Mass-transport processes at the enamel-steel interface were investigated by studying the rheological properties of the enamel and the microstructure of the enamel-steel interface. The thermophysical properties, e.g., the viscosity and spreading behavior of enamel were measured using the rotating bob and the sessile drop techniques, respectively. The results show that the viscosity of the enamel decreases sharply as the FeO concentration increases from 0 to 25 wt pct, while the contact angle changes with the increasing thickness of the NiO precoat. Microstructural characterization also revealed evidence for the presence of an interfacial gradient force (more specifically referred to as the Marangoni convection) confined within the 0- to 80-µm thickness at the enamel-steel interface. This force is responsible for a convective flow, which determines the formation of flow striae at the interface. The striae act as a sink for evolved gases and provide transport away from the enamel-steel interface. In addition, experimental simulation of Marangoni convection (interfacial-gradient force) was carried out by selectively doping the steel surface with excess Fe2O3 powder. The presence of convection flow was confirmed by analyzing the pattern of iron oxide particles dispersed across the surrounding enamel layers. Based on the microstructural characterization and the thermophysical data, we propose a mechanism for mass transport at the glass-steel interface.