Influence of Grain-Growth Inhibitors on Modified (Ba,Sr)(Sn,Ti)O3 for Electrocaloric Application.

The paper reports on effect of grain-growth inhibitors MgO, Y2O3 and MnCO3 as well as Ca modification on the microstructure, dielectric, ferroelectric and electrocaloric (EC) properties of Ba0.82Sr0.18Sn0.065Ti0.935O3 (BSSnT). Furthermore, the effects of the sintering time and temperature on the microstructure and the electrical properties of the most promising material system Ba0.62Ca0.20Sr0.18Sn0.065Ti0.935O3 (BCSSnT-20) are investigated. Additions of MgO (xMgO = 1%), Y2O3 (xY2O3 = 0.25%) and MnCO3 (xMnCO3 = 1%) significantly decreased the mean grain size of BSSnT to 0.4 µm, 0.8 µm and 0.4 µm, respectively. Ba0.62Ca0.20Sr0.18Sn0.065Ti0.935O3 (BCSSnT-20) gained a homogeneous fine-grained microstructure with an average grain size of 1.5 µm, leading to a maximum electrocaloric temperature change |ΔTEC| of 0.49 K at 40 °C with a broad peak of |ΔTEC| > 0.33 K in the temperature range from 10 °C to 75 °C under an electric field change of 5 V µm-1. By increasing the sintering temperature of BCSSnT-20 from 1350 °C to 1425 °C, the grain size increased from 1.5 µm to 7.3 µm and the maximum electrocaloric temperature change |ΔTEC| increased from 0.15 K at 35 °C to 0.37 K at 20 °C under an electric field change of 2 V µm-1. Our results show that under all investigated material systems, BCSSnT-20 is the most promising candidate for future application in multilayer ceramic (MLC) components for EC cooling devices.

Quasi-adiabatic calorimeter for direct electrocaloric measurements.

The electrocaloric effect (ECE) in ferroelectric materials is a promising candidate for small, effective, low cost, and environmentally friendly solid state cooling applications. Instead of the commonly used indirect estimates based on Maxwell's relations, direct measurements of the ECE are required to obtain reliable values. In this work, we report on a custom-made quasi-adiabatic calorimeter for direct ECE measurements. The ECE is measured for two promising lead-free materials: Ba(Zr0.12Ti0.88)O3 and Ba(Zr0.2Ti0.8)O3 bulk ceramics. Adiabatic temperature changes of ΔTEC = 0.5 K at 355 K and ΔTEC = 0.3 K at 314 K were achieved under the application of an electric field of 2 kV/mm for the Ba(Zr0.12Ti0.88)O3 and Ba(Zr0.2Ti0.8)O3 samples, respectively. The quasi-adiabatic ECE measurements reliably match other direct EC measurements using a differential scanning calorimeter or an infrared camera. The data are compared to indirect EC estimations based on Maxwell's relations and show that the indirect measurements typically underestimate the effect to a certain degree.

Modified Differential Scanning Calorimeter for Direct Electrocaloric Measurements.

Solid-state refrigeration using the electrocaloric effect (ECE) in ferroelectric materials is a promising alternative to the conventional vapor-compression technology. In spite of growing interest to the investigation of the ECE, direct measurements of the effect are still rare. In this paper, we report on a modification of a differential scanning calorimeter for direct ECE measurements. The importance of proper estimation of the thermal correction factor and use of proper values of the heat capacitance for correct ECE measurements is discussed. The ECE measurements were performed for Ba(Zr0.2Ti0.8)O3 and Ba(Zr0.12Ti0.88)O3 bulk ceramics. Large electrocaloric temperature changes of 0.54 and 0.34 K are achieved under the application of an electric field of 2 kV/mm for the Ba(Zr0.12Ti0.88)O3 and Ba(Zr0.2Ti0.8)O3 samples, respectively. The relation between the directly measured ECE values and frequently used indirect estimation based on Maxwell's relations is discussed.