Phase transformation behavior and dielectric characteristics of BaTi1−x(Al1/2Nb1/2)xO3 (0.01≤x≤0.40) ceramics

Microstructure, phase transformation behavior and dielectric properties of BaTi_1−x(Al_1/2Nb_1/2)_xO₃ (0.01≤x≤0.40) ceramics were investigated. A high level of (Al_1/2Nb_1/2)⁴⁺ substitution for Ti⁴⁺ ions was not conducive to the stability of the perovskite structure and resulted in the formation of BaAl₂O₄. As x was increased, lattice constants and unit cell volume decreased, reached a minimum at x=0.10 and then increased. The BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics at room temperature experienced a transformation from ferroelectric to paraelectric phase with increasing (Al_1/2Nb_1/2)⁴⁺ concentration. Meanwhile, permittivity of the BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics was markedly reduced, while Q value was slightly increased. Frequency dispersion of dielectric peak was obviously increased as x was increased from 0.01 to 0.10. It is of great interest that a dielectric abnormity represented by a broad dielectric peak at 200-400 K was observed for the composition with x=0.40.     

Percolative effects and giant dielectric tunability of BaTiO3–LuFe2O4 composites

We report on exotic dielectric properties of composite materials consisting of traditional ferroelectric BaTiO₃ and electronic ferroelectric LuFe₂O₄. The composites were synthesized by a simple ceramic processing method with properties that can be tailored by adjusting LuFe₂O₄ concentration. A percolative effect was observed at the volume fraction of ～0.26, which led to an abrupt increase in the dielectric permittivity. For composites with high LuFe₂O₄ fractions, a giant dielectric tunability was observed over a broad temperature interval, which is in strong contrast to traditional ferroelectrics.     

Effect of electric field on the dielectric permittivity of betaine phosphite crystals in the paraelectric phase

Temperature dependences of the dielectric permittivity of betaine phosphite crystals are studied both without and under application of an electric bias. It is shown that, in view of the fact that the high-temperature improper ferroelastic (antiferrodistorsive) phase transition at T _c1=355 K is nearly tricritical, the nonlinear temperature dependence of inverse dielectric permittivity in the paraelectric phase and the effect of the field on the dielectric permittivity can be described within a phenomenological model containing two coupled (polar and nonpolar) order parameters with a negative coupling coefficient. An analysis of the model revealed that, in the case where two phase transitions, a nonpolar and a ferroelectric one, can occur in the crystal, all of its dielectric properties, including the polarization response in a field, can be described by one dimensionless parameter a. For the crystal under study, we have a=?2.5. This value of the parameter corresponds to a second-order ferroelectric transition far from the tricritical point, at which a=?1. It is shown that the polarization response in the paraelectric phase in an electric field calculated within this model differs radically from that in the ferroelectric phase-transition model for which the Curie-Weiss law holds in the paraelectric phase.     

High-pressure dielectric studies of a novel hydrogen-bonded ferroelectric (NH4)2H2P2O6

The hydrostatic pressure effect on the dielectric properties of (NH₄)₂H₂P₂O₆ ferroelectric crystal was studied for pressures from 0.1 MPa to 360 MPa and for temperatures from 100 to 190 K. The pressure–temperature phase diagram obtained is linear with increasing pressure. The paraelectric–ferroelectric phase transition temperature decreases with increasing pressure with the pressure coefficient dT_c/dp=?5.16×10^?2 K MPa^?1. Additionally, the pressure dependences of Curie–Weiss constants for the crystal in paraelectric (C₊) and ferroelectric (C_?) phases are evaluated and discussed. The possible mechanism of paraelectric–ferroelectric phase transition is also discussed.     

Dielectric properties and phase transition of zinc tris(thiourea) sulfate single crystal

The dielectric properties and the ferroelectric to paraelectric phase transition of zinc tris(thiourea) sulfate (ZTS) single crystal have been investigated in a wide range of temperatures and frequencies. In the lower frequency region the real part of dielectric permittivity of the ZTS crystal shows a sudden increase at 323 K. Prominent first-order ferroelectric to paraelectric phase transition at 323 K has been observed in the plot of dielectric permittivity versus temperature at different frequencies. It has been observed that the phase transition occurs in ZTS crystal with a low degree of disorder. Surprisingly, it has been observed for ZTS that the value of the dielectric permittivity is only about 10 at high frequencies and is found to increase to 50 at low frequencies. Dielectric loss has higher values in the paraelectric region.     

