TiN-based composite coatings with and without the addition of Cr were deposited by reactive plasma spraying (RPS) in air. Both sintered and mixed powder of Ti and B4C were used for the RPS process. A thermodynamic model was firstly used to estimate the complicated phase composition of composite coatings prepared by RPS. The phase composition, structures and properties of TiN-based coatings were investigated using XRD, SEM and a Vickers microhardness tester. The results show that the phases in TiN-based coatings do not generate according to priority of Gibbs free energy value due to non-equilibrium reactive course during thermal spraying. The coating deposited using sintered Ti and B4C powder is composed of two main phases (TiN and TiN0.3), two minor phases (Ti2O3 and TiB2), and a small fraction of TiC phase. The composition of the coating deposited using the mixed powder with Cr added is predominantly in the TiN and TiB2 phases, a smaller phase fraction of Ti2O3 and TiO2, and some unreacted Cr. The Vickers microhardness of the coating deposited using sintered powder is higher than that of using mixed powder. The composite coating deposited using mixed powder with the addition of Cr shows superior corrosion resistant to that using sintered powder when tested in 3.5 wt.% NaCl electrolytic solution. (c) 2008 Elsevier B.V. All rights reserved.