Pyroelectric properties of Mn‐doped Aurivillius ceramics with different pseudo‐perovskite layers

The pyroelectric properties of Mn‐doped Aurivillius ceramics with different pseudo‐perovskite layers were investigated. The pyroelectric coefficients for 0.2 wt% Mn‐doped two‐layer CaBi₂Nb₂O₉ (CBN–Mn), three‐layer Bi₄Ti_2.85Nb_0.15O₁₂ (BTN–Mn), and four‐layer CaBi₄Ti_3.95Nb_0.05O₁₅ (CBTN–Mn) ferroelectric ceramics were found to be on the order of 26.0, 54.4, 84.4 μC/m²K at room temperature, respectively. These values were closely associated with the number of octahedral layers in the pseudo‐perovskite blocks. The high pyroelectric coefficient, together with low dielectric permittivity and loss (tan δ < 0.003), results in to high figures of merit for the current responsivity, voltage responsivity, and detectivity. The excellent pyroelectric properties and high Curie temperatures (T_C > 660°C) make the Aurivillius ceramics potential candidates for pyroelectric devices over a broad temperature range.     

Preparation and performance analysis of barium titanate incorporated in corn starch‐based polymer electrolytes for electric double layer capacitor application

Polymer electrolyte membranes composing of corn starch as host polymer, lithium perchlorate (LiClO₄) as salt, and barium titanate (BaTiO₃) as composite filler are prepared using solution casting technique. Ionic conductivity is enhanced on addition of BaTiO₃ by reducing the crystallinity and increasing the amorphous phase content of the polymer electrolyte. The highest ionic conductivity of 1.28 × 10^?2 S cm^?1 is obtained for 10 wt % BaTiO₃ filler in corn starch‐LiClO₄ polymer electrolytes at 75°C. Glass transition temperature (T_g) of polymer electrolytes decreases as the amount of BaTiO₃ filler is increased, as observed in differential scanning calorimetry analysis. Scanning electron microscopy and thermogravimetric analysis are employed to characterize surface morphological and thermal properties of BaTiO₃‐based composite polymer electrolytes. The electrochemical properties of the electric double‐layer capacitor fabricating using the highest ionic conductivity polymer electrolytes is investigated using cyclic voltammetry and charge‐discharge analysis. The discharge capacitance obtained is 16.22 F g^?1. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43275.     

Processing,Dynamic mechanical thermal analysis,and dielectric properties of barium titanate/cellulosic polymer nanocomposites

High dielectric constant BaTiO₃/ethyl cellulose (BT/EC) nanocomposites having BT loadings of up to 13 vol% were fabricated through a simple casting technique. The BT filler powder, synthesized through an ultrasonic‐assisted solid‐state route, was revealed by X‐ray powder diffractometry (XRD) and Raman spectroscopy to be dominantly tetragonal. Scanning electron microscopy (SEM) showed good dispersion of the BT nanoparticles in the EC polymer matrix at lower BT concentrations. However, at higher concentrations, the BT particles form a continuous phase or a “filler network” leading to weak BT/EC interactions. This finding is well supported by the results of the tensile strength and storage modulus. The dielectric properties of the BT/EC nanocomposites were investigated over wide ranges of frequency and temperature. The addition of BT significantly increased the permittivity (ε ′) and dielectric loss (ε ″) and improved the ionic conductivity of the EC. The electric modulus (M″ ) results were analyzed in terms of the Havriliak–Negami function through three distinct relaxation mechanisms (namely α, β*, and β relaxations) in the temperature range 30–150°C. The dc conductivity (σ _dc) results suggest that the BT/EC nanocomposites formed at low BT loading (up to 7.0 vol%) and a temperature of ≤60°C are good candidates for antistatic applications while those formed at higher concentrations and temperatures are recommended for use in electrostatic dissipation applications. POLYM. COMPOS., 38:893–907, 2017. © 2015 Society of Plastics Engineers     

