Dielectric and NMR studies of nanoporous matrices loaded with sodium nitrite

NMR and dielectric studies have been performed on NaNO₂ loaded in mesoporous matrices of MCM-41 and SBA-15 with pore sizes of 20, 37, and 52 Å. The spin-lattice relaxation rate and ²³Na NMR line shape, as well as the complex impedance, were measured within a broad temperature interval including the ferroelectric phase transition in bulk NaNO₂. Two different phases of sodium nitrite, the crystalline and melt phases, are shown to coexist under conditions of a restricted geometry. The crystalline phase undergoes a ferroelectric phase transition. The melt fraction increases with temperature. The existence of two phases accounts for all experimental data on NaNO₂ under conditions of a restricted geometry.     

Ferroelectricity in nanocomposites based on porous glass with inclusions of NaNO<Subscript>2</Subscript>

The dielectric nonlinearity and pyroeffect in matrix composite based on porous glass with inclusions of sodium nitrite are investigated. It is found that the composite polarization turns to zero at a temperature below that of the phase transition in the bulk NaNO₂. The obtained dependence of the pyrocoefficient on temperature also corroborates the existence of the phase transition in sodium nitrite nanoparticles included in the porous matrix.     

Effect of ionizing radiation on the dielectric characteristics of TlInSe<Subscript>2</Subscript> and TlGaTe<Subscript>2</Subscript> single crystals

The temperature dependences of the electrical conductivity and the permittivity of TlInSe₂ and TlGaTe₂ crystals unirradiated and irradiated with 4-MeV electrons at a doze of 10¹⁶ cm⁻² have been investigated. It has been established that electron irradiation leads to a decrease in the electrical conductivity σ and the permittivity ɛ over the entire temperature range under study (90–320 K). It has been revealed that the TlInSe₂ and TlGaTe₂ single crystals undergo a sequence of phase transitions characteristic of crystals of this type, which manifest themselves as anomalies in the temperature dependences σ = f(T) and ɛ = f(T). Electron irradiation at a doze of 10¹⁶ cm⁻² does not affect the phase transition temperatures of the crystals under investigation.     

The giant dielectric tunability effect in bulk Y<Subscript>2</Subscript>NiMnO<Subscript>6</Subscript> around room temperature

The effect of applied dc bias electric field on dielectric permittivity in bulk Y₂NiMnO₆ is investigated in this paper. It is found that a small bias field of 40 V/cm can greatly reduce the dielectric permittivity around the room temperature, compared to the much larger electric field that is required for conventional ferroelectric materials. The observed giant dielectric tunability is retained over a broad range of around room temperature and is most likely related to the charge ordering of Ni²⁺ and Mn⁴⁺ ions. This may further confirm the existence of electronic ferroelectricity in Y₂NiMnO₆.     

Peculiarities of the dielectric,elastic, and anelastic properties of the PbFe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> ferroelectromagnet at the antiferromagnetic phase transition

Peculiarities in the behavior of the dielectric, elastic, and anelastic properties of the PbFe_1/2Nb_1/2O₃ ceramic ferroelectromagnet have been found and investigated near the antiferromagnetic phase transition (Néel temperature T _N = 160 K). It is established that the transition to the antiferromagnetic phase leads to a decrease in the permittivity and elastic compliance. The anomaly of permittivity found near T _N indicates the presence of magnetoelectric interaction in the magnetically ordered phase.     

Phase transitions of SC(NH<Subscript>2</Subscript>)<Subscript>2</Subscript> ferroelectrics in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-based nanoporous matrices

Temperature dependences of the linear permittivity ε' and the third harmonic amplitude γ_3ω of composites prepared by introducing ferroelectrics SC(NH₂)₂ into matrices of porous aluminum oxide Al₂O₃ with pore sizes 60 and 100 nm are determined. It is found that temperature T _c of the ferroelectric phase transition and the temperature T _i of the phase transition from incommensurable phase to the paraphrase increase significantly. The transition shifts increase as pore diameters decrease.     

