Influence of isovalent and heterovalent substitution for Bi<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> on the properties of Bi<Subscript>2</Subscript>Fe<Subscript>4</Subscript>O<Subscript>9</Subscript>-based solid solutions

Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites have been prepared by solid-state reactions at a temperature of 1073 K. X-ray diffraction data indicate that, in the Bi_2–хLa_хFe₄O₉ system, the limiting degree of La³⁺ substitution for Bi³⁺ ions in Bi₂Fe₄O₉ does not exceed 0.05 and that the limiting degree of substitution in the Bi₂Fe_4–2xTi_xCo_xO₉ system lies in the range 0.05 < x < 0.1. The specific magnetization and specific magnetic susceptibility of the samples have been measured at temperatures from 5 to 300 K in a magnetic field of 0.86 T. The field dependences of magnetization obtained for the Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites at temperatures of 300 and 5 K demonstrate that partial isovalent substitution of La³⁺ for Bi³⁺ ions in Bi₂Fe₄O₉ and heterovalent substitution of Ti⁴⁺ and Co²⁺ ions for two Fe³⁺ ions leads to partial breakdown of the antiferromagnetic state and nucleation of a ferromagnetic state.     

Critical Behavior of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>0.95</Subscript>Fe<Subscript>0.05</Subscript>O<Subscript>3</Subscript> Manganite

The critical behavior of perovskite manganite La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ at the ferromagnetic–paramagnetic has been analyzed. The results show that the sample exhibited the second-order magnetic phase transition. The estimated critical exponents derived from the magnetic data using various such as modified d’Arrott plot Kouvel–Fisher method and critical magnetization M(T _C, H). The critical exponents values for the La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ are close to those expected from the mean field model β = 0.504 ± 0.01 with T _C = 275661 ± 0.447 (from the temperature dependence of the spontaneous magnetization below T _C ), γ = 1.013 ± 0.017 with T _C = 276132 ± 0.452 (from the temperature dependence of the inverse initial susceptibility above T _C ), and δ = 3.0403 ± 0.0003. Moreover, the critical exponents also obey the single scaling equation of M(H, ε) = |ε| ^β f _±(H/|ε| ^β+γ ).     

Electrical conductivity of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Tm<Subscript>2</Subscript>O<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> solid solutions

New solid solutions, Bi_2?x?y Tm _x Nb _y O_3+δ, with tetragonal and cubic structures have been synthesized in the Bi₂O₃-Tm₂O₃-Nb₂O₅ system, and their electrical conductivity has been measured at temperatures from 670 to 1020 K. The 1020-K conductivity of the tetragonal solid solution Bi_1.8Tm_0.15Nb_0.05O_3+δ is comparable to that of Bi_1.75Tm_0.25O₃, the best conductor in the Bi₂O₃-Tm₂O₃ system.     

Effect of Bi and Sr doping on morphological and magnetic properties of LaCo<Subscript>0.6</Subscript>Fe<Subscript>0.4</Subscript>O<Subscript>3</Subscript> nanosized perovskites

Nanopowders of La _1?x Bi _x Co_0.6Fe_0.4O₃ (x = 0, 0.1, 0.2) and La _1?2x Bi _x Sr _x Co_0.6Fe_0.4O₃ (x = 0.1) multinary perovskites were synthesized by citrate sol–gel autocombustion method. Crystalline phase and the lattice parameters were obtained from X-ray diffraction pattern. The XRD result shows that all compounds have rhombhohedral crystal structure with \(\bar {\mathbf {R}\mathbf {3}}\)c space group and Bi (x = 0.2) have the presence of secondary peaks. Crystallite size, dislocation density, specific area and strain were calculated from XRD. The elemental composition and micrographs of grain were obtained from EDAX (energy dispersive X-ray analysis) and SEM (scanning electron microscopy), with an average grain size below 400 nm. Surface morphological studies using XPS (X-ray photoelectron spectroscopy) were used to find out the chemical states and surface proportion of oxygen present in samples. Finally, using the vibrating sample magnetometer the room temperature magnetic behaviour of compounds was studied and it was observed that the ferromagnetic behaviour of LaCo_0.6Fe_0.4O₃ was reduced by Bi and Sr doping.     

