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The possibility to exploit commercially the peculiar characteristics of refractory metallic and ceramic materials and in particular of Zirconium diboride ceramics–a class of promising materials for high temperature applications—often depends to a great extent on the ability to join different ceramics one to the other or to special metallic alloys. As the behaviour of a metal-ceramic joint is ruled by the chemical and the physical properties of the interface, the knowledge of wettability, interfacial tensions and interfacial reactions is mandatory to understand what happens at the liquid metal-ceramic interface during joining processes.In the framework of an extensive study aimed at evaluating the wettability and the interfacial characteristics of different metal-ceramic systems, the behaviour of ZrB2 in contact with liquid Ag and its alloys (Cu, Ti, Zr, Hf) has been studied. ZrB2 pure, with different sintering aids or “alloyed” with other ceramic materials (SiC, Si3N4), have been used. The wetting and spreading experiments have been performed by the sessile drop technique under controlled atmospheres. The wetting and spreading characteristics and the interfacial reactions are discussed as a function of time, compositions of the ceramic and of the alloy involved. The interfacial morphologies, analysed by SEM and EDS, show the presence of regular interfaces and adsorption layers and of different bulk phases which are interpreted in terms of the relevant phase-diagrams.