Tribological properties and sulfuric acid corrosion resistance of laser clad CoCrFeNi high entropy alloy coatings with different types of TiC reinforcement

CoCrFeNi, directly added TiC (D-TiC) and in-situ synthesized TiC (I-TiC) reinforced CoCrFeNi high entropy alloy coatings (HEACs) were prepared on the surface of 316 stainless steel (SS) by laser cladding (LC). The HEACs all achieved a dense and uniform structure, the TiC distributed at the grain boundaries (GBs) reduced the dilution rate of the HEACs, and the I-TiC composite coating realised a fine and diffuse distribution of the reinforcing phase compared to the D-TiC HEAC. The introduction of TiC dramatically refined the grain size of HEA system and inhibited the formation of high angle grain boundaries (HAGBs), with the average grain size decreasing from 23.6 µm in the TiC-free HEAC to 12.3 µm in D-TiC HEAC and 9.3 µm in I-TiC HEAC, and the proportion of low angle grain boundaries (LAGBs) of D-TiC and I-TiC composite coatings was even as high as 64.8% and 70.4%. As a result, the density of geometrically necessary dislocations (ρGND) in TiC-containing coatings also increased greatly, and ρGND in CoCrFeNi, D-TiC and I-TiC HEACs were 0.55 × 1015, 1.08 × 1015 and 1.27 × 1015 m−2, respectively. The highest average microhardness values of 420.2 ± 6 HV0.2 was achieved with I-TiC HEAC, which relied on TiC precipitation in a nucleation-growth mode. In electrochemical corrosion tests, the introduction of TiC also provided additional channels for ion diffusion. The ordered and dense passivation film of the I-TiC composite coating impeded sulfuric acid attack effectively, with an Icorr value of only 2.28 × 10−2 ± 0.8 μA/cm2, which was less than that of the substrate as well as the other two HEACs. In both dry sliding friction and wear and corrosive wear experiments, abrasive wear was the dominant wear pattern of I-TiC HEAC due to the increase in local stresses caused by the "point-to-point" contact between the TiC particles and the friction pair. Thanks to the diffuse and homogeneous distribution of the TiC reinforcing phase, I-TiC HEAC exhibited the best tribological performance in both dry sliding friction and wear or corrosive wear experiments with specific wear rates as low as 0.05 mm3/Nm in air and 0.06 mm3/Nm in sulfuric acid.