Eva Sapper

Giant electric-field-induced strains in lead-free ceramics for actuator applications – status and perspective

In response to the current environmental regulations against the use of lead in daily electronic devices, a number of investigations have been performed worldwide in search for alternative piezoelectric ceramics that can replace the market-dominating lead-based ones, representatively Pb(ZrxTi1-x)O3 (PZT)-based solid solutions. Selected systems of potential importance such as chemically modified and/or crystallographically textured (K, Na)NbO3 and (Bi1/2Na1/2)TiO3-based solid solutions have been developed. Nevertheless, only few achievements have so far been introduced to the marketplace. A recent discovery has greatly extended our tool box for material design by furnishing (Bi1/2Na1/2)TiO3-based ceramics with a reversible phase transition between an ergodic relaxor state and a ferroelectric with the application of electric field. This paired the piezoelectric effect with a strain-generating phase transition and extended opportunities for actuator applications in a completely new manner. In this contribution, we will present the status and perspectives of this new class of actuator ceramics, aiming at covering a wide spectrum of topics, i.e., from fundamentals to practice.

On the phase identity and its thermal evolution of lead free (Bi1/2Na1/2)TiO3-6 mol% BaTiO3

Temperature-dependent dielectric permittivity of 0.94(Bi1/2Na1/2)TiO3-0.06BaTiO3 (BNT-6BT) lead-free piezoceramics was studied to disentangle the existing unclear issues over the crystallographic aspects and phase stability of the system. Application of existing phenomenological relaxor models enabled the relaxor contribution to the entire dielectric permittivity spectra to be deconvoluted. The deconvoluted data in comparison with the temperature-dependent dielectric permittivity of a classical perovskite relaxor, La-modified lead zirconate titanate, clearly suggest that BNT-6BT belongs to the same relaxor category, which was also confirmed by a comparative study on the temperature- dependent polarization hysteresis loops of both materials. Based on these results, we propose that the low-temperature dielectric anomaly does not involve any phase transition such as ferroelectric- to-antiferroelectric. Supported by transmission electron microscopy and X-ray diffraction experiments at ambient temperature, we ...

Influence of electric fields on the depolarization temperature of Mn-doped (1-x)Bi1/2Na1/2TiO3-xBaTiO3

The transition between induced long-range order and relaxor-like behavior upon heating is investigated in lead-free (1-x)Bi1/2Na1/2(Ti0.995Mn0.005)O3-xBa(Ti0.995Mn0.005)O3 piezoceramics with x = 0.03, 0.06, and 0.09 (BNT-100xBT:Mn). Temperature-dependent permittivity ɛ′(T) and thermally stimulated depolarization currents (TSDC) of poled samples were measured under identical heating conditions to clarify the depolarization mechanism. In both methods, the influence of electric bias fields on the transition temperature was investigated. Fields applied in the poling direction shift the transition to higher temperatures, with corresponding results in ɛ′(T) and TSDC measurements. While the response of transition temperature to external fields displays a similar trend in all investigated compositions, the shape of TSDC is clearly connected with the composition and, hence, the crystal symmetry of the sample. Furthermore, the comparison of ɛ′(T) and TSDC data reveals a systematic shift between transition temperatu...

Electric-field–temperature phase diagram of the ferroelectric relaxor system (1 − x)Bi1/2Na1/2TiO3 − xBaTiO3 doped with manganese

The electric-field–temperature phase diagram for the lead-free relaxor material (1 − x)(Bi1/2Na1/2)TiO3 − xBaTiO3 (x = 0.03, 0.06, and 0.09) doped with 0.5 mol% Mn (BNT-100xBT:Mn) was established. Transition lines between ergodic or nonergodic relaxor states and the field-induced ferroelectric state were determined at constant temperatures with electric-field-dependent measurements of the polarization as well as of the piezoelectric coefficient and permittivity. Near the depolarization temperature T d, the switching between two ferroelectric poling directions occurs in two steps via an intermediate relaxor state. This effect is closely related to the pinching of the ferroelectric hysteresis loop.

Aging in the relaxor and ferroelectric state of Fe-doped (1-x)(Bi1/2Na1/2)TiO3-xBaTiO3 piezoelectric ceramics

Aging of piezoelectric properties was investigated in lead-free (1 − x)(Bi1/2Na1/2)TiO3-xBaTiO3 doped with 1at. % Fe. The relaxor character of the un-poled material prevents macroscopic aging effects, while in the field-induced ferroelectric phase aging phenomena are similar to those found in lead zirconate titanate or barium titanate. Most prominent aging effects are the development of an internal bias field and the decrease of switchable polarization. These effects are temperature activated, and can be explained in the framework of defect complex reorientation. This picture is further supported by electron paramagnetic resonance spectra indicating the existence of (FeTi ′−VO ••)• defect complexes in the Fe-doped material.

Fatigue effect on polarization switching dynamics in polycrystalline bulk ferroelectrics

Statistical distribution of switching times is a key information necessary to describe the dynamic response of a polycrystalline bulk ferroelectric to an applied electric field. The Inhomogeneous Field Mechanism (IFM) model offers a useful tool which allows extraction of this information from polarization switching measurements over a large time window. In this paper, the model was further developed to account for the presence of non-switchable regions in fatigued materials. Application of the IFM-analysis to bipolar electric cycling induced fatigue process of various lead-based and lead-free ferroelectric ceramics reveals different scenarios of property degradation. Insight is gained into different underlying fatigue mechanisms inherent to the investigated systems.

Unexpectedly high piezoelectricity of Sm-doped lead zirconate titanate in the Curie point region

Large piezoelectric coefficients in polycrystalline lead zirconate titanate (PZT) are traditionally achieved through compositional design using a combination of chemical substitution with a donor dopant and adjustment of the zirconium to titanium compositional ratio to meet the morphotropic phase boundary (MPB). In this work, a different route to large piezoelectricity is demonstrated. Results reveal unexpectedly high piezoelectric coefficients at elevated temperatures and compositions far from the MPB. At temperatures near the Curie point, doping with 2 at% Sm results in exceptionally large piezoelectric coefficients of up to 915 pm/V. This value is approximately twice those of other donor dopants (e.g., 477 pm/V for Nb and 435 pm/V for La). Structural changes during the phase transitions of Sm-doped PZT show a pseudo-cubic phase forming ≈50 °C below the Curie temperature. Possible origins of these effects are discussed and the high piezoelectricity is posited to be due to extrinsic effects. The enhancement of the mechanism at elevated temperatures is attributed to the coexistence of tetragonal and pseudo-cubic phases, which enables strain accommodation during electromechanical deformation and interphase boundary motion. This work provides insight into possible routes for designing high performance piezoelectrics which are alternatives to traditional methods relying on MPB compositions.