Structural studies of the P-T phase diagram of sodium niobate

The crystal structure of sodium niobate (NaNbO₃) has been investigated by energy-dispersive X-ray diffraction at high pressures (up to 4.3 GPa) in the temperature range 300–1050 K. At normal conditions, NaNbO₃ has an orthorhombic structure with Pbcm symmetry (antiferroelectric P phase). Upon heating, sodium niobate undergoes a series of consecutive transitions between structural modulated phases P-R-S-T(1)-T(2)-U; these transitions manifest themselves as anomalies in the temperature dependences of the positions and widths of diffraction peaks. Application of high pressure leads to a decrease in the temperatures of the structural transitions to the R, S, T(1), T(2), and U phases with different baric coefficients. A phase diagram for sodium niobate has been build in the pressure range 0–4.3 GPa and the temperature range 300–1050 K. The dependences of the unit-cell parameters and volume on pressure and temperature have been obtained. The bulk modulus and the volume coefficients of thermal expansion have been calculated for different structural modulated phases of sodium niobate. A phase transition (presumably, from the antiferroelectric orthorhombic P phase to the ferroelectric rhombohedral N phase) has been observed at high pressure (P = 1.6 GPa) and room temperature.     

Low-temperature phase transformations of PbZr(1-x)Ti(x)O(3) in the morphotropic phase-boundary region

We present anelastic and dielectric spectroscopy measurements of PbZr(1-x)Ti(x)O(3) with 0.455 < or = x < or = 0.53, which provide new information on the low-temperature phase transitions. The tetragonal-to-monoclinic transformation is first order for x < 0.48 and causes a softening of the polycrystal Young's modulus whose amplitude may exceed the one at the cubic-to-tetragonal transformation; this is explainable in terms of linear coupling between shear strain components and tilting angle of polarization in the monoclinic phase. The transition involving rotations of the octahedra below 200 K is visible both in the dielectric and anelastic losses, and it extends within the tetragonal phase, as predicted by recent first-principle calculations.     

改性锆钛酸铅温度诱导相变的热释电性

测量结果显示,Pb_0.99Nb_0.02［(Zr_1-xSn_x)_1-yTi_y］_0.98O₃在温度诱导相变时伴随有正的和负的热释电电流峰.电流的方向与相变类型有如下关系：铁电相向反铁电或顺电相转变时形成正的电流峰,反铁电相向铁电或顺电相转变时形成负的电流峰.按照铁电相与反铁电和顺电相之间存在静电势差的观点,可以很好地解释热释电电流的方向与 关键词： 改性锆钛酸铅化合物 温度诱导相变 热释电性     

Dielectric properties of LC mixture with induced antiferroelectric phase

Mixture of two liquid crystalline components exhibits the antiferroelectric phase in a broad temperature range at room temperatures, though the two components separately do not show an antiferroelectric phase in a temperature range applied. The dielectric spectroscopy technique combined with measurements of the selective light reflection was used for identification and characterization of the phases and subphases existing in the mixture. In the SmC*_A phase, the low frequency mode characteristic of antiferroelectric phase has been detected. In the broad temperature range between SmC*_A and SmA* phases, no relaxation mode has been detected. The soft mode registered near the phase transition to SmA* phase follows the Curie-Weiss law.     

New findings in phase transitions of spinel Li1.07Mn1.93O4-delta studied by transmission electron microscopy

Phase transitions and the related phase identifications at different temperatures for spinel Li(1.07)Mn(1.93)O(4-delta) crystals have been studied by transmission electron microscopy. The preliminary results clearly show the existence of at least two types of low-temperature phase: monoclinic and orthorhombic. Oxygen deficiency may raise the phase-transition temperature for the high-temperature (HT) cubic to low-temperature (LT) tetragonal, monoclinic, or orthorhombic phases. When the oxygen deficiency delta is very close to zero, the transition temperature is below room temperature (RT). Therefore, only the HT cubic spinel is observed at RT. When delta=0.182, the transition temperature is higher than RT, so the structures of the LT phases can be studied at RT. This study reveals the structural relationships between the LT phase and the HT phase. These relationships can be summarized as follows: (1) Two orthogonal cubic [440](Cubic)(*) and [440](Cubic)(*) reciprocal vectors are divided into two parts by {220} and {220} super reflections, respectively. This situation resembles the structures caused by correlated tilting and/or distortion of the octahedra in perovskites. (2) One of the cubic <440>Cubic(*) reciprocal vectors is divided into three parts by weak super-reflections. This situation resembles the modulated structure caused by the charge- and orbital-ordering in the perovskite La(1/3)Ca(2/3)MnO(3) of the space group Pnma. (3) One of the cubic <440>(Cubic)(*) reciprocal vectors, e.g. [440](Cubic)(*), is divided into three parts by stronger super-reflections, at the same time some strong reflections of the cubic spinel, e.g. (111)(Cubic)=(320)(Ortho)/2 disappear, indicating that there is a phase transition containing atomic movement. Items (2) and (3) are new findings in the present work.     

