The ultra-fine powders of Al-TiO_2-B_2O_3 system were prepared by ball milling.The multiphase ceramic coating of Al_2O_3-TiB_2 on the surface of Q235 and AZ31B bases were made by solid-phase reaction method.The reaction systems of coatings were designed and properties of the coating were predicted through the Empirical Electronic Theory(EET) in solid and molecules.Behaviors of mechanochemistry and thermal chemistry of Al-TiO_2-B_2O_3 system were investigated by scanning electron microscopy(SEM), diff...