Based on the theory of classical piezoelectricity, the relationship between the generation of multiple piezoelectric effect under applied electric field and boundary conditions is analyzed. The generating process of multiple piezoelectric effect is elaborated and the formulas of secondary direct and tertiary converse piezoelectric effect are deduced. The displacement or voltage generated by primary converse, secondary direct and tertiary converse piezoelectric effect is calculated by using coupled-field analysis function in the Finite Element Analysis software-ANSYS. Experimental research of multiple piezoelectric effect under applied electric field is performed through PZT-5 stack. The experimental result verifies the existence of multiple piezoelectric effect. Experimental data shows that voltage and displacement generated by secondary direct and tertiary converse piezoelectric effect respectively are linear with the applied voltage. Both the simulation and experimental results prove that the theoretical analysis is accurate.

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