- The poor wetting in non-oxide ceramic/metal (M= Au or Cu) systems is usually attributed to the lack of chemical interaction at the solid/liquid interface. In contrast, sessile drop experiments on two non-stoichiometric titanium diboride substrates (TiB 1.9 and TiB 1.95) displayed a surprisingly good wetting. The experimental results are well accounted for by the thermodynamic analysis of the Me–Ti–B systems. According to this analysis, some limited boride dissolution and altering of the substrate composition takes place at the TiB x/Me interface. These changes are more substantial, the stronger the departure from stoichiometry of the initial substrate composition. Minor composition changes are sufficient for improving wetting. Based on the results of the thermodynamic analysis and the wetting experiments, a novel method for the fabrication of Cu infiltrated composites is put forward.