Synchrotron and neutron powder diffraction study of phase transition in weberite-type Nd3NbO7 and La3NbO7

La₃NbO₇ and Nd₃NbO₇ are insulating compounds that have an orthorhombic weberite-type crystal structure and undergo a phase transition at about 360 and 450 K, respectively. The nature of the phase transitions was investigated via heat capacity measurements, synchrotron X-ray and neutron diffraction experiments. It is here shown that above the phase transition temperature, the compounds possess a weberite-type structure described by space group Cmcm (No. 63). Below the phase transition, the high temperature phase transforms into a weberite-type structure with space group Pmcn (No. 62). The phase transformation primarily involves the off-center shifting of Nb⁵⁺ ions inside the NbO₆ octahedra, combined with shifts of one third of the Ln³⁺ (Ln³⁺=La³⁺ and Nd³⁺) ions at the center of the LnO₈ polyhedra towards off-center positions. The phase transition was also proven to have great impacts on the dielectric properties.     

Etude calorimetrique et dilatometrique sous pression des transitions de phase de Pb(Zr0,965Ti0,035)O3 dope

The pressure—temperature phase diagram of the solid solution is drawn by calorimetric measurements. With temperature increasing the observed phase transitions are, according to the pressure: antiferroelectric, ferroelectric, paraelectric, or antiferroelectric, antiferroelectric, paraelectric. The heats of transition are measured and compared with those calculated using the Clausius—Clapeyron relationships for first-order transitions; the deviations observed at some phase transitions are discussed.     

A Raman study of multiferroic LuMnO3

Magnetic and dielectric measurements confirm the multiferroic nature of LuMnO₃. Raman spectra of LuMnO₃ have been recorded in the 77–800 K range covering both the antiferromagnetic transition at 90 K and the ferroelectric–paraelectric transition at 750 K. The changes in the phonon modes frequencies and band-widths indicate the presence of phonon–spin coupling in the antiferromagnetically ordered phase. The ferroelectric–paraelectric transition is accompanied by the broadening and disappearance of many of the phonon modes. Some of the phonon modes also show anomalies at the ferroelectric transition.     

The effect of disorder in Ba2YTaO6 on the tetragonal to cubic phase transition

Synchrotron X-ray diffraction and Raman spectroscopy have been used to study the structure of the complex perovskite Ba₂YTaO₆, at temperatures down to 100 K. Where the Ta and Y cations exhibit long-range rock-salt like ordering, Ba₂YTaO₆ displays a continuous phase transition from a high temperature cubic structure, described in space group Fm3?m, to a tetragonal, I4/m, structure near 260 K. This transition is inhibited if extensive disorder and/or vacancies are/is present in the sample.     

Structural evolution of Na0.5K0.5NbO3 at high temperatures

Changes in structure and dielectric properties at elevated temperatures have been investigated on single-crystals of sodium potassium niobate, Na_0.5K_0.5NbO₃, grown by the flux method. Single-crystal X-ray diffraction studies revealed that the crystals underwent orthorhombic-tetragonal and tetragonal-cubic phase transitions at 465 and 671 K during heating and 446 and 666 K during cooling, respectively. Both transitions were accompanied by volumetric discontinuities of collapse upon heating and expansion upon cooling, suggesting that the transitions were of the first order. The coordination numbers of an Nb showed a decreasing tendency with decreasing temperature, i.e., 6 in cubic, 5+1 in tetragonal and 4+2 in orthorhombic. An Na atom occupied a slightly different position from the K atom in 12-fold coordination, resulting in fewer coordination numbers of 8+4 in cubic and tetragonal and 7+5 in orthorhombic. The spontaneous polarisation (P_s) estimated from the atom positions and formal charges were approximately 0.29 C m⁻² in orthorhombic and 0.18 C m⁻² in tetragonal. The contribution of the alkaline oxide components to P_s was estimated to be approximately 15% in both ferroelectric forms. The temperature-induced transitions were also confirmed through the dielectric constant and dielectric loss at various frequencies and the differential scanning calorimetry.     

Eu doping effects on structural and magnetic properties of (Sr2−xEux)FeMoO6 compounds

Double perovskite compounds (Sr_2−xEu_x)FeMoO₆ (0≤x≤0.3) were prepared by solid-state reaction at high temperature. Crystal structure, magnetic and transport properties of the compounds were investigated. The crystal structure of the compounds changes from an I4/m lattice to an Fm3¯m lattice around x=0.1. The unit-cell volume decreases with the doping level in both the I4/m lattice and the Fm3¯m lattice. The resistivity of the compounds shows a metal-semiconductor transition, and the transition temperature T_M-S increases with the doping level. However, Curie temperature (T_C) of the compounds exhibits a weak dependence on the doping level. The saturation magnetization (M_S) at 100 K varies almost linearly with the anti-site defect concentration and agrees well with the simple FIM model. In contrast to the Ce-, Pr-, Nd- and Sm-doped Sr₂FeMoO₆, the difference of M_S of (Sr_2−xEu_x)FeMoO₆ between 5 and 100 K indicates that the moment of Eu³⁺ is antiparellel to that of Fe³⁺ at low temperature.     

