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The combustion in thermal explosion mode of reactive mixtures of Ti–Ni–graphite(carbides, borides, oxides), under load, was used to produce complex composite materials, densified and joined to a C55 carbon steel support. The ignition of the exothermic reaction, carried out thanks to the rapid high-frequency heating of a green compact up to 1573 K, was followed by an isothermal holding at 1373 K for 360 s. This procedure ensured a perfect mechanical assembly between the composite material and the steel substrate. SEM analysis and concentration profiles carried out at the interface testified to the interdiffusion of iron and titanium atoms between the two materials. The maximum combustion temperature (Tmax.) exceeding 2200 K induced the appearance of a liquid phase that assisted densification and joining, and in which a part of the additions was dissolved before cooling. The starting chemical composition of reactive mixtures largely determined the microstructure, hardness and tribological behavior of the composites after the process. Thereby, the maximum hardness (1235 HV0.15) and the lowest wear rate (1.824 × 10−6 mm3.N−1.m−1) were obtained in the sample containing TiC, Al2O3 and TiB2 hard phases. The manufactured samples exhibit no deterioration of the composite by spalling, regardless of the starting composition. [ABSTRACT FROM AUTHOR]