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Lead-free Ba0.85Ca0.15Zr0.10Ti0.90O3 (BCZT) ceramics with different BaO-Na2O-Nb2O5-WO3-P2O5 (BNNWP) glass content, forming (1-x)BCZT-xBNNWP lead-free ceramics (abbreviated as BCZTx; x=0, 2, 4, 6, and 8wt%) were synthesized using the conventional solid-state processing route. The XRD investigation shows the coexistence of tetragonal and orthorhombic phases in BCZT pure. Likewise, only the tetragonal phase was detected in BCZTx (x = 2-8 wt%) ceramics. The SEM findings indicate that the average grain size decreases as the amount of BNNWP glass additives increases. In addition, BCZT ceramics Amodified with glass additions showed narrower hysteresis loops and a large electric field. The BCZT4 showed the highest recovered energy density of 0.52 J/cm3 at 135kV/cm with an energy storage efficiency of 62.4%, which is increased by 6.6 compared to BCZT0 (0.075 J/cm3). The energy density was also calculated using the Landau-Ginzburg-Devonshire (LGD) theory

Polycrystalline lead-free Ba$_{0.85}$Ca$_{0.15}$Zr$_{0.10}$Ti$_{0.90}$O$_3$ (BCZT), BaTi$_{0.89}$Sn$_{0.11}$O$_3$ (BTSn) and 0.4Ba$_{0.85}$Ca$_{0.15}$Zr$_{0.10}$Ti$_{0.90}$O$_3$-0.6BaTi$_{0.89}$Sn$_{0.11}$O$_3$ (0.4BCZT-0.6BTSn) ferroelectric ceramics were prepared via sol gel process and their structural, dielectric and energy storage properties were studied. Pure perovskite structure was confirmed by X ray diffraction analysis. The evolution of energy storage performances with temperature was studied. A Significant recoverable energy storage density of 137.86 mJ/cm$^3$ and high energy-storage efficiency of 86.19% under a moderate electric field of 30 kV/cm were achieved in the composite 0.4BCZT 0.6BTSn ceramic at 353 $^\circ$K. Moreover, excellent temperature stability (70-130 $^\circ$C) of the energy storage efficiency (less than 3%) was achieved.

Perovskite-type Ba0.9Sr0.1Ti0.9Sn0.1O3(BSTSn) ceramic was synthesized by the sol gel method. The P E hysteresis loops were recorded at different temperatures to investigate the ferroelectric and energy storage properties of BSTSn ceramic. Enhanced recoverable energy density and high energy storage efficiency were found to be 58.08 mJ/cm3 and 84.36 %, respectively at room temperature (RT) under a moderate applied electric field of 20 kV/cm. The electrocaloric effect (ECE) in the BSTSn ceramic was explored using two different approaches based on P E hysteresis loops, and pyroelectric current measurements. The largest electrocaloric (EC) temperature change of 0.63 K was determined using the Maxwell relationship obtained near RT under 20 kV/cm. The corresponding EC responsivity value of 0.31 K.mm/kV is one of the highest reported values in lead-free ferroelectrics near RT. This study demonstrates that the BSTSn ceramic is a promising candidate for solid-state cooling and energy storage applications.

Lead-free Ba0.9Sr0.1Ti0.9Sn0.1O3 (BSTSn) ceramic was prepared by the sol gel method. X-ray diffraction measurement at room temperature reveals the single-phase formation with tetragonal structure refined in the P4mm space group. Raman spectroscopy analysis at room temperature was used to confirm the structure of BSTSn ceramic sintered at 1420C during 5h. The dielectric measurements were examined in the temperature range [-90 250 C] and the frequency range of [100Hz 1MHz]. The maximum dielectric constant was found to be 5484 (1kHz) at room temperature. The diffuse phase transition characteristic at 1kHz was ascribed by the modified Curie Weiss law. Macroscopic polarization field (P E) hysteresis loops recorded at room temperature (RT) confirm the ferroelectric nature of BSTSn ceramic. Impedance spectroscopy analysis of BSTSn sample in the temperature range 300 380 C reveals the presence of two relaxation contributions originated from grains and grain boundaries. Activation energies of grain and grain boundaries resistances were deduced in order to determine the conduction mechanism of the studied sample.