Microstructure and dielectric properties of Dy/Mn doped BaTiO3 ceramics

Dy/Mn doped BaTiO₃ with different Dy₂O₃ contents, ranging from 0.1 to 5.0 at% Dy, were investigated regarding their microstructural and dielectric characteristics. The content of 0.05 at% Mn was constant in all the investigated samples. The samples were prepared by the conventional solid state reaction and sintered at 1290°, and 1350 °C in air atmosphere for 2 h. The low doped samples (0.1 and 0.5 at% Dy) exhibit mainly fairly uniform and homogeneous microstructure with average grain sizes ranged from 0.3 μm to 3.0 μm. At 1350 °C, the appearance of secondary, abnormal, grains in the fine grain matrix and core–shell structure were observed in highly doped Dy/BaTiO₃. Dielectric measurements were carried out as a function of temperature up to 180 °C. The low doped samples sintered at 1350 °C, display the high value of dielectric permittivity at room temperature, 5600 for 0.1Dy/BaTiO₃. A nearly flat permittivity–temperature response was obtained in specimens with 2.0 and 5.0 at% additive content. Using a Curie–Weiss and modified Curie–Weiss low, the Curie constant (C), Curie like constant (C′), Curie temperature (T_C) and a critical exponent (γ) were calculated. The obtained values of γ pointed out the diffuse phase transformation in highly doped BaTiO₃ samples.     

Low-loss and temperature-stable negative permittivity in La0.5Sr0.5MnO3 ceramics

Materials with negative permittivity need to be used at different temperatures, while the negative permittivity behavior affected by large fluctuations in temperature has seldom been studied. In this work, La_0.5Sr_0.5MnO₃ ceramics were prepared by a sol-gel auto-combustion method and subsequent sintering. The negative permittivity behavior, electrical conductivity and reactance of La_0.5Sr_0.5MnO₃ ceramics were systematically studied at various temperatures. The fluctuation in negative permittivity is less than 2.6 % and the dielectric loss (tanδ) is less than 0.2 in the temperature range of 50–600 °C. Based on the key governing properties being achieved, the present work experimentally demonstrates that La_0.5Sr_0.5MnO₃ ceramics, as single-phase oxides, can be used as a feasible alternative metamaterial in a wide temperature range.     

Fabrication and performances of high lithium-ion conducting solid electrolytes based on NASICON Li1.3Al0.3Ti1.7-xZrx(PO4)3 (0≤ x≤ 0.2)

Solid electrolytes are the key component in designing all-solid-state batteries. The Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) structure and its derivatives obtained by doping various elements at Ti and Al site acts as good solid electrolytes. However, there is still scope for enhancing the ionic conductivity using simple precursors and preparation methods. In this study, the Li superionic conductors Li_1.3Al_0.3Ti_1.7-xZr_x(PO₄)₃ (LATZP) with 0 ≤ x ≤ 0.2 have been successfully prepared by the solid-state reaction route. The structural, morphological, and ionic transport properties were analyzed using several experimental techniques including powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and impedance spectroscopy (IS). The presence of two relaxation processes corresponding to grain and grain boundary was studied using various formalisms. We have observed that grain effects dominate at lower temperatures (<100 °C) while the grain boundary at higher temperatures (> 200 °C) on ionic conductivity. The relaxation mechanisms of grain and grain boundaries were investigated by the Summerfield scaling of AC conductivity. The highest total ionic conductivity of 2.48 × 10^-4 S/cm at 150 °C and 5.50 × 10^-3 S/cm at 250 °C was obtained for x = 0.1 in Li_1.3Al_0.3Ti_1.6Zr_0.1(PO₄)₃ sintered at 950 °C/6 h in the air. The ionic conductivity value was found to be higher than the ionic conductivity reported for LATP prepared via solid-state reaction mechanism using the same precursors and conditions.     

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.     