Electron microscopic studies of the antiferroelectric phase in Sr0.60Ca0.40TiO3 ceramic

The structural variants and their coexistence across the antiferroelectric phase transition in Sr_0.60Ca_0.40TiO₃ ceramic has been studied through transmission electron microscopy (TEM) at room temperature and ∼100 °C. A clear evidence of the presence of superlattice reflections, corresponding to the cell doubling along the c-axis of Pbnm (or b-axis along Pnma), occurring during paraelectric to antiferroelectric transition, has been obtained through selected area electron diffraction, convergent beam electron diffraction and lattice-resolution imaging. Coexistence of the Pbnm and Pbcm phases at room temperature has been observed and attributed to the strain/disorder-induced broadening of the first-order antiferroelectric phase transition. Drastic changes in the domain structure during Pbnm to Pbcm transformation have been observed. This clearly indicates that the antiferrodistortive transition responsible for the occurrence of the antiferroelectric phase is of completely different origin and it is not just an additional follow-up of the already-existing ordering due to a⁻a⁻c⁺ tilt schemes in the Pbnm domain. Thermal cycling studies on microstructural changes indicate some kind of memory mechanism, which retains the memory of the original a⁻a⁻c⁺ tilt schemes in the Pbnm phase. This has been attributed to the symmetry conforming short-range order (SC-SRO) of the point defects.     

Phase Diagram and Phase Transitions in the Relaxor Ferroelectric Pb(Fe2/3W1/3)O3-PbTiO3 System

A complete solid solution between relaxor ferroelectric Pb(Fe_2/3W_1/3)O₃ (PFW) and ferroelectric PbTiO₃ (PT), (1−x)PFW-xPT, was synthesized by a B-site precursor method and characterized by X-ray diffraction, differential scanning calorimetry, and dielectric measurements. A phase diagram between PFW and PT has been established. The diffuse phase transition temperature (T_max≈180 K) of PFW was found to continuously increase with the increasing amount of Ti⁴⁺ ions on the B-site. At the same time, the relaxor ferroelectric behavior of PFW is gradually transformed toward a normal ferroelectric state, as evidenced by sharp and nondispersive peaks of dielectric permittivity around T_C for x≥0.25. At room temperature, a transition from a cubic to a tetragonal phase takes place with x increased up to 0.25. A morphotropic phase boundary is located within the composition interval 0.25≤x≤0.35, which separates a pseudocubic (rhombohedral) phase from a tetragonal phase.     

Crystal structures and phase transitions of Sr2CrSbO6

Sr₂CrSbO₆ was synthesized by the conventional solid-state reaction process. X-ray powder diffraction (XRPD) and neutron powder diffraction (NPD) has been used to reinvestigate the structure at room temperature and to study the phase transitions at high- and low-temperature. Rietveld analysis revealed that Sr₂CrSbO₆ crystallizes at room temperature in a monoclinic system having a space group I2/m, with a=5.5574(1) Å; b=5.5782(1) Å; c=7.8506(2) Å and β=90.06(2), no P2₁/n space group as was previously reported. The high-temperature study (300-870 K) has shown that the compound presents the following temperature induced phase-transition sequence: I2/m-I4/m-Fm-3m. The low-temperature study (100-300 K) demonstrated that the room-temperature I2/m monoclinic symmetry seems to be stable down to 100 K.     

The vibrational spectra and crystallographic properties of CsPF6

Indications are that CsPF₆(I) at ambient conditions is cubic with a possible space group of Fm3m-O⁵_h. A slight distortion of the unit cell cannot, however, be ruled out. Assuming Fm3m symmetry the Raman spectra of CsPF₆(I) are consistent with a disordered model in which the PF^?₆ ions are tilted away from the crystallographic axes. The phase transition which occurs below 90 K in CsPF₆ is reflected in the vibrational spectra and further significant changes occur below 60 K particularly in the Raman bands. It is not yet clear whether these changes represent the establishment of long-range order or whether a further phase of CsPF₆ exists below 60 K. A possible structure for CsPF₆ at very low temperatures is discussed.     