Novel features of Sr1-xCaxTiO3 phase diagram: evidence for competing antiferroelectric and ferroelectric interactions

Structural and dielectric evidences are advanced to show that the Sr1-xCaxTiO3 (SCT) system undergoes an antiferroelectric (AFE) phase transition in the composition range 0.18相似文献   

Dynamic mechanism of the ferroelectric to antiferroelectric phase transition in chiral smectic liquid crystals

The temperature-induced phase transition between the chiral smectic phases, antiferroelectric (smectic-C(A)*) and ferroelectric (smectic-C*), is found to occur through solitary wave propagation. We measure the free energy, which shows a double well shape in the entire SmC(A)* temperature range and the global minimum is found to shift from the antiferroelectric order to the ferroelectric order at the transition temperature. However, any significant supercooling is not observed and the transition cannot be described by the first order Landau-de Gennes theory, where the double well potential exists only in a narrow range of temperatures. This implies that the SmC(A)*-SmC* transition can occur only nonhomogeneously through the solitary wave propagation which overcomes the high energy barrier between the two minima.     

Electro-optical Kerr effect in the isotropic phase of the two antiferroelectric liquid crystal mixtures

We have experimentally studied for the first time the electro-optical Kerr effect and the pre-transitional behavior in the isotropic phase of two antiferroelectric liquid crystal mixtures, W-232 and W-204D, composed of rod-like ester molecules exhibiting the direct smectic-A to isotropic (SmA-I) phase transition. The Kerr law has been confirmed for the two compounds and the variation of inverse Kerr constant with temperature above the smectic–isotropic transition temperatures were determined. Both the mixtures with very broad antiferroelectric phase around room temperature have similar sequence of the phases (i.e., Cr-SmC*A-SmC*-SmA-I). Although, the pre-transitional behavior is usually complex in the isotropic phase of the chiral smectic liquid crystal compounds, the investigated compounds showed a similar behavior compared to that of nematic–isotropic behavior.     

High-resolution 31P nuclear magnetic resonance study of phase transitions in TlH2PO4

High-resolution ³¹P nuclear magnetic resonance (NMR) techniques were employed to study a KH₂PO₄-type ferroelectric system, TlH₂PO₄. A marked temperature dependence of the isotropic chemical shift below the ferroelastic phase transition temperature is indicative of an electronic instability. The NMR linewidth showed a discontinuity at the ferroelastic phase transition, and the anisotropy was measured to increase rapidly below the antiferroelectric phase transition. Thus, the changes in the microscopic environments associated with the phase transitions were sensitively reflected in a characteristic manner.     

Effect of Sn substitution on the elastic anomalies and phase transition behaviors of antiferroelectric PbHfO3 single crystals studied by Brillouin scattering

The phase transition sequence of a PbHf_0.7Sn_0.3O₃ single crystal was investigated by using Brillouin spectroscopy. The longitudinal acoustic mode showed three distinct changes at ∼370 K, ∼455 K and ∼495 K which corresponded to the antiferroelectric 1 → antiferroelectric 2 → intermediate → paraelectric phase transitions upon heating. The paraelectric phase was characterized by softening acoustic mode, increasing acoustic damping and the appearance of quasielastic central peaks which were observed upon approaching the phase transition temperature. The relaxation times derived from the acoustic mode anomalies and the central peak were consistent with each other and showed a slowing-down behavior. These precursor phenomena were attributed to the polar clusters having broken inversion symmetry. The substitution of Hf with Sn induced a very soft intermediate phase between the paraelectric and the antiferroelectric phases, where the longitudinal acoustic mode exhibited the lowest mode frequency along with substantially high acoustic damping. The transverse acoustic mode, which was observed in the two antiferroelectric phases, did not appear in the intermediate phase. These results indicated that the average symmetry of the intermediate phase may be cubic consisting of fine ferroelastic domains.     

