The formation mechanism of micro-nano secondary phase in solid-liquid doped TZM alloy

Among the various secondary phases distributed in the TZM (Titanium-Zirconium-Molybdenum) alloy matrix, the ones that can play a strengthening role are often those with a particle size smaller than 1 μm. In this study, titanium sulfate, zirconium nitrate, and fructose were used as raw materials. The TZM alloy with uniform distribution and an average secondary phase particle size of 940 nm (hereinafter referred to as MN-TZM alloy) was prepared through a solid-liquid doping preparation process. The thermodynamic calculation reveals the formation mechanism of the micro-nano-level secondary phase in the MN-TZM alloy. Thermogravimetric analysis (TG-DSC, TG-MS) and transmission electron microscope (TEM) confirmed the calculation results. The generation process of the micro-nano secondary phase evolution can be divided into four parts. The first stage is the process of solute dissolution at room temperature. In the second stage, doping and drying process take place below 100 °C. Third, reduction and secondary phase precursor incubation processes occur from 100 to 700 °C. Fructose decomposes (100 °C) to obtain organic carbon and water. The decomposition of zirconium nitrate (100 °C) yields NH3, H2O, ZrO2 and Zr, while the titanium sulfate decomposes directly at 200– 242 °C to obtain SO2, H2O, TiO2 and Ti. In the last stage, the secondary phase nucleates and grows up (700– 1800 °C). A large variety of micro-nano-scale and even nano-scale secondary phase particles have been discovered, including TiO2, ZrO2, ZrC and TiC. These observations provide necessary information for tracing back the secondary phase precipitation mechanism in the manufacturing process of high-performance molybdenum alloys.