsuccessful in achieving 3G AHSS target mechanical properties regardless of the IA parameters employed. Contrastingly, the CR starting microstructure without Sn micro-alloying was able to meet target 3G mechanical properties via intercritical annealing at 675 °C × 60 s and 120 s, and at 690 °C × 60 s owing to sufficiently rapid carbide dissolution and C/Mn partitioning into the intercritical austenite such that it had sufficient mechanical and chemical stability to sustain a gradual deformation-induced transformation to martensite and maintain high work hardening rates. On the other hand, the martensitic (M) starting microstructure produced higher volume fractions of chemically and mechanically stable lamellar retained austenite regardless of Sn micro-alloying. Intercritical annealing at 650 °C × 60 s and 675 °C × 60 s and 120 s produced 3G AHSS target mechanical properties. It was shown that the stable lamellar retained austenite transformed gradually during deformation. Furthermore, deformation-induced nano-twin formation in the retained austenite was observed, suggesting the TWIP effect being operational alongside the TRIP effect. As a result, a continuous supply of obstacles to dislocation motion was maintained during deformation, which aided in sustaining a high work hardening rate and resulted in a high strength/ductility balance, meeting 3G AHSS target properties. Based on these results, the martensitic starting microstructure without Sn micro-alloying and the M-675 °C × 120 s IA condition were chosen for the selective oxidation and reactive wetting studies. The selective oxidation study determined the effect of a N2-5H2-xH2O (vol%) process atmosphere pO2 (–30, –10, and +5 °C dew point (Tdp)) on the composition, morphology, and spatial distribution of the external and internal oxides formed during the austenitizing and subsequent intercritical annealing cycles. The objective of this study was to identify the process atmosphere for the promising M-675 °C × 120 s heat treatment that would result in a pre-immersion surface that could be successfully galvanized in a conventional galvanizing (GI) bath. The austenitizing heat treatment (775 °C × 600 s) used to produce the martensitic starting microstructure resulted in thick (~ 200 nm) external oxides comprising MnO, MnAl2O4, MnSiO3/Mn2SiO4, and MnCr2O4, regardless of the process atmosphere pO2. However, intermediate flash pickling was successful in dissolving the external oxides to a thickness of approximately 30 nm along with exposing metallic Fe in areas which contained relatively thin external oxides. Furthermore, extruded Fe nodules that were trapped under the external oxides were revealed during the flash pickling process. Overall, flash pickling resulted in a surface consisting of dispersed external oxide particles with exposed metallic substrate and extruded Fe nodules. This external surface remained unchanged during IA owing to the multi-micron (~ 2–8 µm) solute-depleted layer that formed during the austenitizing heat treatment. Subsequent galvanizing in a 0.2 wt% (dissolved) Al GI bath with an immersion time of 4 s at 460 °C was successful in achieving high-quality, adherent galvanized coatings through multiple reactive wetting mechanisms. The dispersed nodule-type external oxides along with exposed substrate and extruded Fe nodules on the pre-immersion surface facilitated direct wetting of the steel substrate and promoted the formation of a robust and continuous Fe2Al5Znx interfacial layer at the steel/coating interface. Additionally, oxide lift-off, oxide wetting, bath metal ingress, and aluminothermic reduction were operational during galvanizing. The galvanized med-Mn steels met 3G AHSS target mechanical properties. Overall, this Ph.D. research showed that it is possible to employ a CGL-compatible thermal processing route for med-Mn steels to successfully produce 3G AHSS target mechanical properties as well as robust galvanized coatings. / Thesis / Doctor of Philosophy (PhD) / One of the largest challenges associated with incorporating the next generation of advanced high strength steels into the automotive industry lies in processing these steels in existing industrial production lines. In that regard, a two-stage heat treatment with an intermediate flash pickling stage and process atmosphere compatible with existing industrial continuous galvanizing line technology was developed for a prototype medium-Mn steel. The heat-treated prototype steel met the target mechanical properties outlined for the next generation of advanced high strength steels. Furthermore, the heat treatment and process atmosphere utilised in this research produced a surface that facilitated the successful galvanizing of the prototype medium-Mn steel. This adherent and high-quality galvanized coating will provide robust corrosion protection if the candidate medium-Mn steel is used in future automotive structural applications.