Properties of Li- and Ta- modified (K,Na)NbO3 piezoceramics with the base composition near the orthorhombic-tetragonal phase boundary have been investigated with respect to variation of temperature, stoichiometry, compositional homogeneity, atmosphere of thermal treatment, and dopants (Ba, Mn). Although the influence of the most of the abovementioned factors has already been reported in the literature, the paper focuses on several aspects of the composition—property relationships that still remain controversial or poorly elucidated. In particular, we show that improvement of compositional homogeniety in these ceramics emphasizes the instability of piezoelectric response with respect to variation of temperature in the vicinity of the orthorhombic-tetragonal phase transition. Ba dopant is shown to suppress conductivity in ceramics sintered in air, though it makes conductivity more sensitive to variation of the oxygen partial pressure. Mn dopant is shown to suppress conductivity and strongly reduce the influence of the oxygen partial pressure on conductivity of the ceramics. Finally, we show that chemical modifications to the ceramic composition, such as Mn dopant or variation of nonstoichiometry affect the piezoelectric response mainly by the shift of the orthorhombic-tetragonal phase transition temperature.

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The influence of sintering atmosphere and copper addition on the microstructural and piezoelectric properties of Mn-doped lead zirconate titanate ceramics (PZT) was investigated. This ceramic powder densifies below 1000 ○ C, enabling the use of copper inner electrodes for a multilayer actuator setup. To simulate the influence of oxidized inner electrodes during sintering, different CuO contents (0 and 1 mol.%) were mixed to the precalcined Mn-doped PZT powder. Ceramic discs were sintered at 950 ○ C in air and analogously in N 2 , or in steam containing N 2 (25 vol.% water vapor content). The electrical characterization of the discs showed that the piezoelectric properties are influenced by the CuO addition as well as by the sintering atmospheres. The large signal piezoelectric constant d à 33 shows an improvement of at least 20% when CuO is added. CuO acts as a sintering aid, and especially when the ceramics are fired in steam-containing N 2 , anomalous grain growth occurs.