Mechanism of phase transitions in the (NH4)2WO2F4 ferroelastic

Precision studies of the thermophysical properties and structure of an (NH₄)₂WO₂F₄ crystal have been performed. It was established reliably that there is a sequence of two phase transitions at T ₁ = 201 K and T ₂ = 160 K characterized by wedging out of an intermediate phase with an increase in pressure. The role of tetrahedral and octahedral ionic groups in the mechanism of the structural transitions was determined.     

Calorimetric and dielectric studies of the (NH4)2MoO2F4 oxyfluoride

The temperature dependences of the heat capacity, dielectric properties, and response to an external pressure and an electric field for the (NH₄)₂MoO₂F₄ oxyfluoride (space group Cmcm, Z = 4) have been studied. A comparative analysis of the data on the entropy of phase transitions, p-T phase diagrams, permittivity, and anomalous heat capacity in combination with the results of previous studies of the related compounds (NH₄)₂WO₂F₄ and (ND₄)₂WO₂F₄ has made it possible to establish that both [MO₂F₄]²⁻ anions and ammonium groups play a substantial role in the mechanism and nature of the structural transformations.     

The phase diagram of (NH4I)x(KI)1−x

The χ,T phase diagram of (NH₄I)_x(KI)_1?x has been determined using neutron diffraction experiments and dielectric spectroscopy. At low temperatures and with decreasing χ, the sequence γ, β, ε and glass phase has been detected. The critical concentration χ_c≈0.55 separates the glassy phase with frozen-in orientational disorder from the ε phase which reveals long-range orientational order. Close to χ_c our experiments reveal evidence for two subsequent glass transitions.     

Structural aspects of the dielectric anomaly in SC(NH2)2 crystals at 161 K

The residual incommensurate modulations in the ferroelectric phase of the SC(NH₂)₂ thiourea are investigated using single-crystal x-ray diffractometry. It is found that the structural states of the ferroelectric phase (T<169 K) depend on the thermal prehistory of the crystal in the temperature range of existence of the incommensurate phase (202-169 K). The dielectric anomaly observed at T _x=161 K is justified structurally.     

Ferroelastic phase transitions in (NH4)2TaF7

The heat capacity, unit cell parameters, permittivity, optical properties, and thermal expansion of the (NH₄)₂TaF₇ compound with a seven-coordinated anion polyhedron have been measured. It has been found that the compound undergoes two successive phase transitions with the symmetry change: tetragonal → (T ₁ = 174 K) orthorhombic → (T ₂ = 156 K) tetragonal. The ferroelastic nature of structural transformations has been established, and their entropy and susceptibility to hydrostatic pressure have been determined.     

Phase transitions in orthorhombic oxyfluoride (NH4)2MoO2F4

(NH₄)₂MoO₂F₄ single crystals were grown and studied using polarization-optical methods, and the birefringence was measured in the temperature range 90–350 K. The following sequence of phase transitions is revealed: G ₀ ? G ₁ ? G ₂. It is established that the phase transition at T ₀₁ ≈ 267 K is of the first order and exhibits thermal hysteresis δT ₀₁ ≈ 0.6 K. A weak anomaly is found in Δn(T) at T ₀₂ ≈ 180 K. The crystals are shown to retain the orthorhombic symmetry during the phase transitions.     

Investigation of thermal expansion,phase diagrams,and barocaloric effect in the (NH4)2WO2F4 and (NH4)2MoO2F4 oxyfluorides

The thermal expansion along the principal crystallographic axes of the (NH₄)₂WO₂F₄ and (NH₄)₂MoO₂F₄ oxyfluorides has been studied. The anomalous behavior of α _i (T) due to the phase transitions has been revealed at T ₁ = 271.4 K and T ₂ ≈ 180 K for the molybdate and at T ₁ = 201.5 K and T ₂ ≈ 161 K for the tungstate. The quantities dT/dp and dT/dσ _i , which characterize the dependence of the phase transition temperatures on the hydrostatic and uniaxial pressures, have been determined from analyzing the results of studies of the thermal expansion and heat capacity with the use of the Pippard relations. The p-T and α _i -T phase diagrams reflect different characters of the influence of the pressure on the stability of the initial and distorted phases of the oxyfluorides. The magnitudes of the extensive and intensive barocaloric effects determined in the vicinity of the structural phase transitions are as follows: ΔS _BCE varies from approximately −10 to −17 J/mol K and ΔT _AD ≈ 8−17 K for the molybdate and ΔS _BCE varies from approximately −10 to −17 J/mol K and ΔT _AD ≈ 8−13 K for the tungstate.     