Properties of fluorine-doped PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> ceramics

We report the first fluorine doping of lead magnesium niobate in the PbMg _{(1 + x)/3}Nb_{(2 ? x)/3}O_{3 ? x} F _x system in a wide composition range, x = 0.025 to 0.625. The fluorine content of the samples is shown to be substantially lower than the intended one because of the fluorine volatilization in the form of HF during synthesis and sintering in air. The ceramics consist of magnesium and lead oxides undetectable by x-ray diffraction, and a perovskite phase whose composition can be represented by the formula PbMg_{(1 + m)/3}Nb_{(2 ? m)/3}O_{3 ? m} F _m , where the fluorine content after sintering is m ≤ 0.12. The PbO and MgO contents of the ceramics depend on the starting mixture composition (x) and heat-treatment conditions (hydrogen fluoride and lead oxide volatilization). As a result of the low fluorine content, the diffraction patterns of the samples show no superlattice reflections, and their lattice parameter varies insignificantly with x. Data are presented on the temperaturedependent dielectric permittivity of ceramic samples sintered and annealed under different conditions.     

Crystallization from high-temperature solutions in the K<Subscript>2</Subscript>O-P<Subscript>2</Subscript>O<Subscript>5</Subscript>-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> system

We have studied general trends of crystallization from high-temperature solutions in the K₂O-P₂O₅-V₂O₅-Bi₂O₃ system at P/V = 0.5?2.0, K/(P + V) = 0.7?1.4, and Bi₂O₃ contents from 25 to 50 wt % and identified the stability regions of BiPO₄, K₃Bi₅(PO₄)₆, K₂Bi₃O(PO₄)₃, and K₃Bi₂(PO₄)_{3 ? x} (VO₄) _x (x = 0?3) solid solutions. The synthesized compounds have been characterized by X-ray powder diffraction and IR spectroscopy, and the structure of two solid solutions has been determined by single-crystal X-ray diffraction (sp. gr. C ₂/c): K₃Bi₂(PO₄)₂(VO₄), a = 13.8857(8), b = 13.5432(5), c = 6.8679(4) Å, β = 114.031(7)°; K₃Bi₂(PO₄)_1.25(VO₄)_1.75, a = 13.907(4), b = 13.615(2), c = 6.956(2) Å, β = 113.52(4)°.     

Electron Spin Resonance Study of Polycrystalline La<Subscript>0.4</Subscript>Bi<Subscript>0.1</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript>

We have inspected the magnetic properties of polycrystalline La_0.4Bi_0.1Ca_0.5MnO₃ using electron spin resonance (ESR) in the temperature range 150–280 K. The temperature dependence of magnetization indicates that the Curie temperature is T _C= 225 K. ESR spectra revealed that the sample is not completely paramagnetic above its Curie temperature through the presence of ferromagnetic interactions in the temperature range 225–270 K which can be attributed to the presence of Griffiths phase in this temperature range. The sample becomes completely paramagnetic above 270 K. The presence of Griffiths phase can be attributed to the disorder induced by the 6 s ² lone pair electrons of Bi³⁺ ions.     

Effect of Zr Addition on Bi<Subscript>1.8</Subscript>Pb<Subscript>0.4</Subscript>Sr<Subscript>2.0</Subscript>Ca<Subscript>1.1</Subscript>Cu<Subscript>2.1</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Superconductor

