Elena Aksel

Advances in lead-free piezoelectric materials for sensors and actuators.

Piezoelectrics have widespread use in today’s sensor and actuator technologies. However, most commercially available piezoelectric materials, e.g., Pb [ZrxTi1−x] O3 (PZT), are comprised of more than 60 weight percent lead (Pb). Due to its harmful effects, there is a strong impetus to identify new lead-free replacement materials with comparable properties to those of PZT. This review highlights recent developments in several lead-free piezoelectric materials including BaTiO3, Na0.5Bi0.5TiO3, K0.5Bi0.5TiO3, Na0.5K0.5NbO3, and their solid solutions. The factors that contribute to strong piezoelectric behavior are described and a summary of the properties for the various systems is provided.

Monoclinic crystal structure of polycrystalline Na0.5Bi0.5TiO3

Bismuth-based ferroelectric ceramics are currently under intense investigation for their potential as Pb-free alternatives to lead zirconate titanate-based piezoelectrics. Na0.5Bi0.5TiO3 (NBT), one of the widely studied compositions, has been assumed thus far to exhibit the rhombohedral space group R3c at room temperature. High-resolution powder x-ray diffraction patterns, however, reveal peak splitting in the room temperature phase that evidence the true structure as monoclinic with space group Cc. This peak splitting and Cc space group is only revealed in sintered powders; calcined powders are equally fit to an R3c model because microstructural contributions to peak broadening obscure the peak splitting.

Phase transition sequence in sodium bismuth titanate observed using high-resolution x-ray diffraction

High resolution powder x-ray diffraction patterns of Na0.5Bi0.5TiO3 at selected temperatures were examined to compare structural changes with observed piezoelectric thermal depoling temperatures. The depoling temperatures do not correlate with discrete phase transition temperatures, and therefore, a structural transition is not the origin of thermal depoling. Rather, a correlation is made with an increase in volume fraction of material which does not obey the long-range Cc space group. The origin of the thermal depoling behavior may be the loss of long-range ferroelectric order by a decreasing proportion of the Cc phase or the associated percolation of disordered nano-scale platelets.

Defect structure and materials “hardening” in Fe2O3-doped [Bi0.5Na0.5]TiO3 ferroelectrics

The effect of Fe2O3-doping on the defect structure and piezoelectric properties of [Bi0.5Na0.5]TiO3 ceramics is studied by means of electron paramagnetic resonance spectroscopy. The results show that the Fe3+ functional centers are incorporated at the perovskite B-site, and clearly can be attributed to the formation of (FeTi′–VO••)• defect complexes with charge compensating oxygen vacancies. Correspondingly, they act as acceptors which promotes materials “hardening.”

Structure and properties of La-modified Na0.5Bi0.5TiO3 at ambient and elevated temperatures

The crystal structure and property changes of sodium bismuth titanate (Na0.5Bi0.5TiO3, NBT) piezoelectric ceramics are reported as a function of La modification (0.5–2.0 at. %) and increasing temperature using high resolution x-ray diffraction, permittivity, depolarization, and polarization and strain hysteresis measurements. La substitution is found to decrease the depolarization temperature of NBT (e.g., 1.5 at. % La substitution lowers the depolarization temperature by 60 °C relative to the unmodified composition) with little impact on the room temperature polarization and strain hysteresis. The room temperature structures of the various NBT compositions were modeled using a mixture of the monoclinic Cc space group and the cubic Pm3¯m phase, where the Pm3¯m phase is used to model local regions in the material which do not obey the long range Cc space group. With increasing La substitution, the lattice parameter distortions associated with the Cc phase approached that of the prototypical cubic unit cell...

Structure and ferroelectricity of nonstoichiometric (Na0.5Bi0.5)TiO3

Stoichiometric (Na0.5Bi0.5)TiO3 (NBT) adopts the ABO3 perovskite structure with the A-site equally occupied by Na+ and Bi3+ ions. However, non-stoichiometric compositions can be synthesized intentionally or unintentionally. To determine the effect of A-site nonstoichiometry on the crystal structure and ferroelectricity of NBT, the composition of (Na0.5−xBi0.5+x)TiO3+x was varied using x = −0.01, −0.005, 0, 0.005, and 0.01. High resolution synchrotron x-ray diffraction and Rietveld refinement revealed that a shift in either direction from x = 0 results in a decrease in the spontaneous ferroelastic strain. Ferroelectric hysteresis and piezoelectric coefficients were found to be optimum in the stoichiometric composition.

Structure and ferroelectricity of nonstoichiometric (Na[subscript 0.5]Bi[subscript 0.5])TiO[subscript 3]

Stoichiometric (Na0.5Bi0.5)TiO3 (NBT) adopts the ABO3 perovskite structure with the A-site equally occupied by Na+ and Bi3+ ions. However, non-stoichiometric compositions can be synthesized intentionally or unintentionally. To determine the effect of A-site nonstoichiometry on the crystal structure and ferroelectricity of NBT, the composition of (Na0.5−xBi0.5+x)TiO3+x was varied using x = −0.01, −0.005, 0, 0.005, and 0.01. High resolution synchrotron x-ray diffraction and Rietveld refinement revealed that a shift in either direction from x = 0 results in a decrease in the spontaneous ferroelastic strain. Ferroelectric hysteresis and piezoelectric coefficients were found to be optimum in the stoichiometric composition.