Dielectric,ferroelectric, and energy storage properties in dysprosium doped sodium bismuth titanate ceramics

In this work, Na_0.5(Bi_1-xDy_x)_0.5TiO₃ (0?≤?x?≤?15%) ceramics were prepared via solid state reaction method and were characterized. A stable and pure perovskite phase was revealed by X-ray diffraction analysis for all compositions and a symmetry change from rhombohedral to orthorhombic phase was detected beyond 10% of Dy substitution. The incorporation of Dy³⁺ into Sodium Bismuth Titanate (Na_0.5Bi_0.5TiO₃) matrix allows a substantial decrease of the coercive field, an increase in the resistivity, and leads to a high stability of the dielectric permittivity (??/?_(150?°C) ≤?±?15%) over a wide temperature range. Furthermore, this system was found to exhibit improved energy storage properties at high temperatures with a maximum energy density of 1.2?J/cm³ obtained for 2%Dy composition at 200?°C. The obtained results are very promising for energy storage capacitors operating at high temperatures.     

Structure and Dielectric Properties of BaTiO3–BiYO3 Perovskite Solid Solutions

(1?x)BaTiO₃–xBiYO₃ [(1?x)BT–xBY] polycrystalline ceramics were prepared by solid‐state reaction method. The ceramics are in tetragonal phase when x ≤ 0.04, transform to pseudocubic at x ≥ 0.06, showing a classic ferroelectric to relaxor transition at x = 0.06, where the phase transition temperature was found to shift to higher temperature with increasing frequency. The dielectric permittivity peaks were analyzed by the modified Curie–Weiss law. Both parameters ΔT_diffuse and ΔT_relaxor were found to increase with increasing BY content, demonstrating a stronger relaxor characteristic.     

Effects of glass additions on the microstructure and dielectric properties of barium strontium titanate (BST) ceramics

Commercial glass frits (lead borosilicate glasses) were employed as the sintering aids to reduce the sintering temperatures of BST ceramics. The effects of the glass content and the sintering temperature on the microstructures, dielectric properties and tunabilities of BST ceramics have been investigated. Densification of BST ceramics of 5 wt% glass content becomes significant from sintering temperature of 1000 °C. The glass content shows a strong influence on the Curie temperature T_c, permittivity and the diffuse transition. X-ray results show all BST ceramics exhibit a perovskite structure and also the formation of a secondary phase, Ba₂TiSi₂O₈. The shift of BST diffraction peaks towards higher angle with increasing the glass content indicates the substitution of Pb²⁺ in Ba²⁺ site, which mainly accounts for the diffuse transition observed in these BST ceramics. BST ceramics with 10 wt% glass additives possess the highest tunability at all four sintering temperatures. A tunability of 12.2% at a bias field of 1 kV/mm was achieved for BST ceramics with 10 wt% glass content sintered at 900 °C.     

Effect of nanofiller concentration on conductivity and dielectric properties of poly(ethylene oxide)–poly(methyl methacrylate) polymer electrolytes

This paper reports the effect of nanofiller concentration on the conductivity and dielectric properties of the poly(ethylene oxide)–poly(methyl methacrylate)–poly(ethylene glycol)–AgNO₃–Al₂O₃ polymer electrolyte system. The preparation of polymer films was done using the solution‐casting technique and characterization of the films was carried out using scanning electron microscopy, differential scanning calorimetry and ionic transport techniques. The ionic conductivity, investigated using impedance spectroscopy, was expected to show interesting behaviour at below and above the melting temperature of poly(ethylene oxide) in the polymer blend films. Complex impedance data were analysed in an alternating current conductivity and dielectric permittivity formalism in order to throw light on the transport mechanism. The effect of nanofiller concentration on conduction and relaxation processes at various temperatures was studied. © 2013 Society of Chemical Industry     