Magnetic and structural anomalies of Na<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>C<Subscript>60</Subscript> (n = 2, 3)

Sodium fullerides Na _n C60 (n = 2, 3) have been synthesized by a liquid phase reaction and investigated with X-ray diffraction (XRD), nuclear magnetic resonance (NMR), electron paramagnetic resonance, and differential thermal analysis. XRD data indicate that the crystal structure of Na₂C₆₀ at 300 K is face centered cubic (FCC). A phase transition from primitive cubic to FCC crystal structure has been observed in this work in Na₂C₆₀ fulleride at 290 K. The transition is accompanied by the step-like change of paramagnetic susceptibility. The crystal structure of Na₃C₆₀ is more complicated than, and different from, what has been reported in the literature. A nearly seven-fold increase of paramagnetic susceptibility with increasing temperature has been observed in the Na₃C₆₀ fulleride at 240–260 K. In the same temperature range, a new line at about 255 ppm appears in the ²³Na NMR spectrum, indicating a significant increase of electron density near the Na nucleus. The observed effect can be explained by a metal-insulator transition caused by a structural transition.     

A comparative Raman study of 0.65(PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>) -0.35(PbTiO<Subscript>3</Subscript>) single crystal and thin film

We report a comparative Raman study of 0.65(PbMg_1/3Nb_2/3O₃)-0.35(PbTiO₃) (PMN-0.35PT) single crystal and thin film. Raman spectra investigation indicates a change in bulk from the high temperature cubic to the tetragonal phase and then to the low temperature Mc monoclinic phase. The transition temperatures are in good agreement with the ones previously observed by dielectric measurements on the same sample. In contrast, we observe no phase transition to the monoclinic phase in the PMN-0.35PT 4000 Å thick film and only a cubic to tetragonal diffuse transition has been determined at high temperature. The enhanced stability of the tetragonal phase and the absence of low temperature monoclinic phase have been attributed to the in plane strain.     

On the nature of the KH<Subscript>2</Subscript>PO<Subscript>4</Subscript> high-temperature transformation

For over two decades, the high-temperature phase transition (HTPT) at around T _p = 180 °C on KH₂PO₄ (KDP), which involves an ionic conductivity increase, constitutes a controversial subject; while most authors ratify a physical transformation (tetragonal → monoclinic phase transition), others defend the chemical transformation. A careful high-temperature phase behavior examination of this acid salt by means of modulated and conventional differential scanning calorimetry, thermogravimetric analysis, simultaneous thermogravimetric and differential scanning calorimetry, impedance spectroscopy, and temperature evolution of X-ray diffraction was performed to provide a possible solution to this long-standing issue. We found that the structural phase transition does not take place. Instead, a chemical transformation occurs at T _p. When KDP is heated through this temperature, the sample initially corresponding to a single phase (tetragonal) transforms to a sample composed of two solid phases: tetragonal KDP, located at its bulk, and monoclinic potassium metaphosphate (KPO₃), located at its surface. Most of the water produced evaporates, but a small portion of liquid water bonds to KPO₃. Because this is of polymeric nature, it takes the role of a host matrix that contains liquid water regions. Consequently, given that part of the water dissolves a portion of surface salt (providing protons), the surface sample system behaves in a similar manner to a polymer electrolyte membrane where the proton transport mechanism includes the vehicle type, using hydronium (H₃O⁺) as a charge carrier. On further heating, the bulk tetragonal KDP phase reduced to its total decomposition. The metastability of the high-temperature phase below T _p is also explained.     

NMR study and electrical properties investigation of Zn<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The α-Zn₂P₂O₇ compound was obtained by conventional solid-state reaction. The sample was characterized by X-ray powder diffraction, solid state ³¹P NMR MAS, and electrical impedance spectroscopy. The solid state ³¹P MAS NMR, performed at 121.49 MHz, shows three isotropic resonances at −21.1, −18.8, and −15.8 ppm, confirming the non-equivalency of the three PO₄ groups in the α-Zn₂P₂O₇ form. They are characterized by different chemical shift tensor parameters with the local geometrical features of the tetrahedra. Electrical impedance measurements of β-Zn₂P₂O₇, form stable for temperature greater than 403 K, were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The AC conductivity obeys the universal power law. The approximation type correlated barrier hopping model explains the universal behavior of the n exponent. The impedance plane plot shows semicircle arcs at different temperatures, and an electrical equivalent circuit has been proposed to explain the impedance results. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements CPE. The simulated spectra show a good correlation with the experimental data.     

