A large body of work has been reported in the last 5 years on the development of lead-free piezoceramics in the quest to replace lead–zirconate–titanate (PZT) as the main material for electromechanical devices such as actuators, sensors, and transducers. In specific but narrow application ranges the new materials appear adequate, but are not yet suited to replace PZT on a broader basis. In this paper, general guidelines for the development of lead-free piezoelectric ceramics are presented. Suitable chemical elements are selected first on the basis of cost and toxicity as well as ionic polarizability. Different crystal structures with these elements are then considered based on simple concepts, and a variety of phase diagrams are described with attractive morphotropic phase boundaries, yielding good piezoelectric properties. Finally, lessons from density functional theory are reviewed and used to adjust our understanding based on the simpler concepts. Equipped with these guidelines ranging from atom to phase diagram, the current development stage in lead-free piezoceramics is then critically assessed.

Perspective on the Development of Lead-free Piezoceramics

Investigations in the development of lead-free piezoelectric ceramics have recently claimed comparable properties to the lead-based ferroelectric perovskites, represented by Pb(Zr,Ti)O3, or PZT In this work, the scientific and technical impact of these materials is contrasted with the various families of “soft” and “hard” PZTs On the scientific front, the intrinsic nature of the dielectric and piezoelectric properties are presented in relation to their respective Curie temperatures (T
 C) and the existence of a morphotropic phase boundary (MPB) Analogous to PZT, enhanced properties are noted for MPB compositions in the (Na,Bi)TiO3-BaTiO3 and ternary system with (K,Bi)TiO3, but offer properties significantly lower The consequences of a ferroelectric to antiferroelectric transition well below T
 C further limits their usefulness Though comparable with respect to T
 C, the high levels of piezoelectricity reported in the (K,Na)NbO3 family are the result of enhanced polarizability associated with the orthorhombic-tetragonal polymorphic phase transition being compositionally shifted downward As expected, the properties are strongly temperature dependent, while degradation occurs through the thermal cycling between the two distinct ferroelectric domain states Extrinsic contributions arising from domains and domain wall mobility were determined using high field strain and polarization measurements The concept of “soft” and “hard” lead-free piezoelectrics were discussed in relation to donor and acceptor modified PZTs, respectively Technologically, the lead-free materials are discussed in relation to general applications, including sensors, actuators and ultrasound transducers

Lead-free piezoelectric ceramics: Alternatives for PZT?

Potassium-sodium niobate lead-free piezoelectric materials: past, present, and future of phase boundaries.

After twenty years of partly quiet and ten years of partly enthusiastic research into lead-free piezoceramics there are now clear prospects for transfer into applications in some areas. This mimics prior research into eliminating lead from other technologies that resulted in restricted lead use in batteries and dwindling use in other applications. A figure of merit analysis for key devices is presented and used to contrast lead-containing and lead-free piezoceramics. A number of existing applications emerge, where the usage of lead-free piezoceramics may be envisaged in the near future. A sufficient transition period to ensure reliability, however, is required. The use of lead-free piezoceramics for demanding applications with high reliability, displacements and frequency as well as a wide temperature range appears to remain in the distant future. New devices are outlined, where the figure of merit suggests skipping lead-containing piezoceramics altogether. Suggestions for the next pertinent research requirements are provided.

Transferring lead-free piezoelectric ceramics into application

Perovskite lead-free dielectrics for energy storage applications

The piezoelectric properties of a solid solution of the binary system, x(Bi1/2Na1/2)TiO3–(1-x)(Bi1/2K1/2)TiO3 [BNKT100x; x=0.50–0.98] were investigated, focusing on depolarization temperature, Td. Fine piezoelectric properties in lead-free piezoelectric ceramics were obtained near the morphotropic phase boundary (MPB) composition between the rhombohedral and tetragonal structures, and the highest electromechanical coupling factor, k33, and piezoelectric constant, d33, were 0.56 for BNKT84 and 157 pC/N for BNKT80, respectively. However, the Td of BNKT80 was low (174 °C). The Td of the MPB composition was low, and the Td near the MPB composition was sharply decreased. It is thought that BNKT70 is a candidate composition for lead-free actuator applications owing to its relatively large piezoelectric constant, d33 (126 pC/N), dynamic d33 (214 pm/V), and high depolarization temperature, Td (206 °C). In this study, we determined depolarization temperature, Td, from the temperature dependence of dielectric and piezoelectric properties.

https://iopscience.iop.org/article/10.1143/JJAP.45.4493/pdf

Electrical Properties and Depolarization Temperature of (Bi1/2Na1/2)TiO3–(Bi1/2K1/2)TiO3 Lead-free Piezoelectric Ceramics