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 Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) ceramics were successfully prepared by sol-gel process, and sintered at 1420 degree. The effect of sintering times (2, 4 and 6 h) on structural, microstructural, electric properties, energy storage, and electrocaloric effect was systematically examined. X-ray diffraction (XRD) results show that all the samples crystallize in the pure perovskite structure. The morphotropic phase transition from the tetragonal to the orthorhombic phase (T-O) was identified and confirmed by Rietveld refinement. The BCZT ceramic sintered at 1420 degree for 4h possesses a good relative density of 98%, and exhibits optimal properties with a high dielectric permittivity ~16310, a large electrocaloric effect coefficient ~ 0.244Kmm/kV and an energy density storage of ~ 10.61 mJ/cm3.

Over the past decades, there has been significant interest in new cooling technology based on the electrocaloric effect. The large electrocaloric effect observed in polymeric and inorganic ferroelectric materials made possible development of dielectric cooling devices of a new generation. We report a significant impact of annealing on the electrocaloric effect observed in 12/65/35 PLZT bulk ceramics. The electrocaloric data were obtained by direct measurements. Electrocaloric results confirm the existence of the significant electrocaloric response in this relaxor ferroelectric PLZT composition exceeding previously obtained electrocaloric values in perovskite relaxor ferroelectrics such as PMN-PT and x/65/35 PLZT ceramics., Comment: arXiv admin note: text overlap with arXiv:2006.05079

Multiferroic composites with the composition (1-x) BaTi0.8Sn0.2O3 - (x) La0.5Ca0.5MnO3 (x =0, 0.3, 0.5, 0.7, 0.9 and 1) were prepared by sol-gel techniques. Rietveld refinements of the composites with 0-3 and 3-0 type connectivities exhibit the formation of pure phases and confirm the fraction of the composite samples. It was found that the composites grain size decreases slightly with increasing the La0.5Ca0.5MnO3 content. Magnetic measurements of the composite ceramics exhibit a gradual increase in saturation and remanent magnetization with increasing La0.5Ca0.5MnO3 content. Dielectric data demonstrate that the composite materials show high values of the dielectric constant in comparison with the parent compound BaTi0.8Sn0.2O3 (BTSO). In addition, an attempt is made to measure the magnetoelectric coupling coefficient and to explain the negative permittivity and losses occurring in these materials at a certain frequency and temperature conditions.

Recent findings of a large electrocaloric (EC) effect in polymeric and inorganic ferroelectric materials open a potential possibility of development of solid-state cooling or heating devices of new generation with better energy efficiency that may be less harmful for the environment. We investigate by using direct measurements, the temperature and electric field dependence of the electrocaloric response in Pb1-xLax(ZryTi1-y)1-x/4O3 bulk ceramics (PLZT) with x=0.06 and 0.12. Here, the properties of the EC response were probed in a part of the PLZT composition phase diagram with low y=0.40 composition, in which the EC effect was not previously studied. Measurement results show the existence of the sizeable EC response in 12/40/60 PLZT sample with the EC temperature change ({\Delta}TEC) of 2.92 K at 430 K and 80 kV/cm. This value exceeds previously obtained {\Delta}TEC values in relaxor ferroelectric x/65/35 PLZT compositions and rivaling the best EC response in lead magnesium niobate-lead titanate ceramics. The electrocaloric responsivity ({\Delta}T/{\Delta}E) value of 0.41x10-6 Km/V determined at a lower electric field of 20 kV/cm and 410 K is comparable to those observed in other perovskite ferroelectrics.

Perovskite manganite La0.5Ca0.5-x xMnO3 (LCMO) nanomaterials were elaborated using the sucrose modified auto combustion method. Rietveld refinements of the X-ray diffraction patterns of the crystalline structure confirm a single-phase orthorhombic state with Pbnm space group (No. 62). The Ca-vacancies were voluntarily created in the LCMO structure in order to study their influence on the magnetic behaviour in the system. The magnetic susceptibility was found to be highly enhanced in the sample with Ca-vacancies. Paramagnetic-to-ferromagnetic phase transition was evidenced in both samples around 254 K. This transition is, characterized by a drastic jump of the susceptibility in the sample with Ca-vacancies. The maximum of entropy change, observed for both compounds at magnetic field of 6T was 2.30 J kg-1K-1 and 2.70 J kg-1K-1 for the parent compound and the lacunar one respectively. The magnetocaloric adiabatic temperature change value calculated by indirect method was 5.6 K and 5.2 K for the non-lacunar and Ca-vacancy compound, respectively. The Ca-lacunar La0.5Ca0.5-x xMnO3 (x=0.05) reported in this work demonstrated overall enhancement of the magnetocaloric effect over the LCMO. The technique used to elaborate LCMO materials was beneficial to enhance the magnetocaloric effect and magnetic behaviour. Therefore, we conclude that this less costly environmentally friendly system can be considered as more advantageous candidate for magnetic refrigeration applications then the commonly Gd-based compounds., Comment: 12 pages,11 figures, Article

