Synthesis,structural evolution,and dielectric properties of a new perovskite solid solution (Pb0.5Sr0.5)(Zr0.5Ti0.5)O3–PbTiO3

To explore lead-reduced dielectric materials in the SrTiO₃–PbTiO₃–PbZrO₃ ternary system, a novel solid solution between relaxor ferroelectric (Pb_0.5Sr_0.5)(Zr_0.5Ti_0.5)O₃ and ferroelectric PbTiO₃, namely (1 − x)(Pb_0.5Sr_0.5) (Zr_0.5Ti_0.5)O₃–xPbTiO₃ (lead–strontium–zirconate–titanate [PSZT]–PT), has been synthesized in the perovskite structure by high-temperature solid-state reaction method in the form of ceramics. The crystal structure and phase symmetry of the materials synthesized were analyzed and resolved based on X-ray powder diffraction (XRD) data through both the Pawley and Rietveld refinements. The results of the structural refinements indicate that at low PT-concentration end of the solid solution system, for example, x = 0.05, the PSZT–PT solid solution exhibits a cubic structural symmetry (with the space group Pm-3m). As the PT concentration (x) increases, the structure of (1 − x)PSZT–xPT gradually transforms from the cubic to a tetragonal (P4mm) phase. In the composition range of x = 0.10–0.25, a mixture of the cubic and tetragonal phases was identified. As the concentration of PT increases, the proportion of the tetragonal phase increases at the expense of the cubic phase. For a composition of x > 0.25, a pure tetragonal phase is observed. The dielectric properties of the materials were studied by measuring the permittivity as a function of temperature at various frequencies. For the composition of x = 0.05, the temperature dependence of dielectric constant shows typical relaxor behavior. For x = 0.35, the dielectric peaks indicate a normal ferroelectric phase transition. Overall, a structural transformation from a central-symmetric, nonpolar cubic phase to a non-centrosymmetric, polar tetragonal phase is induced by the substitution of PT for PSZT in the pseudo-binary solid solution of (1 − x)PSZT–xPT, which also reveals an interesting relaxor to ferroelectric crossover phenomenon.     

Synthesis and electrochemical characterization of La0.75Sr0.25Mn0.5Cr0.5−xAlxO3, for IT- and HT-SOFCs

The main emphasis of this work is to create a new perovskite material with three different compositions (La_0.75Sr_0.25Mn_0.5Cr_0.5−xAlxO₃, x = 0.1, 0.2, 0.3) applied in both Intermediate- and High-temperature Solid Oxide Fuel Cells (IT- and HT-SOFCs). Perovskite-type polycrystalline La_0.75Sr_0.25Mn_0.5Cr_0.5−xAl_xO_3−δ (x = 0.1, 0.2, 0.3) powders were synthesized and formed in a single phase structure by a dry chemistry route (standard solid-state reaction method). The effect of Al doping on physicochemical and surface properties has been discovered. The compounds were crystallized in single phase rhombohedral symmetry (R-3C Space. Group). Total conductivity of Al doping in wet 5% H₂ was higher than both dry 5% H₂ and air. The obtained results enhance the electro-catalytic performance and the material conductivity as well, which will be good for anode materials in IT- and HT-SOFCs and the optimum doping is 10%.     

Synthesis,structure, optical and magnetic properties of Nd1−xAxMn0.5Co0.5O3−δ (A = Ba,Sr and Ca; x = 0 and 0.25)

The structural, optical, and magnetic properties of polycrystalline Nd_1-xA_xMn_0.5Co_0.5O_3−δ (A = Ba, Sr and Ca; x = 0 and 0.25) perovskite oxides were investigated. The powder XRD pattern demonstrates that the unit cell volume decreases with the changing A-site dopant type. The estimated bandgap energy (Eg) from UV–vis spectroscopic for NdMn_0.5Co_0.5O_3−δ, Nd_0.75Ba_0.25Mn_0.5Co_0.5O_3−δ, Nd_0.75Sr_0.25Mn_0.5Co_0.5O_3−δ and Nd_0.75Ca_0.25Mn_0.5Co_0.5O_3−δ are 3.27, 3.82, 3.79 and 3.53 eV respectively. The substitution of divalent element alters the absorption spectrum, while the redshift optical transition was observed with an increasing ionic radius of dopant. Temperature-dependent magnetization exposes that the Curie temperature (TC) gradually decreases with the decreasing size of alkaline earth metals, and glassy nature was observed at a lower applied magnetic field. The observation of TC can be well explained by the considering of the cationic size disorder parameter in A-site than the random distribution of B-site ions.     

