Lead zirconate titanate (PZT) based piezoelectric materials are well known for their excellent piezoelectric properties. However, considering the toxicity of lead and its compounds, there is a general awareness for the development of environmental friendly lead-free materials as evidenced from the legislation passed by the European Union in this effect. Several classes of materials are now being considered as potentially attractive alternatives to PZTs for specific applications. In this paper, attempts have been made to review the recent developments on lead-free piezo materials emphasizing on their preparation, structure–property correlation, etc. In this context, perovskite systems such as bismuth sodium titanate, alkali niobates (ANbO3), etc. and non-perovskites such as bismuth layer-structured ferroelectrics are reviewed in detail. From the above study, it is concluded that some lead-free compositions show stable piezoelectric responses even though they do not match the overall performance of PZT. This has been the stimulant for growing research on this subject. This topic is of current interest to the researchers worldwide as evidenced from the large number of research publications. This has motivated us to come out with a review article with a view that it would give further impetus to the researchers already working in this area and also draw the attention of the others.

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Review: environmental friendly lead-free piezoelectric materials

The current state of efforts to understand the phenomenon of geometric magnetic frustration is described in the context of several key materials. All are transition metal oxides which crystallize with magnetic lattices which are geometrically or topologically prone to frustration such as those based on triangles or tetrahedra which share corners, edges or faces. These include the anhydrous alums, jarosites, pyrochlores, spinels, magnetoplumbites, garnets, ordered NaCl and other structure types. Special attention is paid to materials which do not undergo long range ordering at the lowest temperatures but instead form exotic ground states such as spin glasses, spin liquids and spin ices, and to S = 1/2 based materials.

Geometrically frustrated magnetic materials

Dielectric, ferroelectric and piezoelectric properties of perovskite ferroelectric and bismuth layer-structured ferroelectric (BLSF) ceramics are described as superior candidates for lead-free piezoelectric materials to reduce environmental damages. Perovskite type ceramics seem to be suitable for actuator and high power applications that are required a large piezoelectric constant, d 33 (>300 pC/N) and a high Curie temperature, T c (>200 °C). For BaTiO 3 (BT)-based solid solutions, that is, (1 −  x )BaTiO 3 − x (Bi 0.5 K 0.5 )TiO 3 [BTBK − 100 x ] ceramics, the T c increases with increasing the amount of x . BTBK-20 + MnCO 3 0.1 wt.% ceramic shows the high T c than 200 °C and the electromechanical coupling factor, k 33  = 0.35. In the case of a (Bi 1/2 Na 1/2 )TiO 3  −  b BaTiO 3  −  c (Bi 1/2 K 1/2 )TiO 3 [BNBK (100 a /100 b /100 c )] solid solution ceramics, the d 33 and T c are 191 pC/N and 301 °C for the BNBK (85.2/2.8/12), respectively. On the other hand, BLSF ceramics seem to be excellent candidates as piezoelectric sensors for high temperatures and ceramic resonators with high mechanical quality factor ( Q m ), and low temperature coefficient of resonance frequency (TC- f r ). Donor-doped Bi 4 Ti 3 O 12 ceramics such as Bi 4 Ti 3− x Nb x O 12 [BITN- x ] and Bi 4 Ti 3− x V x O 12 [BITV- x ] show high T c than 650 °C. The k 33 value of the grain-oriented (HF) BITN-0.08 ceramic is 0.39 and is able to keep the same value up to 350 °C. Bi 3 TiTaO 9 (BTT)-based solid solution system, Sr x −1 Bi 4− x Ti 2− x Ta x O 9 [SBTT2( x )] (1 ≦  x  ≦ 2), displays the high Q m value (=13500) in (p)-mode at the x  = 1.25 composition.

http://web1.see.asso.fr/electroceramics/html/cdrom/pdf/Papers/C07-01-Inv.pdf

Current status and prospects of lead-free piezoelectric ceramics

The hydrothermal technique provides an excellent possibility for processing of advanced materials whether it is bulk single crystals, or fine particles, or nanoparticles. The advantages of hydrothermal technology have been discussed in comparison with the conventional methods of materials processing. The current trends in hydrothermal materials processing has been described in relation to the concept of soft solution processing, as a single-step low energy consuming fabrication technique. Also some recent developments in multi-energy processing of materials such as microwave-hydrothermal, mechanochemical-hydrothermal, electrochemical-hydrothermal, sonar-hydrothermal, etc. have been discussed. An overview of the past, present and future perspective of hydrothermal technology as a tool to fabricate advanced materials has been given with appropriate examples.

Hydrothermal processing of materials: past, present and future

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.

Takuya Kohno

Papers

Growth and characterization of lanthanum gallium silicate La3Ga5SiO14 single crystals for piezoelectric applications