Metamagnetism in DyBaCo2O5+x, x≈0.5

The temperature dependence of the paramagnetic susceptibility χ_m(T) taken in 2500 Oe, the resistivity ρ(T), and the thermoelectric power α(T) of DyBaCo₂O_5+x, which has Ba and Dy ordered into alternate (001) planes of an oxygen-deficient perovskite, have revealed a phase segregation in the compositional range 0.3?x<0.5. Orthorhombic DyBaCo₂O_5.51 has, in addition, oxygen vacancies ordered into alternate rows of the DyO_0.51 (001) planes; a cold-pressed polycrystalline sample exhibits a first-order insulator-metal transition at T_IM=320 K, a Curie temperature T_C=300 K, and a broadened metamagnetic transition temperature T_M≈265 K in 2500 Oe. A ferromagnetic M-H hysteresis curve fails to saturate at 5 T, and a minority ferromagnetic phase below T_M has a volume fraction that decreases with decreasing temperature, vanishing below 50 K. Oxygen vacancies in the DyBaCo₂O_5.5 phase suppress the metallic state; interstitial oxygen does not. A thermoelectric power α(T)>0 of DyBaCo₂O_5.51 changing continuously across T_IM is interpreted to manifest a metallic minority phase crossing a percolation threshold; α(T) also provides evidence for a progressive excitation of higher-spin Co(III) with increasing temperature from below 50 K to above T_IM. A previous model of the RBaCo₂O_5.5 phase is extended to account for the Ising spin configuration below T_C, the magnetic order in the presence of higher-spin octahedral-site Co(III), and the α(T) data.     

The p–T phase diagram for ferroelectric bis-thiourea pyridinium nitrate

The effect of temperature and pressure on physical properties of the ferroelectric bis-thiourea pyridinium nitrate inclusion compound has been studied by dielectric spectroscopy and nuclear magnetic resonance (NMR). At ambient pressure the ferroparaelectric phase transition observed at T₂ = 216 K is continuous in contrast to the nonferroelectric phase transition observed at T₁ = 273 K. Under small pressures, the temperatures of the phase transitions T₁ and T₂ increase with increasing pressure. Starting from about 250 MPa, T₁ temperature decreases with increasing pressure, while T₂ temperature increases with increasing pressure. At 450 MPa and 245 K a triple point is observed. Bis-thiourea pyridinium nitrate undergoes a continuous phase transition from the ferroelectric to paraelectric phase under 450 MPa, while above this pressure the phase transition from the ferroelectric to paraelectric phase is discontinuous. The change in the phase transition character is related to the crystallographic change in the group–subgroup relation between the ferro- and paraelectric phases taking place with increasing pressure.     

Phase transition of pyridinium tetrachloroiodate(III), PyHICl4, studied by a single crystal X-ray analysis and dielectric and heat capacity measurements

Change of a local environment of a polar pyridinium ion, which is associated with the phase transition of crystalline pyridinium tetrachloroiodate(III) at T_c = 217 K, was investigated by a single crystal X-ray analysis and dielectric and heat capacity measurements. The site symmetry 2/m of the ion at T > T_c indicates an orientational disorder in the high-temperature phase (HTP). The energy difference ΔE between the stable and meta-stable orientations of the pyridinium ion at the 2/m site was estimated to be ΔE/R ? 560 K at 280 K in the HTP. Below the T_c, an antiferroelectric ordering of the ions was revealed.     

Raman spectroscopic study of K3H(SO4)2 (phases I and II) single crystals

A Raman study of K₃H(SO₄)₂ as a function of temperature reveals that this compound undergoes a phase transition at T_c = 483 K prior to the decomposition at 508 K.     

Structural, magnetic and electronic properties of LaNi0.5Fe0.5O3 in the temperature range 5-1000 K

The structure, magnetism, transport and thermal expansion of the perovskite oxide LaNi_0.5Fe_0.5O₃ were studied over a wide range of temperatures. Neutron time-of-flight data have shown that this compound undergoes a first-order phase transition between ∼275 and ∼310 K. The structure transforms from orthorhombic (Pbnm) at low temperatures to rhombohedral (R3¯c) above room temperature. This phase transition is the cause for the previously observed co-existence of phases at room temperature. The main structural modification associated with the phase transition is the change of tilting pattern of the octahedra from a⁺b⁻b⁻ at low temperatures to a⁻a⁻a⁻ at higher. Magnetic data strongly suggests that a spin-glass magnetic state exists in the sample below 83 K consistent with the absence of magnetic ordering peaks in the neutron data collected at 30 K. At high temperatures the sample behaves as a small polaron electronic conductor with two regions of slightly different activation energies of 0.07 and 0.05 eV above and below 553 K, respectively. The dilatometric data show an average thermal expansion coefficient of 14.7×10⁻⁶ K⁻¹ which makes this material compatible with frequently used electrolytes in solid oxide fuel cells.     

