This article investigates the structures and conductive properties of polycrystals of Na3Fe2(PO4)3 obtained by solid-state and melt synthesis methods using concentrated optical radiation. It has been established that in the melt synthesis method, the material is synthesized under significantly non-equilibrium thermodynamic conditions, leading to the creation of deformations in the sample, which contribute to the enhancement of ionic conductivity. Additionally, the synthesis duration is reduced by half. Through a comparative assessment of the structural parameters and conductive properties of these materials, it is demonstrated that polycrystals obtained by the melt method exhibit better texture and higher ionic conductivity. The occurrence of deformations during the synthesis of α-Na3Fe2(PO4)3 under high temperature-gradient conditions indicates the elasticity of the crystalline framework {[Fe2(PO4)]3−}3∞. It is concluded that the non-equilibrium thermodynamic conditions of α-Na3Fe2(PO4)3 synthesis promote the formation of deformations in the crystalline structure of polycrystals, leading to a partial increase in symmetry and ionic conductivity.
This article studies the influence of solid-phase (type 1 samples) and melt-quenching (type 2 samples) technological modes of obtaining Na3Fe2(PO4)3 polycrystals on their structures and ion-conducting properties. α-Na3Fe2(PO4)3 polycrystals of the 1st type are formed predominantly under an isothermal firing regime, and the synthesis of the 2nd type is carried out under sharp temperature gradient conditions, contributing to the formation of glassy precursors possessing a reactive and deformed structure, in which the crystallization of crystallites occurs faster than in precursors obtained under isothermal firing. The elemental composition of α-Na3Fe2(PO4)3 type 2 polycrystals is maintained within the normal range despite the sharp non-equilibrium thermodynamic conditions of synthesis. The microstructure of the type 1 Na3Fe2(PO4)3 polycrystals is dominated by chaotically arranged crystallites of medium (7–10 μm) and large (15–35 μm) sizes, while the polycrystals of type 2 are characterized by the preferential formation of small (3–4 μm) and medium (7–10 μm) crystallites, causing uniaxial deformations in their structure, which contribute to a partial increase in their symmetry. The advantage of type 2 polycrystals is that they have higher density and conductivity and are synthesized faster than type 1 samples by a factor of 4. The article also considers the issues of crystallization in a solid-phase precursor from the classical point of view, i.e., the process of the formation of small solid-phase nuclei in the metastable phase and their growth to large particles due to association with small crystallites using phase transitions. Possible variants and models of crystallite growth in Na3Fe2(PO4)3 polycrystals, as well as distinctive features of crystallization between two types of samples, are discussed.
In this paper influence of the excess Ca and Cu cations on the critical temperature (Tc) and critical transport current density (Jc) of high-temperature superconducting ceramics of the compositions (HTSC) Bi1.6Pb0.4Sr2Ca2.1Cu3.1Oy, Bi1.6Pb0.4Sr2Ca2.25Cu3.25Oy and Bi1.6Pb0.4Sr2Ca3Cu4Oy synthesized by the glass-ceramic method has been studied. The synthesis of superconducting ceramics was carried out on the basis of the glass phase, obtained by ultra-fast quenching of the melt. Melting of the mixture of starting components was carried out without the use of a crucible under the influence of IR radiant heating. Analysis of the elemental composition of the samples of the initial precursors showed a significant deviation from stoichiometry in oxygen (increase), as well as a decrease in calcium content. The synthesis of HTSC ceramics was carried out at a temperature of 849–850 °C for 96 h with intermediate grinding every 24 h. Studies of the phase composition of ceramic samples by X-ray diffraction have shown that HTSC ceramics consist only of a superconducting high-temperature phase Bi-2223. Studies of current-carrying characteristics by the four-point probe method according to the criterion of 1 µV/cm2 have shown that high-temperature superconducting ceramics of the compositions Bi1.6Pb0.4Sr2Ca2.1Cu3.1Oy, Bi1.6Pb0.4Sr2Ca2.25Cu3.25Oy and Bi1.6Pb0.4Sr2Ca3Cu4Oy have an increased density of critical transport current of 9.12 A/cm2, 7.62 A/cm2 and 7.26 A/cm2, respectively. At the same time, it was found that with a decrease in the content of Ca and Cu cations in HTSC ceramics, an increase in the critical current density is observed.