Structural,dielectric and ferroelectric properties of Ba1−x(Bi0.5Na0.5)xTiO3 ceramics

Lead free Ba_1?x(Bi_0.5Na_0.5)_xTiO₃ (x=0, 0.02, 0.04, 0.06, 0.08, 0.1) ferroelectric ceramics were synthesized by conventional solid state reaction technique. Sintering was done at 1200 °C for 2 h in air atmosphere. The final products have tetragonal symmetry with decreasing c/a ratio confirmed by X-ray diffraction analysis. The grain size varies between 300 nm to 1000 nm for x=0 to 0.1. With increase in Bi_0.5Na_0.5TiO₃ [BNT] content, the room temperature permittivity decreases whereas the Curie temperature (T_c) increases and its highest value was found to be 155 °C for 10 mol% of BNT addition. The ceramics show stable and low dielectric loss characteristics. The remnant polarization (P_r) and the coercive field (E_c) increases monotonously with increase in BNT content. The highest value of 2P_r (=17 μC/cm²) and 2E_c (=22 Kv/cm) was obtained for x=10 mol% BNT addition.     

Dielectric,ferroelectric, and depolarization properties of B-site manganese-doped 0.925(Bi0.5Na0.5)TiO3–0.075BaTiO3 solid solutions

(Bi_0.5Na_0.5)_0.925Ba_0.075(Ti_1−xMn_x)O₃ (x=0, 0.2, 1.0, and 2.0 mol%) ceramics were prepared by solid-state-reaction method to study dielectric, ferroelectric, and depolarization properties. The manganese (Mn) doping can suppress dielectric permittivity and increase relaxor behavior. Coercive field (E_c) increases, while remanent polarization (P_r) decreases as the Mn content increases. P_r exhibits discontinuous anomalies as a function of temperature in all compositions, implying a polarization reorganization of local domains. The depolarization temperature (T_d) reaches the highest value (~152 °C) in 0.2%Mn, and decreases as MnO₂ content increases. The increased T_d in 0.2%Mn is due to two-phase coexistence and structural thermal stability induced by Mn ions. This work suggests that the moderate Mn doping can enhance T_d in lead-free piezoceramics for applications at elevated temperatures.     

Modified structural,optical, magnetic and ferroelectric properties in (1-x)BaTiO3-xBaCo0.5Nb0.5O3-δ ceramics

Lead-free perovskite ceramics with the formula of (1-x)BaTiO₃-xBaCo_0.5Nb_0.5O_3-δ ((1-x)BT-xBCN), exhibit structural phase transition, modified band-gap (E_g), ferromagnetic and ferroelectric orders at room-temperature (RT). All ceramics have no impurity phase but the structural transition from tetragonal to cubic phase is observed with the increase of x. A possible mechanism is proposed to explain the variation of crystal structure. Raman scattering analysis not only proves the existence of doping-induced phase transition but also indicates the changed bonding vibration modes between adjacent atoms. The appearance of two band-gaps in doping samples, the low E_g is about 1.3 eV, obviously smaller than that of 3.2 eV for pure BaTiO₃ (BT), which is attributed to the electronic orbital of Co 3d within the gap of BT. Moreover, the RT ferromagnetic behavior is obtained at x = 0.05, which can be interpreted via the F center exchange model. These results show the potential applications for perovskite oxides on solar energy conversion apparatus and multiferroic devices.     

Structural,dielectric and piezoelectric properties of (Bi0.5Na0.5)TiO3–(Bi0.5K0.5)TiO3–Bi(Zn0.5Ti0.5)O3 thin films prepared by sol–gel method

Lead free (1−x)(0.8Bi_0.5Na_0.5Ti_0.5O₃–0.2Bi_0.5K_0.5TiO₃)–xBiZn_0.5Ti_0.5O₃ (x=0–0.06) (BNT–BKT–BZT) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by a sol–gel processing technique. The effects of BZT content on the structural, dielectric, ferroelectric and piezoelectric properties of the BNT–BKT–BZT thin films were investigated systematically. The BNT–BKT–BZT thin films undergo a transition from ferroelectric to relaxor phase with increasing temperature. The phase transition temperature decreases with the increase of BZT content. The BNT–BKT–BZT thin film with x=0.04 exhibits the best ferroelectric properties (P_max=40 µC/cm² and P_r=10 µC/cm²), largest dielectric constant (ε=560) and piezoelectric constant (d₃₃=40 pm/V). This finding demonstrates that the BNT–BKT–BZT thin film has an excellent potential for demanding high piezoelectric properties in lead free films.     