Novel High‐Temperature Antiferroelectric‐Based Dielectric NaNbO3–NaTaO3 Solid Solutions Processed in Low Oxygen Partial Pressures

The (1?x)NaNbO₃–(x)NaTaO₃ solid solution was investigated for x ≤ 0.4 in terms of new high‐temperature and high‐permittivity dielectric system that is suitable for base metal inner electrode capacitor applications. The addition of Ta significantly enhanced the resistivity of the dielectric, resulting in superior resistivity than the dielectrics‐formulated BaTiO₃ systems that dominate the multilayer ceramic capacitor dielectric devices. The voltage dependence of the permittivity was also superior to BaTiO₃‐based materials, providing higher capacitance at higher temperatures. A transmission electron microscopy study illustrated that the grains had so‐called core‐shell structure. According to the electron diffraction analysis, the core region had an inhomogeneous structure between antiferroelectric and ferroelectric phases, and shell region had an incommensurate ferroelectric‐like structure. The core and shell region had Nb‐ and Ta‐rich composition, respectively, and their interface was compositionally sharp, implying that shell region was formed via a liquid phase during the sintering process with an incongruent Ta dissolution reprecipitation. We anticipate that these or similar materials based on the alkali‐niobate perovskites can be further enhanced to provide capacitor solutions from 150°C to 250°C, which is an important range for a number of new AC–DC invertor and engine control units.     

Characterizations of Fe Doping on B‐Site of (La0.8Ca0.2)(Cr0.9Co0.1)O3−δ Interconnect Materials for SOFCs

The microstructure, lattice parameters, and electrical conductivity mechanisms for Fe doping on B‐site of (La_0.8Ca_0.2)(Cr_0.9Co_0.1)O_3?δ were systematically investigated. The oxygen nonstoichiometry was measured by means of thermogravimetry as a function of oxygen partial pressure. In this study, the concept of defect chemistry is used to explain the relationship between the concentration of electron hole with the electrical conductivity. Based on the result of electrical conductivity in air, it is concluded that the concentration of electron hole at high oxygen activity is larger than that at low oxygen activity. This is due to the fact that (La_0.8Ca_0.2)CrO_3?δ‐based ceramics are p‐type conductors, the electrical conductivity is dominated by the concentration of hole. At higher Fe‐doping level, the compensation mechanism at high oxygen activity is significantly dominated by the formation of oxygen vacancy, that is, ionic compensation. The compensation mechanism at low oxygen activity is significantly dominated by the formation of the formation of Cr⁴⁺, that is, electrical compensation at lower Fe‐doping level. Based on oxygen nonstoichiometry data, it is found that with increasing Fe‐doping amount on B‐site of (La_0.8Ca_0.2)(Cr_0.9Co_0.1)O_3?δ specimens, the initial weight‐stable temperature shifted to lower temperature which might be highly related with the change in compensation mechanism at the temperature.     

Dielectric and pyroelectric properties of barium strontium calcium titanate ceramics

(Ba_0.6Sr_0.3Ca_0.1)TiO₃ powders were prepared by the sol-gel method using a solution of Ba, Sr and Ca acetate and Ti isopropoxide, and the specimens doped with MnCO₃ (0.1 mol%) and Y₂O₃ (0.5 mol%) were fabricated by the cold isostatic press method. The urethane pot and zirconia ball were used in the mixing and grinding process, and the green pellets were sintered at 1450 °C for 2 h in the alumina crucible. The specimen exhibited a dense and void-free grain structure with grain size of about 3 μm. The dielectric constant and the dielectric loss at Curie temperature were 16,600 and 1.2%, respectively. The specimen under a 4 kV cm⁻¹ DC bias field showed the maximum pyroelectric coefficient of 550×10⁻⁹ C cm⁻² K^-1 at Curie temperature. The figure of merit F.M.D¹ for specific detectivity (D¹) of the specimen, applied with DC 8 kV cm⁻¹ bias field, was the highest value of 17.6×10⁻⁹ C cm J⁻¹ at Curie temperature.     

