Third generation advanced high-strength steels (3G-AHSS) have received significant interest from leading auto steel industries and OEMs as candidate materials for reduced mass Body In White (BIW) components due to their unique combination of high specific strength and ductility. However, the continuous hot-dip galvanizing of these steels is challenging due to selective oxidation of the main alloying elements such as Mn, Si, Al and Cr at the steel surface during the annealing step prior to immersion in the galvanizing Zn(Al, Fe) bath, as extensive coverage of the substrate surface by these oxides is detrimental to reactive wetting, good coating adhesion and integrity.
Simulated galvanizing treatments were conducted on two prototype Fe-0.1C-6Mn-2Si (wt pct) 3G steels; one as the reference steel and the other with 0.05 wt pct Sn added to the composition. The combined effects of annealing temperature, time, process atmosphere oxygen partial pressure and 0.05 wt pct Sn addition on the selective oxidation of the steel substrates were determined. Subsequently, the reactive wetting of the steels with respect to the pre-immersion surface structures of the samples annealed for 120 s was examined. Annealing heat treatments were carried out at 800˚C and 690˚C in a N2-5 vol pct H2 process atmosphere under three dew points of –50˚C, –30˚C and +5˚C, covering process atmosphere oxygen partial pressures within the range of 1.20 10-27 atm to 1.29 10-20 atm. MnO was present at the outmost layer of the external oxides on all samples after annealing. However, the morphology, distribution, thickness and surface coverage were significantly affected by the experimental variables. Annealing the reference steel under the low dew point process atmospheres, i.e. –50˚C and –30˚C, resulted in the highest Mn surface concentration as well as maximum surface oxide coverage and thickness. The oxides formed under these process atmospheres generally comprised coarse, compact and continuous film forming nodules, whereas the surface morphologies and distributions obtained under the +5˚C dew point process atmosphere, which was consistent with the internal oxidation mode, exhibited wider spacing between finer and thinner MnO nodules. The grain boundary internal oxide networks had a multi layer structure with SiO2 and MnSiO3 at the oxide cores and shells, respectively. Significant morphological changes were obtained as a result of Sn addition. The continuous film-like external MnO nodules were modified to a fine and discrete globular morphology, with less surface coverage by the oxides and reduced external oxide thickness. Both the external and internal oxidations followed parabolic growth kinetics, where the depth of the internal oxidation zone decreased with Sn addition and decreasing oxygen partial pressure.
Poor reactive wetting was observed for the reference steel substrates that were annealed for 120 s under the –50˚C and –30˚C dew point process atmospheres at 800˚C and under the –50˚C dew point atmosphere at 690˚C, such that no integral metallic coating was formed after the 4 s immersion in the Zn(Al, Fe) bath. By contrast, excellent coating quality was obtained for the Sn-added steels when the –30˚C and +5˚C dew point process atmospheres were employed when annealing at 690˚C. The remainder of the experimental conditions demonstrated good reactive wetting with intermediate coating quality. For the two reference steels annealed at 800˚C under the –50˚C and –30˚C dew point process atmospheres, poor reactive wetting was due to full coverage of the surface by 116 nm and 121 nm thick and continuous MnO films. In the case of the 690˚C –50˚C reference steel with the external layer thickness of only 35 nm, however, poor wetting was attributed to substantial coverage of the surface by continuous, film-like oxides. In both cases, exposure of the underlying substrate to the bath alloy and an intimate contact between the substrate Fe and the bath dissolved Al could not take place and the formation of the Fe2Al5Znx interfacial layer was hidered.
For the processing conditions that satisfactory reactive wetting was obtained despite the pre-immersion selective oxidation of the surfaces, several reactive wetting mechanisms were determined. For the samples with a sufficiently thin external MnO layer, good reactive wetting was attributed to partial reduction of MnO by the bath dissolved Al, as well as bridging of the Mn sub-oxides by the Zn coating or Fe2Al5Znx interfacial intermetallics. Partial or full formation of the Fe2Al5Znx interfacial layer was observed in the successfully galvanized substrates with Fe-Al crystals formed between, underneath and also on top of the reduced oxides. Furthermore, for cases with widely-spaced, fine oxide nodules, it was found that the liquid bath alloy was able to infiltrate the external oxide/substrate interface, resulting in surface oxide lift-off and enhanced coating adhesion. It was globally concluded that the thin, discrete and fine globular morphology of external MnO, resultant of annealing the steel substrates with 0.05 wt pct Sn addition under the process atmosphere oxygen partial pressures consistent with internal oxidation, allowed for an enhanced reactive wetting by the Zn(Al, Fe) galvanizing bath which was manifested by increased amount of Al uptake and population of the Fe2Al5Znx intermetallics at the coating/steel interface. / Thesis / Doctor of Science (PhD)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/22756 |
| Date | January 2018 |
| Creators | Pourmajidian, Maedeh |
| Contributors | McDermid, Joseph R, Materials Science and Engineering |
| Source Sets | McMaster University |
| Language | English |
| Detected Language | English |
| Type | Thesis |
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