Effect of magnetostrictive phase on structural, dielectric and electrical properties of NiFe2O4 + Pb0.93La0.07(Zr0.60Ti0.40)O3 composites

Particulate composites of NiFe₂O₄ (NFO) and Pb_0.93La_0.07 (Zr_0.60Ti_0.40) O₃ (PLZT) were synthesized by solid-state reaction technique. Structure and surface morphological studies were carried out using X-ray diffraction and scanning electron microscopy techniques, respectively. Frequency dependent variation of dielectric constant (), loss tangent (tan δ) and ac resistivity for (x) NFO + (1−x) PLZT composites in the range 100 Hz–5 MHz at room temperature were studied. The temperature dependence of dielectric constant (′), loss tangent (tan δ) was studied in wide temperature range of measurement at fixed frequencies. Also DC resistivity measurements were carried out in the temperature range of 300 K–923 K. Structural, dielectric and electrical properties show notable change due to presence of magnetostrictive NFO phase along with PLZT.     

Temperature behavior of the protonic conductor K4LiH3(SO4)4

The results of the X-ray structural study for the K₄LiH₃(SO₄)₄ single crystal are presented at a wide temperature range. The thermal expansion of the crystal using the X-ray dilatometry and the capacitance dilatometry from 8 to 500 K was carried out. The crystal structures data collection, solution and refinement at 125, 295, 443 and 480 K were performed. The K₄LiH₃(SO₄)₄ crystal has tetragonal symmetry with the P4₁ space group (Z=4) at room temperature as well as at the considered temperature range. The existence of a low-temperature, para-ferroelastic phase transition at about 120 K is excluded. The layered structure of the crystal reflects a cleavage plane parallel to (001) and an anisotropy of the protonic conductivity. The superionic high-temperature phase transition at T_S=425 K is isostructural. Nevertheless, taking into account an increase of the SO₄ tetrahedra libration above T_S, a mechanism of the Grotthus type could be applied for the proton transport explanation.     

Structural studies of the phases in Ba2LaIrO6—New light on an old problem

Accurate and precise structures for the cation-ordered double perovskite Ba₂LaIrO₆ at a number of temperatures are presented. Careful analysis of the synchrotron X-ray and neutron diffraction profiles of Ba₂LaIrO₆ suggests that, at room temperature, this is monoclinic in space group I2/m. Heating the sample to 375 K results in a transition to a rhombohedral phase in R3¯ with further heating resulting in the loss of the tilting of the octahedra, the structure being in Fm3¯m. Cooling the sample induces an additional phase transition to a triclinic structure in I1¯. Details of the various structures are presented.     

Dielectric characteristics of a Ce3+-doped Sr0.61Ba0.39Nb2O6 single crystal with Cole–Cole plots technique

In this paper, we have investigated relaxation mechanisms and dielectric characteristics of an Sr_0.61−xBa_0.39Nb₂O₆Ce_x (abbreviated as SBN61 and x=0.0066) single crystal with dielectric spectroscopy measurements. The crystal undergoes a ferroelectric phase transition at 340 K. The temperature dependence of the real and imaginary part of the complex dielectric susceptibility in the vicinity of ferroelectric–paraelectric phase transition has been studied in the frequency region 100 Hz–10 mHz. The measurement of the dielectric constants of the real and imaginary parts shows strong frequency dependence. The investigations of the dielectric constant using Cole–Cole plots revealed a non-Debye-type dielectric relaxation for Ce⁺³-doped SBN61. It reveals the coexistence of the two dielectric relaxators in the vicinity of the phase transition.     

Structure and antiferroelectric properties of cesium niobate, Cs2Nb4O11

The compound cesium niobate, Cs₂Nb₄O₁₁, is an antiferroelectric, as demonstrated by double hysteresis loops in the electric field versus polarization plot. The crystal structure refinement by X-ray diffraction at both 100 and 297 K shows it to have a centrosymmetric structure in point group mmm and orthorhombic space group Pnna, which is consistent with its antiferroelectric behavior. The 100-K structure data is reported herein. The lattice is comprised of niobium-centered tetrahedra and octahedra connected through shared vertices and edges; cesium atoms occupy channels afforded by the three-dimensional polyhedral network. Antiferroelectricity is produced by antiparallel displacements of niobium atoms along the c-axis at the phase transition temperature of 165 °C. The critical field for onset of ferroelectric behavior in a single-crystal sample is 9.5 kV/cm at room temperature.