High performance lead-free multiferroic composites are desired to replace the lead-based ceramics in multifunctional devices applications. Laminated compounds were prepared from ferroelectric and ferromagnetic materials. In this work, we present laminated ceramics compound by considering the ferromagnetic La0.5Ca0.5MnO3 (LCMO) and the ferroelectric BaTi0.8Sn0.2O3 (BTSO) in two different proportions. Compounds (1-x) LCMO-(x) BTSO with x=1 and 0 (pure materials) were synthesized by the sol gel method and x=0.7 and 0.5 (laminated) compounds were elaborated by welding appropriate mass ratios of each pure material by using the silver paste technique. Structural, dielectric, ferroelectric, microstructure and magnetic characterization were conducted on these samples. X-ray scattering results showed pure perovskite phases confirming the successful formation of both LCMO and BTSO. SEM images evidenced the laminated structure and good quality of the interfaces. The laminated composite materials have demonstrated a multiferroic behavior characterized by the ferroelectric and the ferromagnetic hysteresis loops. Furthermore, the enhancement of the dielectric constant in the laminated composite samples is mainly attributed to the Maxwell-Wagner polarization.

Ba1-xMgx(Ti0.9Zr0.1)O3(x= 0.01 and 0.02) ceramics were prepared using the conventional solid state reaction. Rietveld refinement performed on X-ray diffraction patterns indicates that the samples are tetragonal crystal structure with P4mm space group. By increasing Mg content from 1 to 2% the unit cell volume decreased. Likewise, the grains size is greatly reduced from 10 to 4 micrometer. The temperature dependence of dielectric constants at different frequencies exhibited typical relaxor ferroelectric characteristic, with sensitive dependence in frequency and temperature for ac conductivity. The obtained activation energy values were correlated to the proposed conduction mechanisms.

The site-doping strategy of barium titanate (BaTiO3) is a promising way to develop new lead-free materials for energy with enhanced dielectric and piezoelectric properties. A novel strategy to elaborated pure and crystalline Ba0.85Ca0.15Zr0.1Ti0.9O3(BCZT) ferroelectric powders at low temperature is proposed. It is based on sol-gel method followed by a hydrothermal reaction. The effects of preparation temperature on structure, crystallinity, purity, morphology and particles size distribution of BCZT powders were studied. It was clearly shown that pure and crystalline BCZT could be obtained over 80{\deg}C. Furthermore, the BCZT particles exhibit a spherical shape whose mean size increases from 145 nm at 40{\deg}C to 160 nm at 80{\deg}C. The present study may provide a new strategy to design lead-free ferroelectric materials with enhanced structure and microstructure properties at very low temperature.

The present letter explores the electrocaloric effect (ECE) in the lead free oxide Ba0.8Ca0.2Ti0.95Ge0.05O3 ceramics (BCTG). The electrocaloric responsivity (dT/dE) was determined by two different methods using the Maxwell relationship (dT/dE)~(dP/dT)_E. In a first well-known indirect method, P-E hysteresis loops were measured in a wide temperature range from which the pyroelectric coefficient p_E=(dP/dT)_E and thus (dT/dE) were determined by derivation of P(T,E) data. In the second novel method the pyroelectric coefficient p_E and consequently the electrocaloric responsivity was determined by direct measurements of the pyroelectric currents under different applied electric fields. Within the experimental error good agreement was obtained between two methods with an electrocaloric responsivity equal to 0.18 +/- 0.05 10-6 K.m.V-1 was obtained at about 410 K, Comment: 5 pages, 4 figures