Exploring the electronic structure and optical properties of new inorganic luminescent materials Ba(Si,Al)5(O,N)8 compounds for light-emitting diodes devices

Due to growing demand on discovering new materials for light-emitting diodes devices, many efforts were made to discover and characterize new inorganic materials such as phosphors. Using the full potential method within density functional theory the electronic and optical properties of BaAl₂Si₃O₄N₄ and BaAlSi₄O₃N₅ semiconductors have been investigated. The electronic structure and the optical properties of these phosphors were calculated through a reliable approach of modified Beck-Johnson (mBJ) approach. We found that BaAl₂Si₃O₄N₄ and BaAlSi₄O₃N₅ have wide direct band gaps positioned at Γ about 5.846 and 4.96 eV respectively. The optical properties, namely the dielectric function, optical reflectivity, refractive index and electron energy loss, are reported for radiation up to 15 eV. Our study suggests that BaAl₂Si₃O₄N₄ and BaAlSi₄O₃N₅ could be promising materials for applications in the LEDs devices and optoelectronics areas of research.     

The non-isotropic character of electric and dielectric properties of ammonium zinc chloride crystal

The dielectric constant, ε, and the d.c. conductivity, σ, were measured along the a-, b- and c-axes of (NH₄)₂ZnCl₄ (AZC) crystal in the 300-450 K temperature range. Crystals of AZC grown from aqueous solutions containing excess of ZnCl₂ were used. The value of the dielectric permittivity of AZC is extremely small compared to other ferroelectric crystals. Pronounced broad or step-like peaks at the phase transition temperatures were detected along the a- and b-axes, while ε along the c-axis is temperature independent up to the end of the measuring range. Reciprocal of the dielectric permittivity in the range of the commensurate to incommensurate phase transition obeys a relation similar to the Curie-Weiss law that is valid for second order ferroelectric/paraelectric phase transitions. The constants of the proposed relationship applied to the cooling run are given. The J-E characteristics along the three crystallographic axes were measured in the normal, incommensurate, commensurate and antiferroelectric phases. Hence, the type of conduction mechanism has been estimated. Parameters of Poole-Frenkel and Richardson-Schottky types of conduction mechanism have been determined. The effect of applied electric field on the conductivity measurement was also tested. Conductivity anomalies with different character were observed at the phase transition temperatures. The lnσ−1000/T dependence revealed thermal activation energy of conduction along the a-, b- and c-axes with different values in different phases of AZC.     

Enhancement of dielectric and ferroelectric properties in ferroelectric superlattices

I studied theoretically the enhancement of remanent polarization and dielectric permittivity of interfacial-coupled ferroelectric superlattices based on the Landau–Ginzburg theory. Our model adopts the Landau–Khalatnikov equation to describe hysteresis behavior and takes the time-dependent space-charge-limited conductivity into account to investigate the ferroelectric and dielectric properties of ferroelectric superlattices. The results are in good agreement with recent experimental observations on the enhancement of remanent polarization and permittivity of BaTiO₃/SrTiO₃ superlattices and heterolayered Pb(Zr,Ti)O₃ thin films.     

Crystal stability and the theory of ferroelectricity part II. Piezoelectric crystals

In Part I the dielectric properties of cubic crystals with atoms in special positions were discussed, with particular reference to crystals which become unstable against a transverse optic mode of vibration of long wavelength. These considerations are now extended to crystals of general symmetry, and it is shown that the anomalous temperature dependence of certain dielectric, piezoelectric, and elastic constants in the paraelectric phase of ferroelectric crystals can be described and correlated in a very natural way in terms of crystal stability. A formula relating the dispersion frequency of the anomalous dielectric constant to the spontaneous polarization and the displacements of the atoms in a ferroelectric transition, previously derived for barium titanate, is generalized. The transitions in KH₂PO₄ and in NH₄H₂PO₄, and the ordering of the hydrogen atoms in these crystals, are discussed qualitatively in terms of the stability of normal modes of vibration.     

New Measuring Apparatus for Complex Permittivity at Millimeter-Wave Frequencies

A dielectric rod resonator excited by a nonradiative dielectric waveguide is used for measuring complex permittivity of low loss dielectric materials. The complex permittivties of single crystal sapphire, polycrystalline Ba (Mg_1/2 W_1/2) O₃ and Mg₂ Al₄ Si₅ O₁₈ (cordierite) have been obtained at 60 and 77 GHz by the new apparatus. The first time the measurement results of complex permittivity of brain grey and white matters from 15 to 50GHz utilizing a two-port microstrip test fixture is presented. S-parameters of Test fixture are simulated employing the finite-element method. A new spectrometer for the precision measurement of dielectric permittivity and loss tangent, which is capable of providing high resolution data for the first time over an extended W-band (68-118 GHz) frequency for specimens with a large range of absorption values, including highly absorbing specimens that otherwise would not be possible.     