Study of physical properties of cobalt substituted Pr0.7Ca0.3MnO3 ceramics

An investigation on single phase semiconducting polycrystalline Pr_0.7Ca_0.3MnO₃ and Pr_0.7Ca_0.3MnCo_0.1O₃ crystallized in the orthorhombic system with Pnma space group is reported. We found that σ_DC increases when introducing Co for T<110 K but for T>110 K, it decreases. Also, the contribution of hopping process in conduction mechanism was in agreement with the Jonscher law and Mott theory. Capacitance was extensively dependent on temperature and frequency. A dielectric transition was observed at T=150 K for the doped compound. The temperature dependence of dielectric permittivity is well described by Curie–Weiss law. The parameter of deviation from Curie–Weiss behavior to modified Curie–Weiss law is found to be ΔT_m=30 K. The substitution of Mn by Co was found to destroy the charge order state observed in the parent compound and to induce a ferromagnetic phase at low temperature. The cobalt-substituted sample exhibits a maximum value of magnetic entropy change |∆S^max|=3.2 J kg⁻¹ K⁻¹and a large relative cooling power with a maximum value of 301 J/kg under an applied field of 5 T. Technically, these large values make the prepared material very promising for magnetic refrigeration.     

Dielectric Properties of Ba0.8Ca0.2TiO3–Bi(Mg0.5,Ti0.5)O3–NaNbO3 Ceramics

Ceramics in the system 0.45Ba_0.8Ca_0.2TiO₃–(0.55?x)Bi(Mg_0.5Ti_0.5)O₃–xNaNbO₃, x = 0–0.02 were fabricated by a conventional solid‐state reaction route. X‐ray powder diffraction indicated cubic or pseudocubic symmetry for all samples. The parent 0.45Ba_0.8Ca_0.2TiO₃–0.55Bi(Mg_0.5Ti_0.5)O₃ composition is a relaxor dielectric with a near‐stable temperature coefficient of relative permittivity, ε_r = 950 ± 10% across the temperature range 80°C–600°C. Incorporation of NaNbO₃ at x = 0.2 extends the lower working temperature to ≤25°C, with ε_r = 575% ± 15% from temperatures ≤25°C to >400°C, and tan δ < 0.025 from 25°C to 400°C. Values of dc resistivity ranged from ~10⁹ Ω·m at 250°C to ~10⁶ Ω·m at 500°C. The properties suggest that this material may be of interest for high‐temperature capacitor applications.     

Dielectric and piezoelectric performance of gadolinium‐doped lead lanthanum zirconate titanate

In this article, polycrystalline samples of Gd³⁺ ion‐modified lead lanthanum zirconate titanate PLGZT: (Pb_0.94‐xGd_xLa_0.06)(Zr_0.52Ti_0.48)O₃; x = 0, 2, 4, 6, and 8% have been prepared by the sol‐gel autocombustion strategy. The structural properties of the prepared samples were analyzed by X‐ray diffraction profile (XRD), Fourier transform infrared spectra (FT‐IR), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The samples were assigned to pure PZT perovskite tetragonal structure. Ag electrodes were made on both sides of the disks for measurements of electrical and dielectric properties at different temperatures ranging from 30 to 500°C at various frequencies. The maximum dielectric constant, Curie temperature (T_C), dielectric loss at T_C, and the piezoelectric charge coefficient d₃₃ ranges of the investigated samples were found to be 1850 to 2420, 350 to 399°C, 0.023 to 0.026, and 299 to 532 pC/N, respectively. Higher coefficients were reached for the 4 % Gd substitution. Finally, the obtained results indicate that these materials can be good candidates for ultrasonic transducers.     