The polycrystalline Bi_1.8Pb_0.4Sr_2.0Ca_1.1Cu_2.1 M_xO _y , with M = Zr (x = 0.0, 0.02, 0.04), were synthesized by solid-state reaction method and studied by X-ray diffraction analysis (XRD), scanning electron microscopy equipped with energy dispersive of X-ray analysis (SEM/EDX) and resistivity versus temperature measurements. The influence of the Zr addition on the Tc and microstructure properties of the superconducting compounds has been studied. SEM observations show whiskers grains randomly distributed and microstructural change due to the addition of Zr. The ZrO₂ was incorporated into the crystalline structure of BSCCO system in all samples. The crystallographic structure remains in a tetragonal form where a= b≠c. Generally, all samples exhibit semiconductor behaviour above \(T_{\mathrm {c}}^{\text {onset}}\). The onset critical temperature \(T_{\mathrm {c}}^{\text {onset}}\) increases up to 86 with x = 0.02. There is an enhancement in the critical temperature for doped samples as compared with pure Bi_1.8Pb_0.4Sr_2.0Ca_1.1Cu_2.1O _y .Changes in superconducting properties of ZrO₂ nanoparticle added Bi-2212 system were discussed.     

Enhanced magnetoelectric coupling in La-modified Bi<Subscript>5</Subscript>Co<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>Ti<Subscript>3</Subscript>O<Subscript>15</Subscript> multiferroic ceramics

Multiferroic properties of La-modified four-layered perovskite Bi_5?x La _x Fe_0.5Co_0.5Ti₃O₁₅ (0 ≤ x ≤ 1) ceramics were investigated, by analyzing the magnetodielectric effect, magneto-polarization response and magnetoelectric conversion. X-ray diffraction indicated the formation of pure Aurivillius ceramics, and Raman spectroscopy revealed the Bi ions displacement and the crystal structure variation. The enhancement of ferromagnetic and ferroelectric properties was observed in Bi_5?x La _x Fe_0.5Co_0.5Ti₃O₁₅ after La modification. The evidence for enhanced ME coupling was determined by magnetic field-induced marked variations in the dielectric constant and polarization. A maximum ME coefficient of 1.15 mV/cm·Oe was achieved in Bi_4.25La_0.75Fe_0.5Co_0.5Ti₃O₁₅ ceramic, which provides the possible promise for novel magnetoelectric device application.     

The magnetic properties of BiY<Subscript>2</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> nanoparticles doped with Cr ions

BiY₂Cr _x Fe_5?x O₁₂ (x = 0, 0.05, 0.1, 0.2, 0.3) nanocrystals were synthesized by using a sol-gel method. Samples were characterized by the powder X-ray diffraction (XRD), the thermal gravity analysis (TGA) and the differential thermal analysis (DTA), the vibrating sample magnetometer(VSM) and Mössbauer spectrums. The average sizes of the particles were determined by the Scherrer’s formula. The special Ms and Mössbauer spectra of BiY₂Cr _x Fe_5?x O₁₂ nanocrystals are researched at room temperature. It is seen that the special Mss of samples are initially increased with increasing Cr³⁺ content (x < 0.1), and decreased with increasing content of Cr³⁺ ions (x > 0.1).     

Overlapping Large Polaron Conductivity Mechanism and Dielectric Properties of Al<Subscript>0.2</Subscript>Cd<Subscript>0.8</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> Ferrite Nanocomposite

In this work, the conduction and dielectric properties of Al_0.2Cd_0.8Fe₂O₄ ferrite nanoparticle, which was synthesized by a co-precipitation method, were investigated. Experimental data were taken from 20 Hz to 10 MHz and from 293 to 613 K. AC conductivity of the sample was analyzed within the framework of the overlapping large polaron tunneling (OLPT) mechanism. DC conductivity behavior fits the classical Arrhenius-type conductivity in the examined temperature range. Electrical properties of the material sample have been studied using an impedance spectroscopy technique. The effect of frequency and temperature on dielectric constant (ε ^′), dielectric loss (tan ??), and impedance (Z′ and Z′′) has been discussed in terms of hopping of charge carriers between Fe²⁺ and Fe³⁺ ions. According to results, a relaxation process fits the Cole–Cole model.     