Physical–chemical property and activity evaluation of LaB0.5Co0.5O3 (B = Cr,Mn, Cu) and LaMnxCo1−xO3 (x = 0.1, 0.25, 0.5) nano perovskites in VOC combustion

The correlation between physical–chemical properties and activities of LaB_0.5Co_0.5O₃ (B = Cr, Mn, Cu) nano perovskites was studied in combustion of toluene. LaMn_0.5Co_0.5O₃ showed the highest activity among LaB_0.5Co_0.5O₃ catalysts and further optimization study was focused on LaMn_xCo_1?xO₃ (x = 0.1, 0.25, 0.5). The activity and reducibility of catalysts improved due to partial substitution of Co³⁺ by B cation. No direct relationship was between surface area and catalyst activity. T_50% of 2-propanol over LaMn_0.25Co_0.75O₃, LaMn_0.5Co_0.5O₃, LaMn_0.1Co_0.9O₃ and LaCoO₃ was 168, 200, 220 and 229 °C, respectively. LaMn_0.25Co_0.75O₃ was the optimum catalyst and showed robust stability in combustion of toluene and 2-propanol.     

Study of structural,dielectric, electric,magnetic and magnetoelectric properties of K0.5Na0.5NbO3 − Ni0.2Co0.8Fe2O4 composites

Magnetoelectric composites with general formula (x) Ni_0.2Co_0.8Fe₂O₄- (1- x) (K_0.5Na_0.5)NbO₃ (x = 0, 0.10, 0.20, 0.30, 0.40, 0.50 and 1.0) have been synthesized by solid state reaction method. X-ray diffraction pattern asserts the existence of both the constituent phases in the synthesized composites. FESEM micrographs are used to investigate the microstructure and for calculation of average grain size of the composites. Temperature dependent dielectric properties are investigated as a function of temperature and found to enhance with addition of ferrite in the composites. P-E hysteresis loops obtained for individual (K_0.5Na_0.5)NbO₃ (KNN) phase and composites indicate the ferroelectric ordering in the composites. Saturation and remnant magnetization show increasing trend with increase in NCFO concentration. FC-ZFC magnetization curves indicate charge ordering, metal-insulator transition (Verwey transition) in NCFO and composites. Impedance spectroscopy shows that bulk resistance reduces with increase in temperature, thereby indicating negative temperature coefficient of resistance (NTCR) behaviour of the composites. The magnetoelectric effect is confirmed by measuring magnetoelectric voltage coefficient, α_ME and the maximum value of α_ME is 5.389 mV/cm-Oe for 20% NCFO-80% KNN composite.     

Phase structure,piezoelectric, ferroelectric,and electric-field-induced strain properties of Nb-modified 0.8Bi0.5Na0.5TiO3−0.2Sr0.85Bi0.1TiO3 ceramics

0.8Bi_0.5Na_0.5Ti_(1-x)Nb_xO₃−0.2Sr_0.85Bi_0.1TiO₃ (BNT-SBT-xNb, x = 0.00, 0.01, 0.02, and 0.03) piezoelectric ceramics were prepared by traditional solid state reaction and the influence of Nb substitution on the phase structure, ferroelectric, piezoelectric, and electric-field-induced strain properties in BNT-SBT ceramics were studied. XRD results exhibited that Nb⁵⁺ ions could fully diffuse into BNT-SBT structure to form a solid solution when x = 0.01. P-E loops and S-E curves suggested that the ferroelectric phase transformed to ergodic relaxor state (FE-to-ER) with the increasing the amount of Nb additive, indicating the ferroelectric long-ranged order was disturbed by the excess of Nb. With increasing Nb doping, phase transition temperature from normal ferroelectric to ergodic relaxor (short for T_F-R) could be reduced from 120 °C to 40 °C. Furthermore, for sample with x = 0.01, the normalized strain d₃₃^* got a maximum value ~571 pm/V due to the phase transition from ergodic relaxor to ferroelectric (ER-to-FE) under electric field.     

Polyaniline (PANI)–Co0.5Mn0.5Fe2O4 nanocomposite: Synthesis,characterization and magnetic properties evaluation

Polyaniline (PANI)/Cobalt-manganese ferrite, (PANI)/Co_0.5Mn_0.5Fe₂O₄, nanocomposite was synthesized by oxidative chemical polymerization of aniline in the presence of ammonium peroxydisulfate (APS). Microwave assisted synthesis method was used for the fabrication of core CoFe₂O₄ nanoparticles. The structural, morphological, thermal and magnetic properties of the nanocomposite were investigated in detail by X-ray diffraction (XRD), fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). The average crystallite size of (PANI)/Co_0.5Mn_0.5Fe₂O₄ nanocomposite by the line profile method was 20±9 nm. The magnetization measurements revealed that (PANI)/Co_0.5Mn_0.5Fe₂O₄ nanocomposite has superparamagnetic behavior with blocking temperature higher than 300 K. The saturation magnetization of the composite is considerably low compared to that of CoFe₂O₄ nanoparticles due to the partial replacement of Co²⁺ ions and surface spin disorder. As temperature decreases, both coercivity and strength of antiferromagnetic interactions increase which results in unsaturated magnetization of the nanocomposite.     

