<p> Aluminum is usually added to the zinc bath to form an Fe-Al interfacial layer which retards the formation of a series of Fe-Zn intermetallic compounds during the hot-dip galvanizing process. However, experimentally exploring the inhibition layer formation and obtaining useful experimental data to understand the mechanisms is quite challenging due to short times involved in this process. In this study, a galvanizing simulator was used to perform dipping times as short as O.ls and rapid spot cooling techniques have been applied to stop the reaction between the molten zinc coating and steel substrate as quickly as possible. In addition, the actual reaction time has been precisely calculated through the logged sample time and temperature during the hot-dipping process. The kinetics and formation mechanism of the inhibition layer was characterized using SEM, ICP and EBSD based on the total reaction time. For bath containing 0.2wt% dissolved AI, the results show that FeA13 nucleates and grows during the initial stage of the inhibition layer formation and then Fe2Als forms by a diffusive transformation. The evolution of the interfacial layer formed in a zinc bath with 0.13wt% dissolved AI, including Fe-Aland Fe-Zn intermetallic compounds, was a result of competing reactions. In the initial period, the Fe-Al reaction dominated due to high thermodynamic driving forces. After the zinc concentration reached a critical composition in the substrate grain boundaries, formation of Fe-Zn intermetallic compounds was kinetically favoured. Fe-Zn intermetallic compounds formed due to zinc diffusing to the substrate via short circuit paths and continuously grew by consuming Fe-Al interfacial layer after samples exited the zinc bath due to the limited Al supply. A mathematical model to describe the formation kinetics as a function of temperature for the 0.2wt% Al zinc bath was proposed. It indicated that the development of microstructure of the interfacial layer had significant influence on the effective diffusion coefficient and growth of this layer. However, the model underestimates the AI uptake by the interfacial layer, particularly at higher temperatures. This is thought to be due to the effect of the larger number of triple junctions in the inhibition layer leading to an underestimation of the effective diffusivity. </p> / Thesis / Master of Science (MSc)

Aluminium is usually added to the continuous hot-dip galvanizing bath to improve coating ductility and adhesion through the rapid formation of a thin Fe-Al intermetallic layer at the substrate-liquid interface, thereby inhibiting the formation of brittle Fe-Zn intermetallic compounds. On the other hand, Mn is essential for obtaining the desired microstructure and mechanical properties in advanced high strength steels, but is selectively oxidized in conventional continuous galvanizing line annealing atmospheres. This can deteriorate reactive wetting by the liquid Zn(Al,Fe) alloy during galvanizing and prevent the formation of a well developed Fe-Al interfacial layer at the coating/substrate interface, resulting in poor zinc coating adherence and formability. However, despite Mn selective oxidation and the presence of surface MnO, complete reactive wetting and a well developed Fe-Al interfacial layer have been observed for Mn-containing steels. These observations have been attributed to the aluminothermic reduction of surface MnO in the galvanizing bath. According to this reaction, MnO is reduced by the bath dissolved Al, so the bath can have contact with the substrate and form the desired interfacial layer. Heat treatments compatible with continuous hot-dip galvanizing were performed on four different Mn-containing steels whose compositions contained 0.2-3.0 wt% Mn. It was determined that substrate Mn selectively oxidized to MnO for all alloys and process atmospheres. Little Mn surface segregation was observed for the 0.2Mn steel, as would be expected because of its relatively low Mn content, whereas the 1.4Mn through 3.0Mn steels showed considerable Mn-oxide surface enrichment. In addition, the proportion of the substrate surface covered with MnO and its thickness increased with increasing steel Mn content.A galvanizing simulator equipped with a He jet spot cooler was used to arrest the reaction between the substrate and liquid zinc coating to obtain well-characterized reaction times characteristic of the timescales encountered while the strip is resident in the industrial continuous galvanizing bath and short times after in which the Zn-alloy layer continues to be liquid (i.e. before coating solidification). Two different bath dissolved Al contents (0.20 and 0.30 wt%) were chosen for this study. The 0.20 wt% Al bath was chosen as it is widely used in industrial continuous galvanizing lines. The 0.30 wt% Al bath was chosen to (partially) compensate for any dissolved Al consumption arising from MnO reduction in the galvanizing bath.The Al uptake increased with increasing reaction time following non-parabolic growth kinetics for all experimental steels and dissolved Al baths. For the 0.20 wt% dissolved Al bath, the interfacial layer on the 1.4Mn steel showed the highest Al uptake, with the 0.2Mn, 2.5Mn and 3.0Mn substrates showing significantly lower Al uptake. However, increasing the dissolved bath Al to 0.30 wt% Al resulted in a significantly increased Al uptake being observed for the 2.5Mn and 3.0Mn steels for all reaction times. These observations were explained by the combined effects of the open microstructures associated with the multi-phase nature of an oxide-containing interfacial layer and additional Al consumption through MnO reduction. For instance, in the case of the 1.4Mn steel, the more open interfacial layer structure accelerated Fe diffusion through the interfacial layer and increased Al uptake versus the 0.2Mn substrate for the same bath Al. However, in the case of the 2.5Mn and 3.0Mn substrates and 0.20 wt% Al bath, additional Al consumption through MnO reduction caused the interfacial layer growth to become Al limited, whereas the very open structure dominated growth in the case of the 0.30 wt% Al bath and resulted in the changing the growth kinetics from mixed diffusion-controlled to a more interface controlled growth mode. A kinetic model based on oxide film growth (Smeltzer et al. 1961, Perrow et al. 1968) was developed to describe the Fe-Al interfacial layer growth kinetics within the context of the microstructural evolution of the Fe-Al interfacial layer for Mn-containing steels reacted in 0.20 wt% and 0.30 wt% dissolved Al baths. It indicated that the interfacial layer microstructure development and the presence of MnO at the interfacial layer had significant influence on the effective diffusion coefficient and interfacial layer growth rate. However, in the cases of the 2.5Mn and 3.0Mn steels in 0.20 wt% Al bath, the kinetic model could not predict the interfacial layer Al uptake, since the Fe-Al growth was Al limited. In fact, in these cases, additional Al was consumed for reducing their thicker surface MnO layer, resulted in limiting the dissolved Al available for Fe-Al growth. / Dissertation / Doctor of Science (PhD)