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      Tuning the electrocaloric enhancement near the morphotropic phase boundary in lead-free ceramics

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          Abstract

          The need for more energy-efficient and environmentally-friendly alternatives in the refrigeration industry to meet global emission targets has driven efforts towards materials with a potential for solid state cooling. Adiabatic depolarisation cooling, based on the electrocaloric effect (ECE), is a significant contender for efficient new solid state refrigeration techniques. Some of the highest ECE performances reported are found in compounds close to the morphotropic phase boundary (MPB). This relationship between performance and the MPB makes the ability to tune the position of the MPB an important challenge in electrocaloric research. Here, we report direct ECE measurements performed on MPB tuned NBT-06BT bulk ceramics with a combination of A-site substitutions. We successfully shift the MPB of these lead-free ceramics closer to room temperature, as required for solid state refrigeration, without loss of the criticality of the system and the associated ECE enhancement.

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          Giant electrocaloric effect in thin film Pb Zr_0.95 Ti_0.05 O_3

          Q. Zhang, A. Mischenko, N Mathur … (2005)
          An applied electric field can reversibly change the temperature of an electrocaloric material under adiabatic conditions, and the effect is strongest near phase transitions. This phenomenon has been largely ignored because only small effects (0.003 K V^-1) have been seen in bulk samples such as Pb0.99Nb0.02(Zr0.75Sn0.20Ti0.05)0.98O3 and there is no consensus on macroscopic models. Here we demonstrate a giant electrocaloric effect (0.48 K V^-1) in 300 nm sol-gel PbZr0.95Ti0.05O3 films near the ferroelectric Curie temperature of 222oC. We also discuss a solid state device concept for electrical refrigeration that has the capacity to outperform Peltier or magnetocaloric coolers. Our results resolve the controversy surrounding macroscopic models of the electrocaloric effect and may inspire ab initio calculations of electrocaloric parameters and thus a targeted search for new materials.
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            The giant electromechanical response in ferroelectric relaxors as a critical phenomenon.

            Z Kutnjak, J Petzelt, R Blinc (2006)
            The direct conversion of electrical energy to mechanical work by a material is relevant to a number of applications. This is illustrated by ferroelectric 'relaxors' such as Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PMN-PT; refs 5, 6): these materials exhibit a giant electromechanical (piezoelectric) response that is finding use in ultrasonic and medical applications, as well as in telecommunications. The origins of this effect are, however, still unclear. Here we show that the giant electromechanical response in PMN-PT (and potentially other ferroelectric relaxors) is the manifestation of critical points that define a line in the phase diagram of this system. Specifically, in the electric-field-temperature-composition phase diagram of PMN-PT (the composition being varied by changing the PT concentration), a first-order paraelectric-ferroelectric phase transition terminates in a line of critical points where the piezoelectric coefficient is maximum. Above this line, supercritical evolution is observed. On approaching the critical point, both the energy cost and the electric field necessary to induce ferroelectric polarization rotations decrease significantly, thus explaining the giant electromechanical response of these relaxors.
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              Giant electrocaloric effect in thin-film PbZr(0.95)Ti(0.05)O3.

              A S Mischenko, Q Zhang, J F Scott … (2006)
              An applied electric field can reversibly change the temperature of an electrocaloric material under adiabatic conditions, and the effect is strongest near phase transitions. We demonstrate a giant electrocaloric effect (0.48 kelvin per volt) in 350-nanometer PbZr(0.95)Ti(0.05)O3 films near the ferroelectric Curie temperature of 222 degrees C. A large electrocaloric effect may find application in electrical refrigeration.
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                Author and article information

                Journal
                Journal ID (nlm-ta): Sci Rep
                Journal ID (iso-abbrev): Sci Rep
                Title: Scientific Reports
                Publisher: Nature Publishing Group
                ISSN (Electronic): 2045-2322
                Publication date (Electronic): 17 June 2016
                Publication date Collection: 2016
                Volume: 6
                Electronic Location Identifier: 28251
                Affiliations
                [1 ]Department of Materials, Imperial College London , London, SW7 2AZ, UK
                [2 ]School of Engineering and Materials Science, Queen Mary University of London , 380 Mile End Road, London E1 4NS, UK
                [3 ]Institute of Materials Research, Slovak Academy of Sciences , Watsonova 47, 040 01 Kosice, Slovak Republic
                Author notes
                Article
                Publisher Item ID: srep28251
                DOI: 10.1038/srep28251
                PMC ID: 4911558
                PubMed ID: 27312287
                SO-VID: d12095d2-9e8a-4415-85e0-f4987b67b90a
                Copyright © Copyright © 2016, Macmillan Publishers Limited
                License:

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                Date received : 28 January 2016
                Date accepted : 01 June 2016
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