The dielectric, ferroelectric and piezoelectric properties of perovskite ferroelectric and bismuth layered-structured ferroelectric (BLSF) ceramics are described being superior candidates for lead-free piezoelectric materials to reduce environmental damage. Perovskite-type ceramics seem to be suitable for actuator and high-power applications that require a large piezoelectric constant, d33, and a high Curie temperature, Tc, or a depolarization temperature, Td (>200 °C). For BaTiO3-based solid solutions, (1-x)BaTiO3–x(Bi0.5K0.5)TiO3 (BT–BKT100x) ceramics, Tc increases with increasing amount of x. The BT–BKT20 + MnCO3 (0.1 wt %) ceramic shows a high Tc greater than 200 °C and an electromechanical coupling factor of k33 =0.35. In the case of a(Bi1/2Na1/2)TiO3–b(Bi1/2K1/2)TiO3–cBaTiO3 [BNBK (100a/100b/100c)] solid solution ceramics, d33 is 191 pC/N for BNBK (85.2/2.8/12). KNbO3 (KN)-based ceramics are also a candidate for lead-free piezoelectrics. In Mn-doped KN ceramics, a higher k33 of 0.507 is obtained for KN + MnCO3 (0.1 wt %). On the other hand, BLSF ceramics seem to be excellent candidates as piezoelectric sensors for high temperatures and ceramic resonators with a high mechanical quality factor, Qm, and a low temperature coefficient of resonance frequency, TC-f. The k33 value of the donor (Nb)-doped and grain-oriented (HF) Bi4Ti3-xNbxO12 (BITN-x) ceramic is 0.39 for x=0.08 and is able to keep the same stable value up to 350 °C. Nd(0.01) and V(0.75) co-doped Bi4Ti3O12 ceramics, BNTV(0.01, 0.75), show a relatively low TC-f. Bi3TiTaO9 (BTT)-based solid solution, Srx-1Bi4-xTi2-xTaxO9 [SBTT2(x)] (1x2), displays the high Qm value (=13500) in (p)-mode at x=1.25. For resonator applications, (Sr1-xCax)2Bi4Ti5O18 (SCBT) (0x0.5) ceramics are suitable.

Current Developments and Prospective of Lead-Free Piezoelectric Ceramics

Stoichiometric and nonstoichiometric (Bi05Na05)TiO3 (BNT) ceramics were prepared by a conventional ceramic fabrication process This study revealed that the high conductivity of BNT ceramics is associated with Bi vaporization during sintering An x-ray study revealed that a tetragonal phase exists in the temperature range between 330 and 480 °C in BNT ceramic as well as BNT single crystals In addition, the depolarization temperature Td, rhombohedral-tetragonal phase transition temperature TR-T, and the temperature Tm of the maximum dielectric constant were determined to be 187, approximately 300, and 325 °C, respectively, from the temperature dependences of dielectric properties using unpoled and poled specimens The piezoelectric properties of all vibration modes and the temperature dependences of the piezoelectric properties were measured using fully poled BNT ceramics It was also revealed that BNT ceramics exhibit three thermal depoling processes at Td, between Td and TR-T, and between TR-T and Tm 

Thermal depoling process and piezoelectric properties of bismuth sodium titanate ceramics

(1-x)(Bi0.5Na0.5)TiO3–xSrTiO3 (abbreviated as BNST100x) was prepared by a conventional ceramic fabrication process. The depolarization temperature Td, rhombohedral-tetragonal phase transition temperature TR-T, and the temperature Tm of the maximum dielectric constant were determined from the temperature dependence of the dielectric and piezoelectric properties. It is revealed that BNST100x forms a morphotropic phase boundary of rhombohedral ferroelectric and pseudocubic (tetragonal) paraelectric at x=0.26–0.28 for BNST100x, and a very large strain and normalized strain d33* of 0.29% and 488pm∕V, respectively, were obtained at x=0.28. In addition, it was clarified that the intermediate phase between TR-T (⩾Td) and Tm shows relaxor behavior.

Large electrostrain near the phase transition temperature of (Bi0.5Na0.5)TiO3-SrTiO3 ferroelectric ceramics

In this study, we demonstrated the relationship between the phase diagrams and the electrical properties of (Bi1/2Na1/2)TiO3 (BNT)-based solid solutions. In this study, (1−x)(Bi1/2Na1/2)TiO3–xNaNbO3 and (1−x)(Bi1/2Na1/2)TiO3–xKNbO3 (abbreviated to BNT-NN100x and BNT-KN100x) ceramics were prepared by a conventional ceramic fabrication process, and (1−x)(Bi1/2Na1/2)TiO3–x(Bi1/2K1/2)TiO3 (abbreviated to BNKT100x) ceramic was prepared for comparison. We revealed the phase transition temperatures, such as the depolarization temperature Td, rhombohedral-tetragonal phase transition temperature TR-T, and the temperature Tm of the maximum dielectric constant, from the temperature dependence of dielectric properties using poled and unpoled specimens. As a result, it was shown that the BNT-based solid solutions form three types of phase diagrams. In addition, we clarified the relationship between the phase diagrams and the electrical properties of BNT-NN100x, BNT-KN100x, and BNKT100x. The piezoelectric properties we...

Yuji Hiruma

Papers

Electrical Properties and Depolarization Temperature of (Bi1/2Na1/2)TiO3–(Bi1/2K1/2)TiO3 Lead-free Piezoelectric Ceramics

Current Developments and Prospective of Lead-Free Piezoelectric Ceramics

Thermal depoling process and piezoelectric properties of bismuth sodium titanate ceramics

Large electrostrain near the phase transition temperature of (Bi0.5Na0.5)TiO3-SrTiO3 ferroelectric ceramics

Phase diagrams and electrical properties of (Bi1/2Na1/2)TiO3-based solid solutions