Phase coexistence in proton glass

Abstract

Proton glasses are crystals of composition M_1?x(NW₄)_xW₂A0₄, where M = K,Rb,Cs, W = H,D, A = P, As. For x = 0 there is a ferroelectric (FE) transition, while for x-1 there is an antiferroelectric (AFE) transition. In both cases, the transition is from a paraelectric (PE) state of tetragonal structure with dynamically disordered hydrogen bonds to an ordered state of orthorhombic structure. For an intermediate x range there is no transition, but the hydrogen rearrangements slow down, and eventually display nonergodic behavior characteristic of glasses. We and others have shown from spontaneous polarization, dielectric permittivity, nuclear magnetic resonance, and neutron diffraction experiments that for smaller x there is coexistence of ferroelectric and paraelectric phases, and for larger × there is coexistence of antiferroelectric and paraelectric phases. We present a method for analytically describing this coexistence, and the degree to which this coexistence is spatial and/or temporal. We discuss also the experimental determination of these coexistence parameters.     

Structural phase transition in ferroelectric NH4103

The structural phase transformation between the ferroelectric and paraelectric form of NH₄IO, near 83°C is dominated by tilt motions of IO₆-octahedra within a perovskite-like framework. Simultaneously, small displacements of NH₄ along the polar axis give rise to a switchable spontaneous polarization at low temperatures. As the transition mechanism is governed by the tilting of octahedra and not by the appearance of ferroelectricity, NH₄IO₃ is characterised as an improper ferroelectric material. Although the space group of the high-temperature β-phase is polar, the polarization moment is zero. Raman-active thermal soft modes appear in the ferroelectric phase. The phase transition is first order with anomalies of dielectric, piezoelectric and elastic constants.     

Influence of B2O3 on electrical properties and phase transition of lead-free Ba(Ti0.9Sn0.1)O3 ceramics

The phase transition and electrical properties of Ba(Ti_0.9Sn_0.1)O₃ ceramics with B₂O₃ added were investigated to explore the effect of B₂O₃ addition on enhanced densification and dielectric constant of these ceramics. With increasing B₂O₃ content, a linear reduction of ferroelectric to paraelectric transition temperature was observed. In addition, higher B₂O₃ concentrations enhanced a ferroelectric relaxor behavior in the ceramics. Changes in this behavior were related to densification, second-phase formation and compositional variation of the ceramics.     

Maxwell-Wagner characterization of dielectric relaxation in Ni0.8Zn0.2Fe2O4/Sr0.5Ba0.5Nb2O6 composite

Dense composites were prepared through incorporating the dispersed Ni_0.8Zn_0.2Fe₂O₄ ferromagnetic particles into Sr_0.5Ba_0.5Nb₂O₆ ferroelectric matrix. Extrinsic dielectric relaxation and associated high permittivities of the materials are reported in the composites. We used an ideal equivalent circuit to explain electrical responses in impedance formalism. A Debye-like relaxation in the permittivity formalism was also found. Interestingly, real permittivity (ε′) of the sample containing 30% Ni_0.8Zn_0.2Fe₂O₄ shows obvious independence of the temperature at 100 kHz. Dielectric relaxation and high-ε′ properties of the composites are explained in terms of the Maxwell-Wagner (MW) polarization model.     

Investigating the dielectric properties of potassium iodate polycrystals

Linear and nonlinear dielectric properties of KIO₃ polycrystalline samples are investigated. It is shown that linear dielectric permittivity ε' displays four anomalies corresponding to phase transitions in KIO₃. Anomalies of third-harmonic coefficient γ_3ω are observed at temperatures of 113, 263, and 345 K, corresponding to phase transitions between KIO₃ ferroelectric phases. It is established that the third-harmonic coefficient responsible for the nonlinearity of dielectric properties displays no anomalies during the transition to the paraelectric phase of KIO₃ at approximately 485 K. Possible reasons for there being no such anomaly are discussed.     

