The waterproof and thermal insulation property of foamed concrete is very important. In this study, the ultrafine fly ash (UFA)-based superhydrophobic composite coating was applied onto foam concrete. The UFA-based base coating that closely adhered to the concrete initially improved the waterproofness of the test block, and the silane coupling agent-modified UFA-based surface coating further achieved superhydrophobicity. The UFA on the coating surface and the asperities on the surface jointly formed a lotus leaf-like rough micro–nanostructure. The 154.34° water drop contact angle and 2.41° sliding angle on No. 5 coating were reached, indicating that it was a superhydrophobic surface. The water absorption ratios of the composite coating block were 1.87% and 16.6% at 4 h and 7 days, which were reduced by 97% and 75% in comparison with the original foam concrete. The compressive strength and heat conductivity coefficient after soaking for 4 h of the composite coating block were higher than 4.0 MPa and 0.225 W·m⁻¹·K⁻¹, respectively. The UFA-based superhydrophobic composite coating proposed in this study and applied onto foam concrete is simple and cheap, requires no precise instrument, and can be applied in a large area.

Ultrafine calcium carbonate is a widely used cheap additive. The research is conducted in low degree supersaturation solution in order to study the polymorphic phases’ change and its factors of the calcium carbonate precipitate in the ammonification‐carbonization process of the solution with calcium. Fine particles of calcium carbonate are made in the solution containing 0.015 mol/L of Ca²⁺. Over 98% of the calcium carbonate precipitate without ammonification resembles the morphology of calcite, while the introduction of ammonia can benefit the formation of vaterite. It was inferred that the main cause should be serious partial oversaturation or steric effects. Ammonia also helps to form the twin spherical calcium carbonate. However, particles formed in the process of ammonification‐carbonization in solution with low concentration degree of calcium are not even with a scale of the particle diameter from 5 to 12 μm. Inorganic salts, alcohol, or organic acid salts have significant controlling effect on the particle diameter of calcium carbonate and can help to decrease the particle diameter to about 3 μm. Anionic surfactants can prevent the conglobation of calcium carbonate particles and shrink its diameter to 500 nm–1 μm.