Correlation between reentrant spin glass behavior and the magnetic order-disorder transition of the martensite phase in Ni-Co-Mn-Sb Heusler alloys

We have performed ac susceptibility and dc magnetization measurements in Ni(50-x)Co(x)Mn(38)Sb(12) Heusler alloys. From the ac susceptibility measurements, the existence of reentrant spin glass (RSG) state is observed for x=0-5. It is found that the signature of RSG behavior diminishes with increase in x. This behavior is in contrast to the fact that the exchange bias field increases with x, which reveals that the origins of RSG and exchange bias are different in the present system. It is found that the system enters a frustrated ferromagnetic state just below the Curie temperature of the martensite phase (T(M)(C)) and then the RSG state at low temperature. The strength of the RSG state is critically dependent on the sharpness of the magnetic transition at (T(M)(C)). This proposition is further supported by the thermo-remanent magnetization and low field thermomagnetic measurements.     

Orbital correlations in the pseudocubic O and rhombohedral R phases of LaMnO3

The local and intermediate structure of stoichiometric LaMnO3 has been studied in the pseudocubic and rhombohedral phases at high temperatures (300-1150 K). Neutron powder diffraction data were collected and a combined Rietveld and high real space resolution atomic pair distribution function analysis was carried out. The nature of the Jahn-Teller (JT) transition around 750 K is confirmed to be orbital order to disorder. In the high-temperature orthorhombic (O) and rhombohedral (R) phases, the MnO6 octahedra are still fully distorted locally. More importantly, the intermediate structure suggests the presence of local ordered clusters of diameter approximately 16 A ( approximately 4 MnO6 octahedra) implying strong nearest-neighbor JT antiferrodistortive coupling. These clusters persist well above the JT transition temperature even into the high-temperature R phase.     

Kinetic arrest of the first-order to R3c Pbnm phase transition in supercooled La(x)MnO(3+δ) (x = 1 and 0.9)

We report the occurrence of kinetic arrest of the first-order phase transition from R3c to Pbnm in supercooled La(x)MnO(3±δ) (x = 1 and 0.9, i.e. δ > 0.125). Structural studies have been done, employing low temperature transmission electron microscopy (LT-TEM) and low temperature x-ray diffraction (LT-XRD) techniques. No phase transformation was observed even in La(x)MnO(3±δ) aged for ~12 h at 98 K. The evidence of the occurrence of kinetic arrest was realized at low temperatures through in situ electron beam triggered nucleation and perpetual devitrification of the R3c phase into a Pbnm phase. It was clearly evidenced that the R3c structure of La(x)MnO(3±δ), below its ferromagnetic transition temperature, is metastable and prone to be transformed to a Pbnm orthorhombic structure following initiation by an electron beam trigger. The electron beam transformed Pbnm phase was found to transform back to the R3c phase through a first-order phase transition occurring close to the ferromagnetic to paramagnetic transition (T(c)) during heating. The glass-like kinetics of the arrested R3c phase has been investigated through resistance relaxation measurements, showing a decreasing logarithmic rate of decay of the arrested R3c phase towards the stable Pbnm phase with decreasing temperature, down to 5 K. On the basis of the correlations observed in the resistance-versus-temperature, magnetization-versus-temperature, magnetization-versus-field, resistance relaxation and LT-XRD measurements, the occurrence of kinetic arrest has been attributed to the suppression of Jahn-Teller distortion by double exchange across the insulator-metal transition.     

Phase transition in CdHfO<Subscript>3</Subscript>

The phase transition from an orthorhombic phase (space group Pnma) to a rhombohedral phase (space group R3m) of the CdHfO₃ hafnate is investigated using methods of structural analysis. It is shown that crystal lattices of both phases contain polar structural units (octahedra, cubooctahedra). On this basis, it is assumed that the orthorhombic and rhombohedral phases of the CdHfO₃ compound are the antiferroelectric and ferroelectric phases, respectively.     