Dielectric parameters of mesoporous sieves filled with NaNO<Subscript>2</Subscript>

This paper reports on a dielectric study of MCM-41 molecular sieves with cellular channels of different sizes filled with the NaNO₂ ferroelectric. The temperature dependences of the permittivity and electrical conductivity of sodium nitrite in cellular channels are calculated from experimental data on the permittivity and electrical conductivity of the composite. The calculations are performed using the relationships obtained for the hexagonal matrix with parallel cylindrical inclusions within pores. The observed increase in the conductivity of sodium nitrite in confined geometry at high temperatures is attributed to partial melting. It is shown that the increase in the permittivity of the composite is caused by Maxwell-Wagner relaxation processes.     

Dielectric Properties of Nanoporous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Films Filled with Ferroelectric SC(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>

Temperature dependences of permittivity ε′ and third harmonic amplitude γ_3ω of nanocomposites obtained by embedding ferroelectric SC(NH₂)₂ in porous alumina films with pore sizes of 60 and 100 nm are studied. A substantial increase in the temperatures of ferroelectric phase transition T_c1 and T_c2 and that of phase transition T_i from incommensurate phase to paraphase are also observed. The temperatures of all phase transitions are found to rise as pore diameters shrink.     

A Raman and dielectric study of a diffuse phase transition in (Pb<Subscript>1-x</Subscript>Ca<Subscript>x</Subscript>)TiO<Subscript>3</Subscript> thin films

Dielectric and Raman scattering experiments were performed on polycrystalline Pb_1-xCa_xTiO₃ thin films (x=0.10, 0.20, 0.30, and 0.40) as a function of temperature. The results showed no shift in the dielectric constant (K) maxima, a broadening with frequency, and a linear dependence of the transition temperature on increasing Ca²⁺ content. On the other hand, a diffuse-type phase transition was observed upon transforming from the cubic paraelectric to the tetragonal ferroelectric phase in all thin films. The temperature dependence of Raman scattering spectra was investigated through the ferroelectric phase transition. The temperature dependence of the phonon frequencies was used to characterize the phase transitions. Raman modes persisted above the tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of a breakdown of the local cubic symmetry due to chemical disorder. The lack of a well-defined transition temperature and the presence of broad bands in some temperature interval above the FE–PE phase transition temperature suggested a diffuse-type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films. PACS 77.80.Bh; 77.55.+f; 78.30.-j; 77.80.-e; 68.55.-a     

Modulated magnetic structure in quasi-one-dimensional clinopyroxene NaFeGe<Subscript>2</Subscript>O<Subscript>6</Subscript>

The magnetic structure of the NaFeGe₂O₆ monoclinic compound has been experimentally investigated using the elastic scattering of neutrons. At a temperature of 1.6 K, an incommensurate magnetic structure has been observed in the form of an antiferromagnetic helix formed by a pairs of the spins of the Fe³⁺ ions with helical modulation in the ac plane of the crystal lattice. The wave vector of the magnetic structure has been determined and its temperature behavior has been studied. The analysis of the temperature dependences of the specific heat and susceptibility, as well as the isotherms of the field dependence of the magnetization, has revealed the existence of not only the order-disorder magnetic phase transition at the point T _N = 13 K, but also an additional magnetic phase transition at the point T _c = 11.5 K, which is assumingly an orientation phase transition.     

Phase transition in nanostructured LaMnO<Subscript>3</Subscript>

Nanocrystalline LaMnO₃ samples have been synthesized by the coprecipitation of lanthanum and manganese salt solutions followed by annealing at 800°C in air and then in an argon flow. With the use of X-ray and neutron diffraction analysis, it has been found that the resulting samples had an orthorhombic crystal structure (space group Pbnm). In the nanocrystalline LaMnO₃ samples, an order-disorder phase transition from the low-temperature phase to the high-temperature phase occurs at (220 ± 10)°C, which is much lower than the value of 477°C for bulk LaMnO₃. The phase transition is due to the removal of the Jahn-Teller distortion of the Mn³⁺O₆ oxygen octahedrons and is accompanied by a decrease in the unit cell volume of lanthanum manganite over a narrow temperature range.     

