Phase transitions and macroscopic properties of NaNO3 embedded into porous glasses

The crystal structure and dielectric response of nanocomposite materials on base of porous glasses with average pore diameters of 320, 46 and 7 nm with embedding sodium nitrate have been studied by neutron diffraction and dielectric spectroscopy in low and high temperature phases up to melting. In porous glasses with 46 and 7 nm pores NaNO₃ forms dendrite nanoclusters with "diffraction" sizes of 50(2.5) and 20(2) nm. Decreasing of particle sizes results in decreasing of T_c (temperature of order-disorder orientational transition) and T_melt and in smearing of structure phase transition. The values of critical exponent β for orientational transition are estimated from temperature dependences of intensities of superstructure elastic peaks for these three types of nanocomposite materials.     

Properties of porous glasses with embedded ferroelectric materials

Methods of introducing two ferroelectric materials, viz. NaNO₂ and (CH₃NH₃)₅Bi₂Cl₁₁ (PMACB), into porous glass matrices and the results of dielectric, pyroelectric, thermal expansion and SEM investigations are presented. The best filling degree was achieved for NaNO₂ introduced from the melt, whereas a significantly worse filling effect was achieved for a water solution as the introducing agent. A splitting was observed in the temperature dependence of dielectric permittivity related to the incommensurate phase of NaNO₂ embedded in porous glass from a water solution, whereas no incommensurate phase was observed in the case of glass filled with NaNO₂ from the melt. The confined materials turned out to possess ferroelectric properties and exhibited phase transitions. The negative size effect was observed for porous glasses filled with NaNO₂ and PMACB. The above conclusions are based on the anomaly of dielectric, pyroelectric and dilatometric properties observed in the phase transition regions.     

Energy transfer from Bi3+ sensitizing the luminescence of Eu3+ in clusters embedded into sol–gel silica glasses

Y³⁺(La³⁺), Eu³⁺ and Bi³⁺ ions co-doped sol–gel silica glasses were synthesized. Photoluminescence spectra show that there is energy transfer from Bi³⁺ ions to the emission band of Eu³⁺ ions. The co-dopants Y³⁺ or La³⁺ have strong effects on the local structure and luminescence of Eu³⁺ ions. For 0.5 mol% Eu³⁺ ions doped glasses, the co-doping of 1 mol% Bi³⁺ and 1 mol% Y³⁺ is the most appropriate for the sensitization from Bi³⁺ to Eu³⁺. The sensitization effectiveness from Bi³⁺ ions to Eu³⁺ ions was studied by changing the amount of Bi³⁺ and Y³⁺, and clusters containing rare earth ions and Bi³⁺ ions dominate the energy transfer processes. The comparison of luminescent R-values (the intensity ratio of ⁵D₀ → ⁷F₂/⁵D₀ → ⁷F₁ in Eu³⁺ ions) between glasses containing La³⁺ and containing Y³⁺ verifies the formation of clusters in sol–gel glasses. As a favorable configuration for energy transfer, the accurate design and synthesis of clusters-contained glasses may provide a new kind of luminescent materials.     

Magnetic phase transitions in LaMnO3+λ

Magnetic properties of nonstoichinometric lanthanum manganite LaMnO_3+λ as a function of the Mn⁴⁺ concentration (from 0 to 27%) and temperature (from 77 to 300 K) are investigated. The Mn⁴⁺ ions concentration depends on the degree of oxidation λ. It is shown that at 0–10% Mn⁴⁺ there exists an antiferromagnetic ordering and at 10–14% — mixed ferro-antiferromagnetic ordering, while at Mn⁴⁺ concentration exceeding 14% the ferromagnetic ordering takes place. The concentrational antiferromagnetic-ferromagnetic transition at 14% Mn⁴⁺ is due to the crystal structural O' — O orthorhombic transition. In ferromagnetic O-orthorhombic lanthanum manganite the phase ferromagnetic-paramagnetic transition occurs via intermediate magnetic state where in the paramagnetic matrix there are noninteracting ferromagnetic impurity clusters. The presence of such magnetic state gives rise to anomalous behaviour of magnetic and galvanomagnetic properties of LaMnO_3+λ near Curie temperature.     

Photoluminescence of PbS quantum dots embedded in glasses

Optical properties and photoluminescence of PbS quantum dots (QDs) embedded in glasses were investigated. Formation and radius of PbS QDs were carefully controlled though heat-treatment and modification of host glass composition. Heat-treatment conditions for precipitation of 3–10 nm radius QDs for the tunable photoluminescence in the 1–2 μm wavelength range were identified. Glasses doped with PbS QDs provide potential as robust materials for broadband fiber-optic amplifiers.     

