PbMg1/3Nb2/3O3dielectric aging in the freezing temperature region.

Aging of the relaxors and PbMg1/3Nb2/3O3in particular was extensively studied in last two decades. Most of the results were related to the low temperature glass-like region. No systematic data around the freezing temperatures were reported. To cover this still missing information we have studied the evolution of the dielectric spectra in the broad frequency region from 10-1 Hz to 106 Hz both below and above the freezing temperatureTf≈240 K. Below freezing temperature the existence of the earlier reported waiting time-frequency scaling at frequencies below ≈50 Hz is confirmed. At higher frequencies this deviation from the scaling is observed that can be tentatively attributed to the complexity of the relaxing entities. AboveTfaging is observed only in the restricted frequency interval below the maximum of the dielectric loss spectrum. The observed effect can be attributed to the hardening and narrowing of the dielectric loss spectra and decreasing of the dielectric strength with time. The explanation is proposed based on the concept of the creation of the degenerate polar nanoregions covering several chemically ordered regions (COR) (multi PNRs-MPNRs). These MPNRs are large compare to the PNRs located at the single CORs and some of them may become frozen resulting in the described spectra changes.

Structural heterogeneity and diffuse scattering in morphotropic lead zirconate-titanate single crystals.

Complementary diffuse and inelastic synchrotron x-ray scattering measurements of lead zirconate-titanate single crystals with composition near the morphotropic phase boundary (x=0.475) are reported. In the temperature range 293 K

The negative phonon confinement effect in nanoscopic sodium nitrite.

A nanocomposite of porous glass and a NaNO(2) ferroelectric (channels of approximately 7 nm diameter) was studied using infrared reflectivity, THz transmission and Raman spectroscopy as a function of temperature in the range of 300-500 K, including the ferroelectric transition. From the infrared and THz response the effective dielectric function was calculated and compared with the dielectric functions calculated from the Bruggeman and Lichtenecker models of the effective medium, using the known data on the polar phonon modes of the NaNO(2) single crystals. The results show good qualitative agreement, indicating that the stiffening of the effective modes is due to local depolarization fields on the glass-ferroelectric interfaces. The nonpolar Raman modes show no substantial modification compared to those of the bulk NaNO(2). Some signatures of the ferroelectric transition were even seen. The results indicate that the intrinsic size effect (phonon confinement) is negligible in this nanocomposite.

Multiscale local ordering in the prototypical uniaxial relaxor Sr0.6Ba0.4Nb2O6 single crystal at room temperature.

The structure and diffuse scattering in uniaxial relaxor Sr0.6Ba0.4Nb2O6 single crystal have been studied by x-ray diffraction at room temperature. Two different kinds of local ordering with different correlation lengths and different shapes of correlation functions have been revealed. The values of correlation lengths have been determined from analysis of experimental data. These types of orderings are connected with the intrinsic structure of crystal and can promote the appearance of relaxor properties.

Critical scattering and incommensurate phase transition in antiferroelectric PbZrO3 under pressure.

Antiferroelectric lead zirconate is the key ingredient in modern ferroelectric and piezoelectric functional solid solutions. By itself it offers opportunities in new-type non-volatile memory and energy storage applications. A highly useful and scientifically puzzling feature of this material is the competition between the ferro- and antiferroelectric phases due to their energetic proximity, which leads to a challenge in understanding of the critical phenomena driving the formation of the antiferroelectric structure. We show that application of hydrostatic pressure drastically changes the character of critical lattice dynamics and enables the soft-mode-driven incommensurate phase transition sequence in lead zirconate. In addition to the long known cubic and antiferroelectric phases we identify the new non-modulated phase serving as a bridge between the cubic and the incommensurate phases. The pressure effect on ferroelectric and incommensurate critical dynamics shows that lead zirconate is not a single-instability-driven system.

Translational dynamics of water in the nanochannels of oriented chrysotile asbestos fibers.

We performed a high-resolution quasielastic neutron scattering study of water dynamics in fully hydrated oriented chrysotile asbestos [chemical formula Mg3Si2O5(OH)4] fibers. The fibers possess sets of macroscopically long, parallel channels with a characteristic diameter of about 5 nm. Freezing of water in the channels was observed at about 237 K. Measurements at 280, 260, and 240 K revealed a translational dynamics of water molecules with the relaxation time slower by more than an order of magnitude compared to bulk water. The Q dependence of the quasielastic broadening was typical of a translational diffusion motion with a distribution of jump lengths, similar to that observed in bulk water. The relaxation time showed no significant anisotropy in the measurements with the scattering vector parallel and perpendicular to the fiber axes.

Diffusion of benzene confined in the oriented nanochannels of chrysotile asbestos fibers.

We used quasielastic neutron scattering to study the dynamics of benzene that completely fills the nanochannels of chrysotile asbestos fibers with a characteristic diameter of about . The macroscopical alignment of the nanochannels in fibers provided an interesting opportunity to study anisotropy of the dynamics of confined benzene by means of collecting the data with the scattering vector either parallel or perpendicular to the fibers axes. The translational diffusive motion of benzene molecules was found to be isotropic. While bulk benzene freezes at 278.5 K, we observed the translational dynamics of the supercooled confined benzene on the time scale of hundreds of picoseconds even below 200 K, until at about its dynamics becomes too slow for the resolution of the neutron backscattering spectrometer. The residence time between jumps for the benzene molecules measured in the temperature range of 260 K to 320 K demonstrated low activation energy of 2.8 kJ/mol.