Dynamical studies of highly deuterated betaine phosphate near the antiferroelectric phase transition

The dielectric response and the Raman spectra of single crystals of deuterated betaine phosphate are studied around the antiferroelectric phase transition. The dielectric data between 10 MHz and 11 GHz can be explained on the basis of a simple Debye-relaxation with a critical slowing-down of the relaxation rate on approachingT _C . Using the Cole-Davidson form of the dielectric function we succeeded in fitting the data in the whole frequency range from 10 MHz to 11 GHz and from 64–400 GHz over a temperature range from 145–280 K. Raman spectra clearly indicate that the doubling of the unit cell does not take place at the antiferroelectric transition temperature, but some degrees below.     

Investigation of new chiral fluorosubstituted compound exhibiting room temperature antiferroelectric phase

Influence of the electric field upon alignment of molecules in ferro- and antiferroelectric phases has been studied for two fluoro-substituted compounds exhibiting antiferroelectric phase at room temperature. Two different relaxation processes have been revealed in the ferroelectric as well as antiferroelectric phase. Low temperature value of spontaneous polarization is ca. 130 nC/cm² for both substances studied. The substances align very well in the external electric field — a mono-domain of the ferroelectric SmC* phase can be obtained in about 3.5 hours.     

Cooperative Jahn-Teller phase transition in LaMnO3 studied by X-ray absorption spectroscopy

The local structure of LaMnO3 across the Jahn-Teller (JT) transition at T(JT)=750 K was studied by means of x-ray absorption near edge structure and extended x-ray absorption fine structure at the Mn K-edge. Our results indicate a similar electronic local structure for Mn atoms above and below T(JT) and a dynamical tetragonal JT distortion of MnO6 octahedra above T(JT). The structural transition is originated by the ordering of tetragonally distorted octahedra. The entropy content of the transition is analyzed within the framework of the three-state Potts model with nearest neighbor antiferrodistortive coupling.     

Pressure-induced phase transition(s) in KMnF3 and the importance of the excess volume for phase transitions in perovskite structures

We report a pressure-dependent investigation of KMnF(3) by x-ray diffraction up to 30 GPa. The results are discussed in the framework of Landau theory and in relation to the isostructural phase transition in SrTiO(3). The phase transition temperature near 186 K in KMnF(3) shifts to room temperature at a critical pressure of P(c) = 3.4 GPa; the pressure dependence of the transition point follows ΔP(c)/ΔT(c) = 0.0315 GPa K(-1). The transition becomes second order under high pressure, close to the tricritical point. The phase transition is determined by the rotation of MnF(6) octahedra with their simultaneous expansion along the rotation axis. The rotation angle was found to increase to 10.5° at 24 GPa. An additional anomaly was observed at higher pressure around 25 GPa, suggesting a further phase transition.     

Structure and dynamics of dense monolayers of no adsorbed on Rh(111) in equilibrium with the gas phase in the Torr pressure range

Using scanning tunneling microscopy, we show the phase transition between new structures of NO on Rh(111) in equilibrium with the gas phase near 300 K, in the Torr pressure range. Two phases with (2 x 2) and (3 x 3) periodicity transform into each other as the pressure and temperature change around the equilibrium P-T line. By measuring P and T at coexistence, we determined the heat of adsorption in the (3 x 3) structure. From the phase boundary dynamics, the activation energy barrier between phases were estimated. The results demonstrate that unique information can be obtained from high-pressure and high-temperature studies.     

Field induced modification of SmC1–SmCA1 transition temperature of a fluorinated antiferroelectric liquid crystal

The temperature and frequency dependent dielectric relaxation data and simultaneous observation of optical texture reveal co-existence of ferroelectric (SmC¹) and antiferroelectric (SmC_A¹) phases in the pre-transition regime of the antiferroelectric liquid crystal (AFLC) sample viz. (R)-4-[1-methyl-2-(2,2,3,3,3-pentafluoropropyloxy)ethyloxy)carbonyl]phenyl 4′-decyloxybiphenyl-4-caboxylate. Interestingly, this sample shows irreversible change in the antiferroelectric to ferroelectric (AFE → FE) phase transition temperature (T₀) for consecutively increasing bias field treatment in successive cycles. The lowest upper bound of the threshold field for AFE → FE transition at the boundary of the said phases is found to be ∼1 kV cm⁻¹.