Phase diagram of the relaxor (1−x)Pb(Zn1/3Nb2/3)O3-xPbTiO3 investigated by dielectric and Raman spectroscopies

Lead zinc niobate-lead titanate[(1−x)Pb(Zn_1/3Nb_2/3)O₃-xPbTiO₃] (PZN-PT) crystals with x=4.5% and x=12% have been investigated using dielectric and Raman measurements over a range of temperatures. Above room temperature, dielectric measurements show that both compositions exhibit structural phase transitions according to the phase diagram proposed by Kuwata et al. [Ferroelectrics 387 (1981) 579]. Below room temperature, an anomaly at around 180 K for the x=12% sample is observed, suggesting another phase transition. Raman measurements are used to study all phase transitions.     

The phase diagram of (NH4I)x(KI)1−x

The χ,T phase diagram of (NH₄I)_x(KI)_1−x has been determined using neutron diffraction experiments and dielectric spectroscopy. At low temperatures and with decreasing χ, the sequence γ, β, ε and glass phase has been detected. The critical concentration χ_c≈0.55 separates the glassy phase with frozen-in orientational disorder from the ε phase which reveals long-range orientational order. Close to χ_c our experiments reveal evidence for two subsequent glass transitions.     

A study of the phase diagrams of (NH4)3Ga1−x ScxF6 ammonium cryolites

This paper reports on the results of analyzing p-T and x-T phase diagrams and calorimetric properties of solid solutions in (NH₄)₃Ga_1?x Sc_xF₆ cryolites with scandium concentrations x=0.0, 0.1, 0.35, 0.4, 0.6, 0.8, and 1.0. The thermodynamic parameters of the phase transitions observed in the studied compounds are determined. The generalized phase diagram and successive structural transformations in a series of (NH₄)₃ Me ³⁺F₆ ammonium cryolites are discussed.     

Phase transitions in oxyfluoride (NH4)2WO2F4

(NH₄)₂WO₂F₄ single crystals are grown, and their polarization-optical, calorimetric, and birefringence properties are studied in the temperature range 90–350 K. A first-order structural phase transition is found to occur at T ₀₁↑ = 202 K with thermal hysteresis of ΔT ₀₁ ≈ 6–12 K. The phase transition is accompanied by twinning and modification of the symmetry . An additional weak anomaly in the differential scanning calorimeter signal is found at T ₀₂ ≈ 170 K. The total thermal effect of both anomalies is ∑ΔH _i = 3200 ± 400 J/mol and ∑ΔS _i = 16.5 ± 2.0 J/mol K. The phase transition at T ₀₁ is of the order-disorder type.     

Nonlinear dielectric response in the mixed K0.91(NH4)0.09H2PO4 crystal

The influence of bias and variable electric fields on the dielectric response of the K_0.91(NH₄)_0.09H₂PO₄ single crystal has been studied in the vicinity of the ferroelectric phase transition temperature T _C. Below T _C, the nonlinear response is caused mainly by the domain mechanism. This is confirmed, in particular, by observations of chaotic oscillations in a series RLC-circuit containing the studied sample as a capacitor C and excited by a sinusoidal voltage. Peculiarities of the behavior of the dielectric nonlinearity are found near the Curie temperature, which are explained by the emergence of an intermediate heterophase state.     

Mössbauer study of (NH4)2FeCl5·H2O

Mössbauer spectra of the compound (NH₄)₂FeCl₅·H₂O have been studied as a function of temperature. Two phase transitions are observed in the temperature range between 7 K and 9 K. The transition at 9 K is structural and presents an unusually high thermal hysteresis. AroundT=8 K the substance orders magnetically and different Fe³⁺ contributions are present.     