Neutron diffraction study of the (BiFeO3)1-x(PbTiO3)x solid solution: nanostructured multiferroic system.

Neutron diffraction studies performed on the solid solution of (BiFeO(3))(1-x)(PbTiO(3))(x) reveal a mixture of two nanoscale phases with different crystal structures: a rhombohedral BiFeO(3)-based phase and a tetragonal PbTiO3-based phase. The ratio of Fe(3)+ and Ti(4)+ ions in the two phases is practically constant; only the proportion of the phases changes. The magnetic moments in the BiFeO(3)-based phase, in contrast to BiFeO(3), deviate from the basal plane. The temperature evolutions of the spin components along the hexagonal axis and within the perpendicular plane are different, leading to a spin re-orientation transition. The antiferromagnetic order in the PbTiO(3)-based phase corresponds to a simple structure with the propagation vector (1/2, 1/2, 1/2). The temperature dependence of the antiferromagnetic moment in the tetragonal phase at x = 0.5 indicates a canted antiferromagnetic order and a net ferromagnetic moment. A strong magnetic coupling between the two constituting phases due to the nanoscale character of the phases and well-developed interface between nanoparticles has been observed. The system of (BiFeO(3))(1-x)(PbTiO(3))(x) demonstrates an interesting scenario, where the proximity effects in the unstable system play a crucial role in the appearance of the unusual magnetic properties.

Lattice dynamics in the paraelectric phase of PbHfO3 studied by inelastic x-ray scattering.

We report the results of an inelastic x-ray scattering study of the lattice dynamics in the paraelectric phase of the antiferroelectric lead hafnate PbHfO3. The study reveals an avoided crossing between the transverse acoustic and transverse optic phonon modes propagating along the [1 1 0] direction with [1 -1 0] polarization. The static susceptibility with respect to the generally incommensurate modulations is shown to increase on cooling for the entire Γ-M direction. We consider different approaches to the data analysis that correspond to different models for the temperature evolution of the dynamic susceptibility function. A number of similarities and differences between the lattice dynamics of PbHfO3 and PbZrO3 are described.

The origin of antiferroelectricity in PbZrO3.

Antiferroelectrics are essential ingredients for the widely applied piezoelectric and ferroelectric materials: the most common ferroelectric, lead zirconate titanate is an alloy of the ferroelectric lead titanate and the antiferroelectric lead zirconate. Antiferroelectrics themselves are useful in large digital displacement transducers and energy-storage capacitors. Despite their technological importance, the reason why materials become antiferroelectric has remained allusive since their first discovery. Here we report the results of a study on the lattice dynamics of the antiferroelectric lead zirconate using inelastic and diffuse X-ray scattering techniques and the Brillouin light scattering. The analysis of the results reveals that the antiferroelectric state is a 'missed' incommensurate phase, and that the paraelectric to antiferroelectric phase transition is driven by the softening of a single lattice mode via flexoelectric coupling. These findings resolve the mystery of the origin of antiferroelectricity in lead zirconate and suggest an approach to the treatment of complex phase transitions in ferroics.

Local lattice dynamics and the origin of the relaxor ferroelectric behavior.

Relaxor ferroelectricity is observed in many strongly disordered ferroelectric solids. However, the atomistic mechanism of the phenomenon, particularly at high temperatures, is not well understood. In this Letter we show the local lattice dynamics as the origin of relaxor ferroelectricity through the first use of the dynamic pair-density function determined by pulsed neutron inelastic scattering. For a prototypical relaxor ferroelectric, Pb(Mg(1/3)Nb(2/3))O(3), we demonstrate that the dynamic local polarization sets in around the so-called Burns temperature through the interaction of off-centered Pb ions with soft phonons, and the slowing down of local polarization with decreasing temperature produces the polar nanoregions and the relaxor behavior below room temperature.

Magnetic ordering and phase transition in MnO embedded in a porous glass.

We present the results of a neutron diffraction study of the antiferromagnet MnO embedded in a porous glass. The type of magnetic ordering and the structural distortion are similar to those of the bulk, but the ordered magnetic moment of 3.84(4)muB/ion is strongly reduced and the Néel temperature is enhanced. The magnetic transition is second order, in contrast to the first order transition of the bulk. The size of the magnetic region is smaller than the average size of the nanoparticles. The reasons for this behavior are discussed.

Temperature evolution of sodium nitrite structure in a restricted geometry.

The NaNO2 nanocomposite ferroelectric material in porous glass was studied by neutron diffraction. For the first time, the details of the crystal structure including positions and anisotropic thermal parameters were determined for the solid material, embedded in a porous matrix, in ferro- and paraelectric phases. It is demonstrated that in the ferroelectric phase the structure is consistent with bulk data, but above transition temperature the giant growth of amplitudes of thermal vibrations is observed, resulting in the formation of a "premelted state." Such a conclusion is in good agreement with the results of dielectric measurements published earlier.