Expanded Perlite Reinforced Magnesium Phosphate Cement-Based Fireproof Coating: Composition Optimization, Fire Resistance and High-Temperature Phase Evolution Mechanism

To develop a high-performance inorganic fireproof coating suitable for steel structures, this study utilized magnesium phosphate cement (MPC) as the matrix and introduced expanded perlite (EP) as a lightweight aggregate. The effects of EP content (40–55%) and magnesium-to-phosphorus ratio (M/P = 4:1–7:1) on the dry density, compressive strength, bond strength, and fire resistance of the coating were systematically investigated. X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) were employed to reveal the phase evolution and microstructure evolution mechanisms at high temperatures. The results indicate that increasing EP content significantly reduces the dry density and thermal conductivity of the coating, enhancing thermal insulation performance. However, excessive incorporation leads to the deterioration of mechanical properties, with an optimal EP content of 45%. The M/P ratio influences the interfacial bond strength and high-temperature structural stability by regulating the proportion of the hydration product K-struvite (KMgPO4·6H2O) and residual MgO. Compressive strength peaked at M/P = 6:1 (0.80 MPa), while bond strength was optimal at M/P = 5:1 (0.097 MPa), corresponding to the best fire resistance (back-side temperature of 180.4 °C). At high temperatures, K-struvite dehydrates and transforms into anhydrous KMgPO4, which, together with residual MgO and crystallized SiO2 from EP, forms a dense ceramic skeleton, ensuring the structural integrity of the coating. Comprehensive performance evaluation determined the optimal mix ratio as M/P = 5:1 and EP content = 45%. The coating with this ratio exhibits a dry density of approximately 560 kg/m3, a 14-day compressive strength of 0.53 MPa, a bond strength of 0.097 MPa, and a back-side temperature of 180.4 °C under flame exposure, demonstrating a favorable balance of lightweight character, mechanical integrity, and thermal insulation performance suitable for steel structure fire protection applications.