Heat capacity, structural disorder, and the phase transition in cryolite (NH4)3Ti(O2)F5

The heat capacity, T-p phase diagrams, and unit cell parameters of cryolite (NH₄)₃Ti(O₂)F₅ were studied over a wide temperature range. A phase transition was found near 226 K, and its thermodynamic characteristics and their dependence on the crystallization conditions were determined. The coordinates and thermal parameters of atoms in the Fm3m phase were refined. An analysis of the electron density distribution and the transition entropy showed that the mechanism of the structural transition involves, above all, rotation of the Ti(O₂)F₅ octahedra. Possible models of disordering of tetrahedral ammonium groups are considered.     

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.     

La substitution in four-layers Aurivillius phase SrBi4Ti4O15

Ceramics with the nominal composition of SrBi_4−xLa_xTi₄O₁₅ have been prepared within the range of 0≤x≤1.8, and the dielectric properties are investigated. Single phase SrBi_4−xLa_xTi₄O₁₅ solid solution exists until the secondary phase of La_2/3TiO₃ appears at x=1.6. The Curie temperature is 520 °C for pure SrBi₄Ti₄O₁₅, and it shifts to low temperature with increasing x, which is due to the smaller structural distortion caused by La³⁺ substitution. In addition, the dielectric constant anomaly is suppressed with the substitution. No dielectric relaxation behavior is observed. When x≥1.2, the paraelectric state is attained in the present ceramics. La³⁺ substitution effects on the SrBi₄Ti₄O₁₅ ceramics are also compared with the previous work on Bi_4−xLa_xTi₃O₁₂.     

Synthesis,structural and electrical properties of Ti modified Bi2Sn2O7 pyrochlore

Polycrystalline ceramic samples of Bi₂Sn_2−xTi_xO₇ (x=0.00, 0.2, 0.4, 0.6 and 0.8) have been synthesized by standard high temperature solid state reaction method. The effect of homovalent cation (titanium) substitution on the Sn-site on the structural and electrical properties of the pure Bi₂Sn₂O₇ ceramic have been studied by X-ray diffraction followed by SEM, dielectric and dc conductivity studies. The structural analysis indicates that the increase of titanium contents do not lead to any secondary phase. The frequency and temperature dependent dielectric studies have been carried out. It is found that the Ti doping reduces the material particle size. The size of the particles are strongly influenced by the addition of titanium to the system. The substitution of Ti for Sn ions affected the degree of disorder and modified the dielectric properties leading to more resistive ceramic compounds. The activation energies of all the compounds were calculated using the relation σ=σ₀exp(−Ea/kT).     

On the low temperature phase transition in (NH4)2SO4

An ultracryostat and multidecameter were used to determine the temperature dependence of the dielectric constant ?′ and dielectric loss ?″ over a wide range of frequencies of single crystals and polycrystalline samples of (NH₄)₂SO₄ in the region of the low temperature phase transition. A sharp increase was observed in the values of ?′ and ?″ at about ?50°C. In addition, a dielectric dispersion was detected and found to be more pronounced in the high temperature phase. This dispersion was attributed to piezoelectric resonance. The observed sudden increase in the values of the dielectric constant and dielectric loss below ? 50°C was attributed to the ferroelectric nature of the low temperature phase of (NH₄)₂SO₄.A DTA thermogram showed a sharp peak at ? 50°C which indicated that the phase transition is one of first order type. A TMA thermogram showed that this transformation was associated with a rapid increase in the expansion coefficient. Such an increase in the lattice parameter might be attributed to the enhanced rotation of electric dipoles associated with the distorted NH₄⁺ and SO₄^2? ions. The distortion of both the ammonium and sulfate ions in addition to their expected orientational motion are suggested to be responsible for the ferroelectric behaviour of ammonium sulfate below ?50°C.A transition to a metastable hexagonal state at about ?40°C is thought to occur, and this transformation is found to be irreversible.     

Mössbauer study on a two-dimensional random mixture with competing spin anisotropies K2Ni1−x Fe x F4

Mössbauer measurements have been made on a two-dimensional (2D) random mixture K₂Ni_1?x Fe _x F₄ with competing spin anisotropies. The concentration versus temperature phase diagram predicted by Oguchi and Ishikawa for mixed systems with competition between orthorhombic anisotropies has been shown to exist in K₂Ni_1?x Fe _x F₄. The coexistence of two kinds of Mössbauer spectra is seen in the transition regions, and is believed to be an intrinsic property of this system.     

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.