Domain,dielectric and optical studies in antiferroelectric (Pb,La) (Zr,Sn, Ti)O3 single crystals

Antiferroelectric (Pb, La) (Zr, Sn, Ti)O₃ (PLZST) single crystals have been successfully grown by flux method using PbO–PbF₂–B₂O₃ as the flux. The obtained crystals are pale yellow in color and translucent. Domain structures, dielectric constants and optical transmission measurements have been performed on the 〈001〉-oriented PLZST single crystals. Two types of domains, namely, 90° and 180° domains, are observed. The extinction of 90° domains at P/A: 0° reveals a tetragonal structure in the crystal. The sequence of phase transitions from antiferroelectric to ferroelectric and then paraelectric has been established with increasing temperature. According to the modified Curie–Weiss relationship, the PLZST crystal is in an intermediate state between normal and relaxor antiferroelectrics. The broad optical transparent region (from 0.4 to 7.0 μm) and high optical transmittance (up to 65%) indicate that PLZST crystals are promising for optical uses.     

Determination of the magnetoelectric coupling coefficient from temperature dependences of the dielectric permittivity for multiferroic ceramics Bi5Ti3FeO15

In the multiferroic materials, the dielectric and magnetic properties are closely correlated through the coupling interaction between the ferroelectric and magnetic order. We attempted to determine the magnetoelectric coupling coefficient from the temperature dependences of the dielectric permittivity for multiferroic Bi₅Ti₃FeO₁₅. Multiferroic ceramics Bi₅Ti₃FeO₁₅ belong to materials of the Aurivillius-type structure. Multiferroic ceramics Bi₅Ti₃FeO₁₅ was synthesized via sintering the Bi₂O₃ and Fe₂O₃ mixture and TiO₂ oxides. The precursor material was ground in a high-energy attritorial mill for 5 hours. This material was obtained by a solid-state reaction process at T = 1313 K. We investigated the temperature dependences of the dielectric permittivity for the different frequencies. From the dielectric measurements, we determined the temperature of phase transition of the ferroelectric-to-paraelectric type at about 1013 K. Based on dielectric measurements and theoretical considerations, the values of the magnetoelectric coupling coefficient were specified.     

Ferroelectricity and ferromagnetism in fine-grained multiferroic BaTiO3/(Ni0.5Zn0.5)Fe2O4 composites prepared by a novel hybrid process

Dense, homogeneous, and fine-grained multiferroic BaTiO₃/(Ni_0.5Zn_0.5)Fe₂O₄ composite ceramics are synthesized by a novel powder-in-sol precursor hybrid processing route. This route includes the dispersion of nanosized BaTiO₃ ferroelectric powders prepared via conventional sold-state ceramic process into (Ni_0.5Zn_0.5)Fe₂O₄ ferromagnetic sol-gel precursor prepared via a sol-gel wet chemistry process. The composite ceramics show coexistence of obvious ferroelectric and ferromagnetic hysteresis loops at room temperature. Very low dielectric loss of about 0.02–0.0067 in the range of 10 kHz–10 MHz can be achieved, which is about an order of magnitude lower than the results of many reports using conventional processes at room temperature. The combination of high permeability and permittivity with low losses in the ceramics enables significant miniaturization of electronic devices based on the ceramics.     

Ferrielectric dielectric behaviour and the nature of phase transition of ammonium sulphate

Phenomenological treatments of ferrielectrics are made in terms of two non-equivalent sublattice polarizations in the paraelectric phase. Unlike the Curie-Weiss behaviour of usual proper ferro- and antiferro-electrics, the dielectric susceptibility does not depend linearly on temperature. Particularly in the case of a first order phase transition, the Curie-Weiss constant seems to be unusually small. As an example, the dielectric properties of (NH₄)₂SO₄, which was known to be a peculiar ferroelectric, is discussed from the ferrielectric point of view. The true Curie-Weiss constant is of a comparable order of magnitude to that of the order-disorder ferroelectric.     

Investigation of the ferroelectric–relaxor crossover in Ce-doped BaTiO3 ceramics by impedance spectroscopy and Raman study

BaCe _x Ti_{1? x} O₃ (x?=?0.06, 0.10, and 0.20) solid solutions were prepared via conventional the solid-state reaction and sintered at 1500°C for 4?h, resulting in dense single phase ceramics with homogeneous microstructures. The electric field dependence of permittivity of the BaCe _x Ti_{1? x} O₃ ceramics was investigated in detail, together with the ferroelectric–paraelectric phase transition features. A transformation from normal to relaxor ferroelectrics was observed by increasing the Ce concentration. For low-Ce content, a substitution of Ce on both A and B site positions was proposed from the dielectric study and confirmed by Raman analysis.