Phase structure,ferroelectric properties,and electric field-induced large strain in lead-free 0.99[(1−x)(Bi0.5Na0.5)TiO3-x(Bi0.5K0.5)TiO3]–0.01Ta piezoelectric ceramics

Lead-free 0.99[(1−x)(Bi_0.5Na_0.5)TiO₃-x(Bi_0.5K_0.5)TiO₃]–0.01Ta piezoelectric ceramics were prepared by a conventional solid-state reaction process. The ferroelectric properties, and strain behaviors were characterized. Increase of the (Bi_0.5K_0.5)TiO₃ content induces a phase transition from coexistence of ferroelectric tetragonal and rhombohedral to a relaxor pseudocubic phase. Accordingly, the ferroelectric order is disrupted significantly with the increase of (Bi_0.5K_0.5)TiO₃ content and the destabilization of the ferroelectric order is accompanied by an enhancement of the unipolar strain, which peaks at a value of 0.35% (corresponding to a large signal d₃₃ of 438 pm/V) in samples with 20 mol% (Bi_0.5K_0.5)TiO₃ content. Temperature dependent measurements of both polarization and strain from room temperature to 120 °C suggested that the origin of the large strain is due to a reversible field-induced nonpolar pseudocubic-to-polar ferroelectric phase transformation.     

Structure,dielectric and ferroelectric properties of 0.92Na0.5Bi0.5TiO3–0.06BaTiO3–0.02K0.5Na0.5NbO3 lead-free ceramics: Effect of Co2O3 additive

0.92Na_0.5Bi_0.5TiO₃–0.06BaTiO₃–0.02K_0.5Na_0.5NbO₃+x wt% Co₂O₃ (NBKT–xCo, x=0, 0.2, 0.4, 0.6, 0.8) lead-free ferroelectric ceramics were prepared via a conventional solid state reaction method. Effects of Co₂O₃ additive on crystallite structure, microstructure, dielectric and ferroelectric properties of the NBKT–xCo ceramics were studied. X-ray diffraction results showed that the rhombohedral–tetragonal morphotropic phase boundary existed in all the ceramics, with relative amount of tetragonal phase varying with the content of Co₂O₃. Average grain size, maximum value of dielectric constant, Curie temperature and ferroelectric properties of the ceramics were close related to the content of Co₂O₃. The dielectric anomaly caused by the phase transition between the ferroelectric phase and the so-called “intermediate phase” was observed in the ceramics with x≤0.2, while it disappeared with further increasing x. All the ceramics showed a diffuse phase transition between the “intermediate phase” and the paraelectric phase. The change in the ferroelectric properties with changing the content of Co₂O₃ was discussed by considering the competitive effects among grain size, relative amount of the tetragonal phase and oxygen vacancies.     

Preparation and dielectric properties of (Sr1−xCax)Fe0.5Nb0.5O3; (x=0.0, 0.1, 0.2) ceramics

In the present work, strontium calcium iron niobate ((Sr_1?xCa_x)Fe_0.5Nb_0.5O₃; SCFN) (x=0, 0.1, and 0.2) powders were synthesized for the first time using a molten salt technique. The pure phase perovskite obtained at a relative low calcination temperature of 800 °C was characterized using the X-ray diffraction technique (XRD). SCFN ceramics were fabricated and their properties were investigated. The XRD data of the SCFN ceramics was consistent with an orthorhombic symmetry. However, the solubility of Ca in the SCFN ceramics had an upper limit at x=0.1. All ceramics showed a large dielectric constants. The Ca doping inhibited grain growth, but produced an improvement in dielectric–temperature stability. Furthermore, the doping reduced loss tangent, especially for the x=0.1 sample. These results suggest that the SCFN ceramics prepared from molten salt synthesis exhibit a good dielectric performances, compared to many high dielectric materials that have been prepared using the conventional method.     

