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In this work, La0.8Sr0.2MnO3 (LSMO) nanopowders are synthesized using two different methods: Pechini (LSMO-PC) and auto-combustion (LSMO-AC). Nanoparticle sizes, structural, magnetic, and magnetocaloric properties were determined and compared. The X-ray diffraction confirms the coexistence of two phases; rhombohedral symmetry with space group R-3c and orthorhombic symmetry with space group Pbnm, with the rhombohedral phase dominating. The scanning electron microscope images show that LSMO-PC has larger nanoparticle sizes (~495 nm) than LSMO-AC (~195 nm). The samples exhibit ferromagnetic properties with distinct hysteresis loops and Curie temperatures 340 K and 290 K for LSMO-PC and LSMO-AC respectively. The variation of the magnetic entropy was measured indirectly using the Maxwell approach with increasing magnetic field. For LSMO-PC it reaches a maximum -dSM=1.69 J/kg.K at 340 K and dH= 5 T. The associated adiabatic temperature change dTM is 1.04 K. While LSMO-PC demonstrates superior magnetic and magnetocaloric properties, LSMO-AC displays significant magnetocaloric thermal stability. The obtained values make LSMO-PC and LSMO-AC promising candidates for eco-friendly room-temperature magnetocaloric applications.

Analytical results obtained within Landau-Ginzburg-Devonshire approach and effective media models, predict that the synergy of size effects and Vegard stresses can significantly enhance the electrocaloric cooling (up to 7 times) of the BaTiO3 nanoparticles in comparison with a bulk BaTiO3. To compare with the considered effective media models, we measured the capacitance-voltage and current-voltage characteristics of the dense nanocomposites consisting of (28-35) vol.% BaTiO3 nanoparticles incorporated in organic polymers and determined experimentally the effective dielectric permittivity and losses of the composites. Generalizing obtained analytical results, various ferroelectric nanoparticles spontaneously stressed by elastic defects, such as oxygen vacancies or any other elastic dipoles, which create a strong chemical pressure, can cause the giant electrocaloric response of dense ferroelectric nanocomposites. We have shown that the advantages of the studied lead-free dense nanocomposites are the good tunability of electrocaloric cooling temperature due to the size effects in ferroelectric nanoparticles and the easy control of the high electrocaloric cooling by electric fields. This makes the dense ferroelectric nanocomposites promising for cooling of conventional and innovative electronic elements, such as FETs with high-temperature superconductor channels., Comment: 42 pages, including 7 figures and 3 appendices

Multiferroic CoFe2O4-Ba0.95Ca0.05Ti0.89Sn0.11O3 core-shell nanofibers (CFO@BCTSn NFs) were synthesized by a sol-gel co-axial electrospinning technique. The scanning electron microscope and transmission electron microscope were used to check nanofibers' core-shell structure/configuration. X-ray diffraction and a high-resolution transmission electron microscope were used to confirm the spinel structure of CFO and the perovskite structure of BCTSn. The magnetic character of the resultant CFO@BCTSn NFs was determined by SQUID magnetometry. The piezoelectricity was verified using piezo-response force microscopy, which revealed an entirely covered ferroelectric shell outline, in accordance with SEM and TEM observations. The magnetoelectric (ME) coefficient was measured as a function of the applied external DC magnetic field. The maximum ME coefficient obtained for the CFO@BCTSn NFs was 346 mV cm-1 Oe-1. The high magnetoelectric coupling suggests that CFO@BCTSn NFs could be a promising candidate for magnetic field sensor and magnetoelectric device applications.

Multiferroic particulate composites $(1-x)$ Ba$_{0.95}$Ca$_{0.05}$Ti$_{0.89}$Sn$_{0.11}$O$_3$-$(x)$CoFe$_2$O$_4$ with ($x$ = 0.1, 0.2, 0.3, 0.4 and 0.5) have been prepared by mechanical mixing of the calcined and milled individual ferroic phases. X-ray diffraction and Raman spectroscopy analysis confirmed the formation of both perovskite Ba$_{0.95}$Ca$_{0.05}$Ti$_{0.89}$Sn$_{0.11}$O$_3$ (BCTSn) and spinel CoFe$_2$O$_4$ (CFO) phases without the presence of additional phases. The morphological properties of the composites were provided by using Field Emission Scanning Electron Microscopy. The BCTSn-CFO composites exhibit multiferroic behavior at room temperature, as evidenced by ferroelectric and ferromagnetic hysteresis loops. The magnetoelectric (ME) coupling was measured under a magnetic field up to 10 kOe and the maximum ME response found to be 0.1 mV /cm/ Oe for the composition 0.7 BCTSn-0.3 CFO exhibiting a high degree of pseudo-cubicity and large density.