Effect of BiI<Subscript>3</Subscript> doping on the optical properties of CaI<Subscript>2</Subscript>

The effect of BiI₃ doping on the optical absorption spectra and roentgeno-, photo-, and thermoluminescence of CaI₂ scintillator crystals has been studied in the temperature range 90–295 K. The crystals were grown by the Bridgman-Stockbarger method. Doping of CaI₂ with BiI₃ from the melt gives rise to absorption bands centered at 466, 400, and 350 nm, which can be interpreted as the A, B, and C bands due to electronic transitions from the ¹ S ₀ state to the ³ P ₁, ³ P ₂, and ¹ P ₁ levels of a free Bi³⁺ ion. The absorption band at 270–290 nm is assignable to near-activator excitons. Changes in spectral composition and the reduction in luminescence intensity caused by Bi³⁺ doping of CaI₂ are associated mainly with the reabsorption of the emission from centers characteristic of the host by activator centers. Under x-ray excitation, the spectrum of heavily doped crystals shows, in addition, a weak emission centered around 620 nm, which is probably due to an impurity phase. The light sum of CaI₂:Bi³⁺ under x-ray excitation is small and is due to shallow traps. Upon Bi³⁺ substitution on the cation site of CaI₂, the excess charge of the activator is probably compensated by unintentional O^2? impurity and vacancy pairs near Bi³⁺ centers—one vacancy in a neighboring cation site and the other in a neighboring anion site.     

Effects of Ge<Superscript>4+</Superscript> acceptor dopant on sintering and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript> lead-free piezoceramics

Lead-free (K_0.5Na_0.5)(Nb_1-xGe _x )O₃ (KNN-xGe, where x = 0-0.01) piezoelectric ceramics were prepared by conventional ceramic processing. The effects of Ge⁴⁺ cation doping on the phase compositions, microstructure and electrical properties of KNN ceramics were studied. SEM images show that Ge⁴⁺ cation doping improved the sintering and promoted the grain growth of the KNN ceramics. Dielectric and ferroelectric measurements proved that Ge⁴⁺ cations substituted Nb⁵⁺ ions as acceptors, and the Curie temperature (T_C) shows an almost linear decrease with increasing the Ge⁴⁺ content. Combining this result with microstructure observations and electrical measurements, it is concluded that the optimal sintering temperature for KNN-xGe ceramics was 1020°C. Ge⁴⁺ doping less than 0.4 mol.%can improve the compositional homogeneity and piezoelectric properties of KNN ceramics. The KNN-xGe ceramics with x = 0.2% exhibited the best piezoelectric properties: piezoelectric constant d₃₃ = 120 pC/N, planar electromechanical coupling coefficient k_p = 34.7%, mechanical quality factor Q_m = 130, and tanδ = 3.6%.     

Magnetic Entropy Change by Mean-Field Theory for the Second-Order Phase Transition Manganite Nd<Subscript>0.6</Subscript>Sr<Subscript>0.3</Subscript>Ca<Subscript>0.1</Subscript>Mn<Subscript>0.975</Subscript>Fe<Subscript>0.025</Subscript>O<Subscript>3</Subscript>

In this work, we are going to show the method based on mean-field scaling for the Nd_0.6Sr_0.3Ca_0.1Mn_0.975Fe_0.025 O₃ sample, where from scaling of experimental magnetization data, the mean-field exchange parameter λ and the f function of the equation of state \(M(T,H)=B_{S} [\frac {\left ({H+H_{\text {ex}}} \right )}{T}]\) are directly determined. The scaling approach allows finding the dependence of H _ex on T or higher powers of M, which determine the order of the phase transition. Quantum spin number has been determined. In this study, we use \(\left | {\Delta S_{M} (T)} \right |\) obtained from isothermal magnetization measurements; we compare this result to mean-field theory fittings from a novel scaling method through the use of theoretical results S, g, and λ. The obtained results by mean-field theory are suitable and in good agreement with the classical Maxwell relation.     