Optical and dielectric studies of phase transitions in single crystals of NaNbO<Subscript>3</Subscript>-Gd<Subscript>1/3</Subscript>NbO<Subscript>3</Subscript> solid solutions

The temperature dependences of the permittivity ? and the false-color image patterns obtained by the rotating polarizer method for single crystals of (1 ? x)NaNbO_3?x Gd_1/3NbO₃ (x = 0.003, 0.090) solid solutions with different degrees of diffuseness of the phase transition are investigated. A multifractal analysis of the false-color images has revealed anomalies in the temperature dependences of the parameter ?_∞ of the multifractal spectrum. For a sample with a sharp phase transition (x ≈ 0.003), the temperature of this anomaly is in good agreement with the temperature of the jumps in the permittivity ?(T) and birefringence. For an NNG crystal with x ≈ 0.09, which exhibits a diffuse maximum of ?(T), the temperatures of the anomalies of ?_∞(T) differ in the central and peripheral regions, which correlates with the distribution of Gd over the crystal.     

Specific features of the thermal,magnetic, and dielectric properties of multiferroics BiFeO<Subscript>3</Subscript> and Bi<Subscript>0.95</Subscript>La<Subscript>0.05</Subscript>FeO<Subscript>3</Subscript>

Thermophysical, magnetic, and dielectric properties of multiferroic BiFeO₃ and Bi_0.95La_0.05FeO₃ ceramic compounds were comprehensively studied. Anomalies of the permittivity near an antiferromagnetic phase transition related to the structural variations were detected. The temperature T _N was determined from the temperature dependences of the thermal expansion coefficient, heat capacity, and differential susceptibility. It is shown that the transition point is shifted to higher temperatures as the rare-earth La ion substitutes for Bi. It is established that an insignificant substitution of lanthanum for bismuth enhances the magnetic properties of bismuth ferrite and the magnetodielectric effect.     

Polarization 1/<Emphasis Type="Italic">f</Emphasis> noise in ferroelectric PbFe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> with a diffused phase transition

The dispersion of complex permittivity in ferroelectric PbFe_1/2Nb_1/2O₃ with diffused phase transition at frequencies of 20 Hz-10 kHz was studied. Dielectric measurements revealed that polarization 1/f noise occurs in the region of coexistence of polar and nonpolar phases. It was found that the temperature dependence of parameter α exhibits a singularity when the temperature of the local order parameter rises. Our analysis of the experimental data enables us to say that the source of the noise is the fluctuations of spontaneous polarization.     

X-ray emission study of the electronic structure of nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Valence states of metal ions and the phase composition of nanocrystalline Al₂O₃ (of the original oxide and the oxide irradiated by high-energy Fe⁺ ions) are studied by using x-ray emission Al L_{2, 3} and O Kα spectra. It is established that the shape of the Al L_{2, 3} spectra strongly changes as one goes from the original (bulk) Al₂O₃ to nanocrystalline oxide, while the O Kα spectra remain practically unchanged. Moreover, irradiation by high-energy Fe⁺ ions results in slight additional changes in the x-ray spectral characteristics of the aluminum oxides under study. The obtained experimental data are compared with the results of theoretical calculations of the electronic structure of α and γ phases of Al₂O₃ performed using the LDA formalism. Using the results of x-ray spectral studies, electronic structure calculations, and x-ray diffraction analysis, it is shown that the revealed spectral differences between the nanocrystalline state of aluminum oxide and the bulk material can be interpreted as a phase transition from the α phase to the γ phase of Al₂O₃ with an addition of bayerite.     

Dielectric spectra of Bi<Subscript>0.98</Subscript>Nd<Subscript>0.02</Subscript>FeO<Subscript>3.00</Subscript> multiferroic thin films in the terahertz frequency range

Transmission and reflection spectra of Bi_0.98Nd_0.02FeO_3.00 multiferroic thin films on MgO single-crystal substrates have been measured using submillimeter spectroscopy (on a backward-wave tube spectrometer) and Fourier-transform infrared spectroscopy in the frequency range from 8 to 1000 cm⁻¹ at room temperature. The complex permittivity spectra of the films have been calculated in terms of the layered medium model. It has been revealed that a decrease in the film thickness leads to a considerable increase in the losses in a range of 30 cm⁻¹ and the corresponding fivefold increase in the static permittivity (to 500 for a film 32 nm thick). This phenomenon has been discussed in the framework of the phenomenological theory of phase transitions.