Effect of AgNO3–MnCl2 mixed fillers on the physical properties of polystyrene films

This study deals with the effects of various filling levels of a mixture of two transition compounds [(X)AgNO₃(10 ? X)MnCl₂] on the structural, electrical, and magnetic properties of atactic polystyrene (PS) films. X‐ray diffraction (XRD) scans showed two main peaks for unfilled PS films. Crystalline peaks were unexpectedly detected with the filling and could be correlated to the formation of clusters. The IR transmission spectra revealed characteristic PS peaks. Certain IR peaks could be taken as evidence for the formation of polaron and bipolaron bound states in the polymeric matrix. The direct‐current (DC) electrical conduction measurements suggested that the conduction mechanism could be attributed to phonon‐assisted charge carrier hopping according to the interpolaron hopping model. The DC magnetic susceptibility results at 90–235 K obeyed the Curie–Weiss law. The negative values of the paramagnetic Curie temperature (θ_p) indicated the possibility of an antiferromagnetic exchange interaction, whereas the positive values of θ_p suggested a ferromagnetic exchange interaction at low temperatures. An electron spin resonance (ESR) spectrum at X = 0% revealed a broad Lorentzian signal. This suggested the presence of aggregated Mn²⁺ and was confirmation of cluster formation found in XRD studies. On the other hand, ESR spectra at higher values of X depicted hyperfine structures characterized by the six unresolved lines of the manganese nucleus, indicating the existence of isolated Mn²⁺. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95:1333–1341, 2005     

Evolution of the Physical Properties of FeCl3 Filled Polystyrene Films

ABSTRACT

The present work investigates the effect of various filling levels (FLs) of FeCl₃ on the structure and physical properties of polystyrene (PS) films. X-ray diffraction scans revealed two main peaks, the amorphous and the polymerization peaks. The infrared transmission spectra depicted the main PS characterizing peaks. The direct current (dc) electrical conduction was attributed to the interpolaron charge carrier hopping. The temperature dependence of dc magnetic susceptibility exhibited Curie–Weiss behavior. The positive values of the paramagnetic Curie temperature (θ_p) indicate the predominance of a ferromagnetic exchange interaction between the magnetic centers at low temperatures, whereas the negative value of θ_p at 9% FL suggests the existence of an antiferromagnetic exchange interaction. The electron spin resonance (ESR) investigations imply the presence of isolated and aggregated Fe⁺³ ions at intermediate and higher FLs, respectively, in the polymeric matrix.     

Valence state and ionic conduction in Mn‐doped MgO partially stabilized zirconia

The mechanism of the enhancement in the ionic conductivity resulting from cubic phase stabilization in MgO partially stabilized zirconia (MgPSZ) by Mn doping was studied by examining the local Zr‐O structure. Cubic phase (14 vol%) in MgPSZ was increased with the addition of MnO₂, and 10 mol% Mn‐doped MgPSZ exhibited the highest cubic phase fraction (98.72%), which was analyzed by Rietveld refinement. In addition, only the cubic phase, not the monoclinic and tetragonal phases, was observed in the TEM‐SAED pattern of 10 mol% Mn‐doped MgPSZ. Doped Mn exhibited a high Mn²⁺/Mn⁴⁺ ratio, which was identified by X‐ray photoelectron spectroscopy (XPS). In addition, it indicates that oxygen vacancy formation by substitution of Mn²⁺ in the Zr⁴⁺ site in MgPSZ increased cubic phase fraction. Ionic conductivity of MgPSZ was improved by the cubic phase increase attributed to Mn doping, and 10 mol% Mn‐doped MgPSZ exhibited higher ionic conductivity than MgPSZ. To investigate the mechanism of the ionic conductivity improvement, Zr‐O local structure in Mn‐doped MgPSZ was analyzed by Zr K‐edge EXAFS of MgPSZ, and the number of bonding of the Zr‐O first shell decreased with increased Mn substitution. Therefore, it was considered that the oxygen vacancy generation led to an increase in the cubic phase and the number of ionic conduction sites.