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The influence of TiCl3 solution on the room temperature (r.t.) resistivity and electrical properties of Ba0.92Ca0.08TiO3 PTCR ceramics was studied. The results indicate that the PTC effect can be improved significantly when an appropriate amount of TiCl3 in solution is added to the original materials. Some of the doped Ti3+ ions segregate at grain boundaries behaving as acceptors by substituting for Ti site or valence varying (from Ti3+ to Ti4+). As a result, the surface charge density Ns) increases and the barrier height at grain boundaries (φ) is enhanced.