Structure and temperature-dependent phase transitions of lead-free Bi1/2Na1/2TiO3–Bi1/2K1/2TiO3–K0.5Na0.5NbO3 piezoceramics

Abstract

Structure and phase transitions of (1 − y)((1 − x)Bi1/2Na1/2TiO3xBi1/2K1/2TiO3)–yK0.5Na0.5NbO3 (x; y) piezoceramics (0.1 ≤ x ≤ 0.4; 0 ≤ y ≤ 0.05) were investigated by transmission electron microscopy, neutron diffraction, temperature-dependent x-ray diffraction, and Raman spectroscopy. The local crystallographic structure at room temperature (RT) does not change by adding K0.5Na0.5NbO3 to Bi1/2Na1/2TiO3xBi1/2K1/2TiO3 for x = 0.2 and 0.4. The average crystal structure and microstructure on the other hand develop from mainly long-range polar order with ferroelectric domains to short-range order with polar nanoregions displaying a more pronounced relaxor character. The (0.1; 0) and (0.1; 0.02) compositions exhibit monoclinic Cc space group symmetry, which transform into Cc + P4bm at 185 and 130 °C, respectively. This high temperature phase is stable at RT for the morphotropic phase boundary compositions of (0.1; 0.05) and all compositions with x = 0.2. For the compositions of (0.1; 0) and (0.1; 0.02), local structural changes on heating are evidenced by Raman; for all other compositions, changes in the long-range average crystal structure were observed.

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ACKNOWLEDGMENTS

E-M.A. acknowledges support for this work by the LOEWE-center AdRIA on adaptronics. M.H. acknowledges support from the BMBF (Bundesministerium für Bildung und Forschung) under Grant No. 05K10ODA. J.L.J. and B.K. acknowledge partial support by the U.S. National Science Foundation (NSF) under award number DMR-0746902 and the U.S. Department of the Army under W911NF-09-1-0435. Use of the Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The authors thank Robert Dittmer and Matthew Suchomel for assistance with the x-ray measurements, Thomas Hansen for the assistance with neutron measurements, Lars Riekehr for TEM specimen preparation, and Michael Wagner for assistance with Raman spectroscopy and sample preparation.

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Anton, EM., Schmitt, L.A., Hinterstein, M. et al. Structure and temperature-dependent phase transitions of lead-free Bi1/2Na1/2TiO3–Bi1/2K1/2TiO3–K0.5Na0.5NbO3 piezoceramics. Journal of Materials Research 27, 2466–2478 (2012). https://doi.org/10.1557/jmr.2012.195

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