Zdravko Kutnjak

Organic and inorganic relaxor ferroelectrics with giant electrocaloric effect

The electrocaloric effect (ECE) in inorganic thin film and organic relaxor ferroelectrics is investigated by directly measuring the ECE around room temperature. The results reveal that giant ECEs can be obtained in the high energy electron irradiated poly(vinylidene fluoride-trifluoroethylene) relaxor copolymer and in the La-doped Pb(ZrTi)O3 relaxor ceramic thin films, which are much larger than that from the normal ferroelectric counterparts. The large ECE observed, compared with normal ferroelectrics, is likely caused by the large number of disordered fluctuating polarization entities in relaxor ferroelectrics which can lead to extra entropy contributions and larger ECE.

Comparison of directly and indirectly measured electrocaloric effect in relaxor ferroelectric polymers

We report the directly measured electrocaloric effect (ECE) (the adiabatic temperature change ΔT) of relaxor ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) terpolymer and its blend with poly(vinylidene fluoride-chlorotrifluoroethylene). The results show that the directly measured ΔT in the relaxor terpolymer is much larger than that deduced from Maxwell relation and that the relaxor terpolymer possesses a giant ECE at room temperature. The large difference between the directly measured ΔT and that deduced indicates that the Maxwell relation, which is derived for ergodic systems, is not suitable for deducing ECE in the relaxor ferroelectric polymers, which are nonergodic (polar-glass) material systems.

Influence of the critical point on the electrocaloric response of relaxor ferroelectrics

The electrocaloric effect (ECE), i.e., the conversion of electric energy into heat, is of great importance for application in new generation cooling or heating devices that would be friendlier to the environment. Here, utilizing direct measurements of the ECE change of the temperature ΔT via a high resolution calorimeter, we study the ECE as a function of the magnitude of the electric-field step E in the vicinity of the critical point in several bulk relaxor ferroelectric ceramic systems. Relatively large ΔT of ∼2 to 3 K were obtained at modest fields of 90 kV/cm, even in the case of ceramic materials. The effective responsivity ΔT/E as a function of the electric field shows a characteristic peak near the critical point, which demonstrates the importance of proximity to the critical point for the enhancement of the electrocaloric effect. Experimental results are in good agreement with the theoretical calculations based on the spherical random-bond random-field model.

Enhanced electrocaloric effect in ferroelectric poly(vinylidene-fluoride/ trifluoroethylene) 55/45 mol % copolymer at ferroelectric-paraelectric transition

The electrocaloric effect (ECE) of the ferroelectric poly(vinylidene-fluoride/trifluoroethylene) 55/45 mol % copolymer was directly measured over a broad temperature range using a specially designed calorimetry method. The data reveal a large ECE occurring at the ferroelectric-paraelectric (FE–PE) phase transition where an adiabatic temperature change ∼12 °C was induced under a field of 120 MV/m, which is much higher than that previously observed at above the FE–PE transition. The directly measured ECE also confirms the earlier results deduced from the indirect method. The experimental data also show that there are secondary effects contributing to the observed ECE in the polymer.

Electrocaloric effect in relaxor ferroelectrics

A theoretical model for the electrocaloric effect (ECE) in relaxor ferroelectrics is presented. By solving a self-consistent relation for the ECE temperature change ΔT and minimizing numerically the mean field free energy for relaxors, the field and temperature dependence of ΔT is calculated. The corresponding harmonic Landau coefficient a=a(T), which differs from the ferroelectric case by always being positive, is derived from the spherical random bond-random field model, and the fourth-order coefficient b is treated as a phenomenological parameter, which can be either positive or negative. For b<0, a line of field-induced first-order relaxor-to-ferroelectric phase transitions exists in relaxors, which terminates at a liquid-vapor type critical point ECP,TCP. The critical behavior close to ECP,TCP is analyzed. It is shown that near the first-order phase transition a temperature or field interval or gap formally appears, where ΔT cannot be found. However, domain formation in the coexistence range should r...

Upper bounds on the electrocaloric effect in polar solids

Physical upper bounds on the electrocaloric effect (ECE) in bulk polar solids are derived using thermodynamic and statistical mechanics arguments. It is shown that the maximum ECE temperature change ΔT under saturation can be estimated from the dielectric data, such as the saturation polarization and effective Curie constant, as well as from the orientational degeneracy Ω of the elementary dipolar entities in the system and the specific heat of the material. Also obtained is a universal relation for the theoretical maximum value of ΔT, which depends only on Ω and the molar specific heat.

Bulk relaxor ferroelectric ceramics as a working body for an electrocaloric cooling device

The electrocaloric effect (ECE), i.e., the conversion of the electric into the thermal energy has recently become of great importance for development of a new generation of cooling technologies. Here, we explore utilization of [Pb(Mg1∕3Nb2∕3)O3]0.9[PbTiO3]0.1 (PMN-10PT) relaxor ceramics as active elements of the heat regenerator in an ECE cooling device. We show that the PMN-10PT relaxor ceramic exhibits a relatively large electrocaloric change of temperature ΔTEC > 1 K at room temperature. The experimental testing of the cooling device demonstrates the efficient regeneration and establishment of the temperature span between the hot and the cold sides of the regenerator, exceeding several times the ΔTEC within a single PMN-10PT ceramic plate.

Negative electrocaloric effect in antiferroelectric PbZrO3

The dielectric and thermal properties of a typical antiferroelectric (AFE) material are investigated by minimising numerically the free energy as given by the Kittel model of AFEs. The phase line of second-order phase transitions in the phase diagram is shown to change to a first-order line at the tricritical point T3cp, E3cp. The static dielectric susceptibility and the electrocaloric (EC) effect are calculated as a function of temperature and the applied electric field E. It is found that in a given range of electric fields and temperatures the EC effect has negative values but generally becomes positive above the AFE ordering temperature T0. The dielectric susceptibility shows characteristic peaks at the phase transitions between the field-induced polar and the AFE antipolar phase, and diverges at the tricritical point. We present experimental results for a negative EC effect, which have been obtained by direct EC measurements in PbZrO3 ceramics, and agree qualitatively with the above model.

Large electrocaloric effect in lead-free K0.5Na0.5NbO3-SrTiO3 ceramics

The electrocaloric effect (ECE), i.e., the adiabatic temperature change ΔTEC, of the lead-free relaxor ferroelectric 0.85K0.5Na0.5NbO3-0.15SrTiO3 (KNN-STO) ceramics is investigated. The ECE data obtained by a direct method show the existence of a large ECE near the temperature of the dielectric permittivity maximum. Due to the high break-down electric field, a large ΔTEC exceeding 1.2 K at 300 K and 1.9 K at 340 K was observed at 159 kV/cm in a broad temperature range of 80 K. Such a high ECE response near the room temperature is comparable to that found in lead-based ceramic materials, thus making KNN-STO a strong candidate to replace lead-based materials in future electrocaloric applications.

Theoretical and experimental study of the nanoparticle-driven blue phase stabilisation

Abstract.We have studied theoretically and experimentally the effects of various types of nanoparticles (NPs) on the temperature stability range