The electrocaloric (EC) effect and energy storage properties of eco-friendly ferroelectric Ba0.9Sr0.1Ti1-xSnxO3 (BSTS-x) ceramics prepared by the conventional solid-state reaction method were studied. Significant energy efficiency exceeding 80% was found in our samples. In particular, BSTS-5 and BSTS-10 samples exhibit 92% and 88% efficiency, respectively, over a wide temperature range around room temperature (RT). Direct EC measurement and an indirect method based on the thermodynamic approach were used to characterize the EC effect, and both yielded consistent results. The largest electrocaloric responsivity of 0.73 K mm/kV was obtained for BSTS-0 at 368 K with an adiabatic temperature change DT(EC) of 0.55 K at a low applied electric field of only 7.4 kV/cm. With increasing Sn-content, the EC response of BSTS-x ceramics decreases, while their diffuseness increases over an extensive temperature range, centered at RT. A significant coefficient of performance (COP > 26) was found for our samples. The obtained results demonstrate the possibility of designing eco-friendly materials with higher EC effect and energy efficiency for potential solid-state refrigeration and energy storage devices.

Lead-free ba0.85ca0.15zr0.1ti0.9o3 (bczt) ceramic powders were synthesized using the sol-gel method. to achieve high-energy storage and large electrocaloric effect in bulk ceramics the ceramics thickness was reduced. dielectric, ferroelectric, energy storage, and electrocaloric properties were investigated for bczt ceramic with 400 {\mu}m. here, pure crystalline structure and homogenous microstructure were identified by xrd analysis and sem measurements, respectively. the dielectric measurements revealed a maximum dielectric constant associated with ferroelectric-paraelectric phase transition. the maximum of {\epsilon} was 7841 around 352 k. furthermore, the bczt ceramic showed improved energy storage and electrocaloric properties. a high recoverable energy density wrec of 0.24 j/cm3 and a total energy density wtotal of 0.27 j/cm3 with an efficiency coefficient of ~ 88% at 423 k under an electric field of 55 kv/cm was obtained. besides, the maximum value of {\delta}t = 2.32 k, the electrocaloric responsivity {\zeta} = 0.42 k mm/kv, the refrigeration capacity rc= 4.59 j/kg and the coefficient of performance cop = 12.38 were achieved around 384 k under 55 kv/cm. the total energy density wtotal and the temperature change {\delta}t were also calculated by exploiting the landau-ginzburg-devonshire (lgd) theory. the theoretical results matched the experimental findings. these results suggest that the synthesized bczt ceramic with the reduced thickness could be a promising candidate for energy storage and electrocaloric applications.

This work focuses on the microstructure, magnetic properties and magnetocaloric effect of CoFe$_2$O$_4$ (CFO) nanoparticles elaborated by sol-gel auto combustion method. The XRD investigation indicates that CFO is crystallized in a cubic spinel structure and the SEM micrograph shows a fine quasi-spherical with an average grain sizes of 160 nm. The temperature dependence of the Raman spectra reveals the ferromagnetic to paramagnetic (FM-PM) transition started from 723 K and the magnetization versus temperature measurements shows the Curie temperature located at T$_{\rm C}$ = 785 K. Large value of magnetocaloric temperature change of $\Delta$T =11.2 K with a high RCP of 687.56 J Kg$^{-1}$ are achieved indirectly via the Maxwell approach making our CFO nanopowder suitable candidate for both environmentally friendly magnetic refrigeration and medical applications at ambient temperature.

Structural, dielectric, ferroelectric, energy storage properties, and electrocaloric effect were studied in lead-free ceramic Ba$_{0.95}$Ca$_{0.05}$Ti$_{0.89}$Sn$_{0.11}$O$_3$ (BCTSn) elaborated by sol-gel method. Phase purity structure was confirmed from X-ray data using Rietveld refinement analysis which revealed the coexistence of tetragonal (P4mm) and orthorhombic (Amm2) symmetries at room temperature. Phase transitions were detected by dielectric and differential scanning calorimetry results. Energy storage properties were determined from P-E hysteresis, and the electrocaloric properties were calculated indirectly via the Maxwell approach. The large value of electrocaloric temperature change of $\Delta$T=0.807 K obtained at a relatively small field of 30 kV cm$^{-1}$ and high energy storage efficiency can make BCTSn ceramic a promising candidate for environmentally friendly refrigeration and energy storage applications.

Lead-free BaTi0.89Sn0.11O3 (BTSn) ceramic was elaborated via a solid-state reaction method and its dielectric, ferroelectric, energy storage, electromechanical as well as electrocaloric properties were investigated at 25 kV/cm. Pure perovskite structure was confirmed by X-ray diffraction analysis. The maximum of the dielectric constant was found to be 17390 at 41 {\deg}C. The enhanced total energy density, the recovered energy density, and the energy storage efficiency of 92.7 mJ/cm3, 84.4 mJ/cm3, and 91.04%, respectively, were observed at 60 {\deg}C, whereas the highest storage efficiency of 95.87 % was obtained at 100 {\deg}C. At room temperature, the electromechanical strain and the large-signal piezoelectric coefficient reached a maximum of 0.07 % and 280 pm/V. The large electrocaloric effect of 0.71 K and the electrocaloric responsivity of 0.28. 10-6 K.mm/kV at 49 {\deg}C under 25 kV/cm were indirectly calculated via Maxwell relation from the ferroelectric polarization P (T, E) that was determined from the P-E hysteresis loops. By exploiting the Landau-Ginzburg-Devonshire (LGD) phenomenological theory, the electrocaloric response was estimated to be of 0.61 K at 50 {\deg}C under 25 kV/cm. We conclude that BTSn lead-free ceramic is a promising candidate for potential applications in high-efficiency energy storage devices and solid-state refrigeration technology.

