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By the sessile drop technique, the wettability of Cu/W systems with the additions of Ni and Cr has been studied under vacuum atmosphere. Effects of Ni and Cr contents and wetting temperatures on the wettability and the wetting mechanisms of copper on W substrate have been investigated in detail. The results show that the wetting angles of Cu on the W substrate are decreased with an increase in the content of Ni or Cr, and also decrease with raising the wetting temperatures. SEM, EPMA, and X-ray diffraction have been used to analyze the interracial characteristics of the CuNi/W and CuCr/W systems. The results reveal that there is a transition layer about 2-3 μm in the interface of Cu-4.0 wt pet Ni/W, in which the intermetallic phase Ni4W is precipitated. As to CuCr/W system, no reaction occurs at the interface. The two factors are that the contents of Cr and Ni and the infiltration temperature must be chosen appropriately in order to control the interfacial dissolution and reaction when the Cu-W alloys are prepared by the infiltration method.