Formation Mechanism of Ti–Si Multi-Layer Coatings on the Surface of Ti–6Al–4V Alloy

Titanium alloys are widely used in aerospace applications due to their high specific strength and exceptional corrosion resistance. In this study, a silicide coating with a multi-layer structure was designed and prepared via a pack cementation process to improve the high-temperature oxidation resistance of titanium alloy. A new theory based on the Le Chatelier’s principle is proposed to explain the generation mechanism of active Si atoms. Taking the chemical potential as a bridge, a functional model of the relationship between the diffusion driving force and the change in the Gibbs free energy of reaction diffusion is established. Experimental results indicate that the depth of the silicide coating increases with the siliconization temperature (1000–1100 °C) and time (0–5 h). The multi-layer coating prepared at 1075 °C for 3 h exhibits a thick and dense structure with a thickness of 23.52 μm. This coating consists of an outer layer of TiSi2 (9.40 μm), a middle layer of TiSi (3.36 μm), and an inner layer of Ti5Si3 (10.76 μm). Under this preparation parameter, increasing the temperature or prolonging the holding time will cause the outward diffusion flux of atoms in the substrate to be much larger than the diffusion flux of silicon atoms to the substrate, thus forming pores in the coating. The calculated value of the diffusion driving force FTiSi = 2.012S is significantly smaller than that of FTiSi2 = 13.120S and FTi5Si3 = 14.552S, which perfectly reveals the relationship between the thickness of each layer in the Ti–Si multi-layer coating.