The effects of 2% Zr introduction in Ba0.8Ca0.2TiO3 (BCT) system on its electrical and the electrocaloric properties was investigated.

Lead-free Ba0.85Ca0.15Zr0.10Ti0.90O3 (BCZT) ceramics have demonstrated excellent dielectric, ferroelectric and piezoelectric properties in comparison to lead-based materials. The synthesis of pure and crystalline BCZT nanopowders at low temperatures of 25, 80 and 160 C was reported previously by using a sol-gel method followed by a hydrothermal route. In this study, the structural, dielectric and ferroelectric properties of sintered BCZT ceramics at 1250 {\deg}C for 10h were investigated. XRD measurements revealed the presence of a single perovskite phase at room temperature with the coexistence of the orthorhombic and tetragonal symmetries. The increase of grain size and the ceramic density in BCZT ceramics result in an enhancement of the dielectric and ferroelectric properties of BCZT ceramics. More interestingly, the synthesis temperature of BCZT powders with high dielectric and ferroelectric properties could be decreased to a low temperature of 160 {\deg}C, which is about 1200 {\deg}C lower when compared with solid-state reaction and 840 {\deg}C lower when compared with sol-gel methods. The BCZT ceramics elaborated at 160 {\deg}C revealed excellent electrical properties. Hence, the use of low-temperature hydrothermal processing can be encouraging for the synthesis of lead-free ceramics with high dielectric and ferroelectric properties.

Ferroelectric ceramics (Ba0.85Ca0.15)(Ti0.9Zr0.1-xSnx)O3 (x=0.00, 0.02, 0.04, 0.06) were prepared by a sol-gel method. Structural investigation revealed the co-existence of tetragonal (P4mm) and orthorhombic (Pmm2) symmetries at room temperature for the undoped ceramic, while only a tetragonal structure (P4mm) was observed for the doped ceramics. Dielectric measurements indicate a dielectric relaxation process at high temperatures which is essentially related to the hopping of oxygen vacancies. Furthermore, a down shifting of the Curie temperature (TC) with increasing Sn4+ doping rate has been revealed. The temperature profiles of the Raman spectra unveiled the existence of polar nanoregions (PNRs) above the Curie temperature in all ceramics. The ferroelectric properties were found to be related to the microstructure. Electrocaloric effect was investigated in this system that revealed an electrocaloric responsivity of 0.225 10-6 K m/V for the composition with x = 0.04 Sn doping, where other remarkable physical properties were also observed.

By using the semi-wet synthesis method, lead-free ferroelectric materials Ba0.9Sr0.1Ti1-xSnxO3 with x = 0, 0.02, 0.05, and 0.10 (abbreviated as BSTS) were prepared and their structural, electric and electrocaloric properties were investigated. The X-ray diffraction (XRD) patterns show that the samples calcined at 950{\deg}C have well crystallized into perovskite structure suggesting the substitution of Ti4+ by Sn4+ in BST lattice. With increasing content of Sn, the enhancement of the dielectric permittivity was observed for (0

The existence and feasibility of the multicaloric, polycrystalline material 0.8Pb(Fe1/2Nb1/2)O3-0.2Pb(Mg1/2W1/2)O3, exhibiting magnetocaloric and electrocaloric properties, are demonstrated. Both the electrocaloric and magnetocaloric effects are observed over a broad temperature range below room temperature. The maximum magnetocaloric temperature change of ~0.26 K is obtained with a magnetic-field amplitude of 70 kOe at a temperature of 5 K, while the maximum electrocaloric temperature change of ~0.25 K is obtained with an electric-field amplitude of 60 kV/cm at a temperature of 180 K. The material allows a multicaloric cooling mode or a separate caloric-modes operation depending on the origin of the external field and the temperature at which the field is applied.

It has been considered that polar nanoregions in relaxors form at Burns temperature Td approx 600 K. High-temperature dielectric investigations of Pb(Mg1/3Nb2/3)O3 (PMN) and 0.7PMN-0.3PbTiO3 reveal, however, that the dielectric dispersion around 600 K appears due to the surface-layer contributions. The intrinsic response, analyzed in terms of the universal scaling, imply much higher Td or formation of polar nanoregions in a broad temperature range, while high dielectric constants manifest that polar order exists already at the highest measured temperatures of 800 K. The obtained critical exponents indicate critical behavior associated with universality classes typically found in spin glasses.