Self-organization model for a cell system: Ferroelectric, ferroelastic, and magnetic states and related phase transitions

A model is proposed to explain the stability, phase state transformations, and coexistence of different phases for fungi cell ensembles (in particular, dimorphism and linear-to-spiral structure transitions with the Earth’s magnetic field screened). This model is based on (i) cell-connected soft polarization modes induced by charge compensation and related ferroelectric and ferroelastic phase transitions and (ii) intracell mobile orbit-spin-lattice clusters with competitive ferromagnetic-diamagnetic behavior and with orbitlattice and spin-lattice interactions. This model makes it possible to explain the structural and magnetic properties of the systems under consideration. In particular, the Lifshitz invariants in the free energy explain the formation of orbit-lattice and spin-lattice spiral and ring-type structures that are formed when the Earth’s magnetic field is effectively screened. The model proposed is not restricted to mitochondria, containing orbit-spin-lattice clusters based on the Fe³⁺/Fe²⁺ states (considered here).     

Structural phase transitions in the LaMnO3+λ system

Structural phase transitions in the LaMnO_3+λ system are studied at various temperatures and with different Mn⁴⁺ ion concentrations. Two structural phase transitions are established. The O′-orthorhombic – O-orthorhombic transition (O′ O transition) is due to removing the cooperative Jahn-Teller distortions and occurs in the Mn⁴⁺ concentration range from 10 to 14% at room temperature. The temperature of this transition varies from 710 K for the stoichiometric LaMnO₃ to room temperature for LaMnO_3.07. The O-orthorhombic – rhombohedral transition (O R transition) is due to the change of the rotation axis of the undistorted MnO₆ octahedra from [100] and [110] to [11 1]. The temperature of this transition varies from 1010 K for LaMnO₃ to 230 K for LaMnO_3.135. The structural phase diagram of temperature vs composition is plotted, indicating the existence of regions of the phase with different structures.     

Improper ferromagnetic phase transitions in crystals

A complete set of possible improper phase transitions leading to polarization and magnetization of crystals is found from tensor bases of representations of the black-and-white point group of crystal symmetry by using the multiplication table of irreducible representations. The dependences of the secondary order parameter on the primary order parameter are presented for different classes of the symmetry group.     

Laser-induced phase transitions in PbI2

Pure crystals of PbI₂ have been grown using zone-refining system. The structural phase transition 12 R → 2 H has been observed when exposed to ruby laser light. The results have been explained on the basis of structural considerations of PbI₂ and compared with the earlier existing findings in literature.     

Polymorphism and phase transitions in TlS

The conditions for synthesis and the range of existence of the monoclinic TlS modification in the Tl-S system have been determined by means of differential thermal, X-ray diffraction, and microstructural analyses. It was shown that the monoclinic phase is a structural analogue of TlGaSe₂. Possible variants of formation of structural sheets and the nature of phase transitions in the monoclinic TlS modification are discussed.     

Temperature evolution of copper oxide nanoparticles in porous glasses

The temperature evolution of copper oxide nanoparticles in the temperature range of 1.5–250 K has been investigated by thermal-neutron diffraction. CuO particles were obtained by Cu(NO₃)₂ · 3H₂O decomposition directly in the pores of porous glass with an average pore diameter of 7 nm. The characteristic nanoparticle size and linear thermal expansion coefficients have been determined.     

Structure and phase transitions in trigonal Cs3Sb2I9 crystals

The atomic structure of Cs₃Sb₂I₉ single crystals was refined using X-ray diffraction data (sp. gr. P3m1; wR = 1.58% and R = 3.07%). The phase transitions revealed earlier were found to be accompanied by the appearance of superstructural reflections. At T _c1 = 86 K, the reflections indicating doubling of the c parameter. At T _c2 = 73 K, a first-order phase transition takes place accompanied by “freezing” of the satellites h, k + 1/2, l + 1/2 reflections. In the temperature range from 73 to 78 K, an incommensurate phase providing the satellites h, k + 1/2 + δ, l + 1/2 is formed.     

Structural phase transitions in heteroepitaxial ferroelectric films

The changes in the structural—deformational characteristics occurring during the phase transitions in the crystal lattice of epitaxially grown thin (Ba,Sr)TiO₃ films on the (001) cleavage of MgO crystals have been studied. It is shown that microdeformations along the surface normal of the wall of a c-domain film increase with the temperature and attain maximum values in the vicinity of the phase transition. No decrease in the dimensions of the coherent-scattering regions was observed. The comparison of the deformation of the “average” lattice and microdeformations led to the assumption that the transition from the paraelectric to the ferroelectric phase is accompanied by the dislocation-induced formation of a dipole-glass-type intermediate phase at the temperatures exceeding that of the phase transition.     