In this work, the features of the structure-conductivity relationship in polar (α) and ion-conducting (β and γ) phases of Na3Fe2(PO4)3 polycrystals obtained by the melt-quenching method have been investigated. Na3Fe2(PO4)3 polycrystals are synthesized by isothermal firing of glassy precursors (after grinding and pressing). The glassy precursors were prepared by melting a pre-calcined (350 C) mixture of initial reagents under the influence of thermal and infrared radiation energy and rapid cooling of the melt (or quenching). It was found that the deformations of the structure of polycrystals α-Na3Fe2(PO4)3 during synthesis by melt-quenching lead to an increase in the conductivity in polar (α) and ion-conducting (β and γ) phases because they contribute to the reduction of structural distortions of the samples. Polycrystals Na3Fe2(PO4)3 obtained by the melt-hardening method have high-quality crystallites, high density, and conductivity, and their synthesis is faster than samples obtained by other methods. The established advantages of synthesized polycrystals of α-Na3Fe2(PO4)3 are probably connected with deformations of structure and chemical activity of glassy precursors caused by nonequilibrium thermodynamic conditions of synthesis. For the first time, it was possible to detect domain structures in polycrystals of α-Na3Fe2(PO4)3 obtained by the melt-quenching method, which confirms the polarity of the α-phase, the appearance of which is associated with the ordered displacement of the cationic sublattice relative to the anionic sublattice under the influence of monoclinic distortion of the crystal framework.
The article investigates the dielectric and conductive properties of the polar α-phase of Na3Fe2(PO4)3 polycrystals synthesized by solid-phase (sample type 1), melt (type 2), and melt-quenching (type 3) methods. To enable a rapid assessment of the dielectric properties of the polar α-phase of Na3Fe2(PO4)3, the thermo-polarization mobility parameter μTp(T, E(ω)) was introduced. By studying the dielectric properties, it was concluded that the polar α-phase of type 1 samples consists of large and small dipoles and ordered sodium cations, which possess low values of μTp(T, E(ω)), indicating the presence of strong interaction forces between the crystal lattice and the cationic part of the polycrystal. Additional studies of the samples’ conductivity confirm this conclusion. Studies of the polar α-phase of Na3Fe2(PO4)3 in type 2 samples have established that their structure contains dipoles and sodium cations with higher values of μTr(T, E(ω)), and also exhibits higher conductivity than Type 1 samples. These data indicate a weakening of the interaction forces between the cationic and anionic components in type 2 polycrystals due to a partial increase in crystal symmetry. The results of studies of the polar α-phase of type 3 samples show that their structure contains dipoles and sodium cations with higher values of μTr(T, E(ω)), and also exhibits higher conductivity than type 2 samples. It is concluded that the structure of type 3 samples is characterized by weak interaction forces between the cationic and anionic parts as a result of an increase in the symmetry of the polar α-phase of Na3Fe2(PO4)3, caused by sharply graded temperature conditions during the synthesis of polycrystals. By studying the dielectric properties of cathode materials, it is possible to obtain information on the extent of interactions between the cationic and anionic components in polycrystals. It is, therefore, appropriate to use this approach when investigating a wide range of new dielectric and ion-conducting materials.
This article presents the results of studies of the structure and conductive properties of Na3Fe2(PO4)3 polycrystals synthesized by solid-phase and melt (using concentrated optical radiation) methods. It has been established that with the melt method, the synthesis of the material occurs under significantly nonequilibrium temperature-gradient conditions, which leads to the creation of deformations in the sample that contribute to an increase in ionic conductivity. The ability of the Na3Fe2(PO4)3 structure to adapt to anomalous deformations that occur under temperature-gradient conditions indicates the elasticity of the crystalline framework {[Fe2(PO4)]3-}3∞. Through a comparative assessment of the structural parameters and conductive properties of these materials, it is shown that polycrystals obtained by the melt method have a better texture and greater ionic conductivity. The advantage of this method is that the duration of the synthesis of α-Na3Fe2(PO4)3 is halved. It is concluded that this method is applicable to obtain effective polycrystals of other compositions.