High- and low-field dielectric responses and ferroelectric properties of (Bi0.5Na0.5)Zr1−xTixO3 ceramics

Bismuth sodium zirconate titanate (Bi_0.5Na_0.5)Zr_1?xTi_xO₃ with (x=0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) ceramics was fabricated by a conventional sintering technique at 850–1000 °C for 2 h. From X-ray diffraction study, three regions of different phases were observed in the ceramic system; i.e., orthorhombic phase region (0≤x≤0.2), mixed-phase region (0.3≤x≤0.4), and rhombohedral phase region (0.5≤x≤0.6). It was observed that the phase evolution from orthorhombic to rhombohedral symmetry resulted in a noticeable increase of the dielectric properties. The results from the high- and low-field dielectric responses indicated that the dielectric properties of both BNZ and BNZT ceramics were dominantly attributed to the reversible contribution. It was also noticed that grain size showed only partial influence on the increase of low-field dielectric constant in Ti-rich BNZT ceramic.     

Morphotropic phase boundary and electrical properties of lead-free (K0.5Bi0.5)TiO3–Bi(Ni0.5Ti0.5)O3 relaxor ferroelectric ceramics

Lead-free relaxor ferroelectric ceramics (1?x)(K_0.5Bi_0.5)TiO₃–xBi(Ni_0.5Ti_0.5)O₃ were prepared by a conventional solid-state route, the phase transition behavior and corresponding electrical properties were investigated. A typical morphotropic phase boundary (MPB) between rhombohedral and tetragonal ferroelectric phases was identified to be in the range of 0.05<x<0.07 where the optimum piezoelectric and electromechanical properties of d₃₃=126 pC/N and k_P=18% were achieved. Most importantly, a high Curie temperature ~320 °C, around which the material shows a typical relaxor ferroelectric behavior characterized by the presence of diffuse phase transition and frequency dispersion, was obtained in MPB compositions, significantly higher than those of some existing MPB lead-free titanate systems. These results demonstrate a tremendous potential of the studied system for device applications.     

Effect of mechanical milling on structural,dielectric and magnetic properties of BaTiO3–Ni0.5Co0.5Fe2O4 multiferroic nanocomposites

The coexistence of ferroelectricity and ferromagnetism has triggered great interest in multiferroic materials. Multiferroic with strong room temperature magnetoelectric (ME) coupling can provide a platform for future technologies. In this paper, we have investigated the effect of mechanical milling on the properties of multiferroic nanocomposites synthesized by mixing barium titanate (BaTiO₃) (BT) and nickel cobalt ferrite (Ni_0.5Co_0.5Fe₂O₄) (NCF). This process has resulted into reliable disposal of a given quantity of NCF nanoparticles in BT grid and composite samples of different particle sizes (<500 nm) have been obtained by varying the duration of ball-milling for 12, 24, and 48 h. The presence of NCF within BT powder has been confirmed by X-ray Diffraction (XRD) and magnetization measurements (MH). Structural analysis was performed by using Reitveld refinement method that shows that the tetragonality of BaTiO₃ structure get reduced in submicron range. Variations in ferroelectric and dielectric properties with reduction in particle size/milling duration have been studied by P-E loop tracer and Impedance analyzer. The dielectric constant value of 400 has been observed for BT-NCF0 that increases to 9.7 K for composite sample ball mill at 48 h whereas remnant polarization increases to 4.2 μC/cm². These composites with high dielectric constant that changes with temperature and particles size find application in energy storage devices, sensor and memory devices.     

Crystal structure,microstructure and electrical properties of (1−x−y)Bi0.5Na0.5TiO3–xBi0.5K0.5TiO3–yBiFeO3 ceramics near MPB prepared via the combustion technique

(1?x?y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBiFeO₃ (BNKFT-x/y with 0.12≤x≤0.24, 0≤y≤0.07) lead-free piezoelectric ceramics have been prepared by the combustion technique. The effects of amounts of x and y on structures and electrical properties were examined. Powders and ceramics can be well calcined and sintered at 750 °C for 2 h and 1025–1050 °C, respectively. The results indicated that the crystalline structure and microstructure changed with the increase of x and y concentrations. XRD results of BNKFT-x/0.03 and BNKFT-0.18/y ceramics with 0.12≤x≤0.24 and 0≤y≤0.07 showed the rhombohedral–tetragonal morphotropic phase boundary (MPB). The addition of y caused a promoted grain growth while the addition of x suppressed the grain growth. The highest density (ρ=5.85 g/cm³), superior dielectric properties at T_c (ε_r=7846 and tan δ=0.02), remnant polarization measured at 40 kV/cm (P_r = 20.1 μC/cm²) and piezoelectric coefficient (d₃₃=213 pC/N) were obtained for x=0.18 and y=0.03.