Negative dielectric loss phenomenon in porous sol–gel glasses

The broadband dielectric spectroscopy method was employed to investigate glasses of a fine porosity produced via regular and fast sol–gel routes with different catalysts. The study was carried out in the frequency range 20 Hz to 1 MHz and temperature interval −100 to +300 °C. The process discussed in the paper demonstrates unusual dielectric behavior. Dielectric losses of this process are negative, in certain regions of frequency and temperature, and the corresponding real part of the dielectric permittivity increases with increasing frequencies, according to Kramers–Kronig relationships. This exceptional process is located in different temperature regions for each sample. The concentration and type of acids, used as catalysts, influence the amplitude and the temperature–frequency ranges of the negative losses process (NLP). In order to decipher the physical nature of the process, the experimental study has been accompanied by a theoretical one. It was shown that the NLP in the porous sol–gel samples can be attributed to the local non-compensated matrix-anchored charges, which accumulate both inside the glassy matrix bulk and on the interface of the pores therein.     

Anomalous behaviour of LaMnO3 with small structure distortions in magnetic phase transitions range

The magnetic field effect on conductivity and intensity of the magnetic neutron diffraction reflections as well as magnetization of lanthanum manganite with different crystal lattice distortions in the ferromagnetic-paramagnetic transitions range are investigated. It is shown that in the investigated samples near the paramagnetic-ferromagnetic transition temperature at H = 0 there exists a relatively wide transition range where the magnetic ordering occurs with a relatively small external magnetic field applied.     

Sequence of phase transitions in PbHfO<Subscript>3</Subscript>

The temperature changes in the PbHfO₃ structure in the temperature range of 20 < t < 400°C have been studied by X-ray powder diffraction. The sequence of phase changes with an increase in temperature was found to be as follows: orthorhombic phase Pbam (O1), orthorhombic phase C2mm (O2), tetragonal phase P4mm (T), and cubic phase Pm3m (C). The C2mm and P4mm phases are ferroelectric, which is confirmed by measuring the dependences ɛ(t). The similarity of the transition pattern obtained with the known transition sequences for ferroelectric (barium titanate, potassium niobate, and lead titanate) and antiferroelectric (lead zirconate) oxides is analyzed.     

铁电晶体KNbO3的研究进展

本文评述了近年来国内外对铁电晶体KNbO3在激光倍频和声表面波应用研究方面取得的显著进展,简述了新近生长该晶体的几种方法.最后对KNbO3晶体产业化前景作出了评估.     

Temperature dependencies of intensities of f-f transitions in Pr and Dy in glasses

Absorption spectra of Pr³⁺ and Dy³⁺ embedded in three glass matrices (SiO₂-P₂O₅-GeO₂, Al₂O₃-B₂O₃-SiO₂ and LiB₃O₅) have been studied in detail in the near infrared spectral range. The temperature related behavior of the intensity, width and position of the observed absorption lines were studied. It has been shown that f-f transitions in the studied glasses are mainly allowed by static odd distortions of the ligand environment, and these distortions decrease with a rise in temperature. Comparative analysis of the parameters of the absorption lines and their temperature dependencies in different materials have enabled us to ascertain the difference of size, symmetry and dispersion of distortions of the nearest environment of these rare earth ions in different glasses.     

Optical,X-ray,and calorimetric studies of phase transitions in ND4BeF3

Phase transitions in ND₄BeF₃ crystals at T₁ = 330 and T₂ = 245 K were studied by specific heat (DSC) and X-ray lattice parameters measurements in function of temperature. These ferroelastic transitions are accompanied by anomalous heat absorption, sudden changes in the unit cell parameters and crystal symmetry. Formation of domain structure in particular phases examined under a polarizing microscope is also described. Domain walls of the type (100), (010), and (001) observable at room temperature indicate on the triclinic symmetry of the Phase II. Above T₁ the crystal becomes orthorhombic. First-order phase transition at T₂ causes the symmetry of the crystal in the Phase III to be monoclinic with the c-axis unique. The phase transition diagram is proposed and compared with the phase situation in nondeuterated NH₄BeF₃ crystals.     

High pressure effects on liquid viscosity and glass transition behaviour,polyamorphic phase transitions and structural properties of glasses and liquids

Since the pioneering work of Bridgman it has been known that pressure affects the glass transition of polymers and liquid state viscosities. Usually the T_g and viscosity both increase as a function of pressure as expected from ‘free volume’ theories. However, H₂O provided a notable exception in that the viscosity passes through a minimum at low temperature. It was thought that this might be linked to the anomalous thermal expansion behavior. However further research on geologically important aluminosilicate liquids revealed that they could show anomalous viscosity decreases with increasing pressure and this behavior is given a structural interpretation as five-fold coordinated Si⁴⁺ and Al³⁺ species are formed. Also the existence of polyamorphism or density-driven liquid–liquid phase transitions in certain systems can lead to anomalies in the T_g or η vs. P relations. This may be the case for H₂O, for example. Current research is focusing on investigating structural changes in liquids and glasses at high pressure as the rich variety of behavior is becoming recognized. Both experimental studies and computer simulations are important as the underlying phenomonology is linked to changes in the glass or liquid structure as a function of densification.