High-temperature crystal chemistry of Na<Subscript>6</Subscript>(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>O(MoO<Subscript>4</Subscript>)<Subscript>4</Subscript>

Thermal deformations of Na₆(UO₂)₂O(MoO₄)₄ were studied by high-temperature powder X-ray diffraction. The compound crystallizes in the triclinic system, space group Р\(\bar 1\), a = 7.636(7), b = 8.163(6), c = 8.746(4) Å, α = 72.32(9)°, β = 79.36(4)°, γ = 65.79(5)°, V = 472.74(4) ų. It is stable in the temperature interval 20–700°С. The thermal expansion coefficients (TECs) are α₁₁ = 25.5 × 10^–6, α₂₂ = 7.8 × 10^–6, and α₃₃ = 1.1 × 10^–6 (°C)^–1. The orientation of the TEC pattern relative to the crystallographic axes is a₃₃^Z = 45°, a₃₃^X = 122°, a₂₂^Z = 59°, and a₂₂^X = 66°. The anisotropy of the thermal expansion is due to specific features of the crystal structure of the compound.     

Spin Glass in a Geometrically Frustrated Magnet of ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Nanoparticles

We investigated the magnetic properties of a geometrically frustrated magnet of ZnFe₂O₄ nanoparticles by carrying out the comprehensive measurements of dc magnetization and ac susceptibility. Spin glass is confirmed to occur in this weakly Fe(Zn)-ionic-inversed sample. The common characteristics of spin glass including the aging, the memory, and the rejuvenation effects were observed. By using the critical-power law to study the spin dynamics, the spin-glass transition temperature T_g is obtained to be 18 K and the dynamic exponent zν is 8.0. The weak exchange interaction disorder introduced by the ferrimagnetic J_AB interaction, together with the weak nonmagnetic dilute disorder induced by the ionic inversion, is responsible for the formation of spin glass in the ZnFe₂O₄ nanoparticles.     

Study of Magnetic Entropy Change in Nd<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>0.98</Subscript>Fe<Subscript>0.02</Subscript>O<Subscript>3</Subscript> by Means of Theoretical Models

Magnetic entropy change (?ΔS _M ) of Nd_0.67 Ba_0.33Mn_0.98Fe_0.02O₃ perovskite have been analyzed by means of theoretical models. An excellent agreement has been found between the (ΔS_M) values estimated by Landau theory and those obtained using the classical Maxwell relation. In order to estimate the spontaneous magnetization M _{s pont}(T), we used the mean-field theory to analyses the (ΔS_M) vs. M ² data. The obtained M _{s pont}(T) values are in good agreement with those found from the classical extrapolation from the Arrott plots(H/M vs. M ²), confirming that the magnetic entropy is a valid approach to estimate the spontaneous magnetization in our system. At a relatively low magnetic field, a phenomenological model has been used to estimate the values of the magnetic entropy change. The results are in good agreement with those obtained from the experimental data using Maxwell relation.     

Ionic conductivity of BaF<Subscript>2</Subscript> + ZnF<Subscript>2</Subscript> + CdF<Subscript>2</Subscript> + YbF<Subscript>3</Subscript> optical fluoride ceramic

The electrical conductivity of an optical fluoride ceramic in the quaternary system BaF₂ + ZnF₂ + CdF₂ + YbF₃ has been determined in the temperature range 338–722 K using impedance spectroscopy (5 to 5 × 10⁵ Hz). The 500-K ionic conductivity of the ceramic is σ = 3.3 × 10^–4 S/cm, which corresponds to the electrical characteristics of single crystals of the best conducting nonstoichiometric M_1–x R _x F_{2 + x} (M = Sr, Ba; R = La–Nd; x = 0.3–0.5) fluorite phases. We have observed nonmonotonic variation (breaks) in temperature-dependent σ, which is due to competing fluoride ion transport processes in different parts of the ceramic sample. The highly conductive state of the BaF₂ + ZnF₂ + CdF₂ + YbF₃ fluoride ceramic seems to be due to the formation of structural regions corresponding to a Ba_1–x Yb _x F_{2 + x} solid solution.     

Crystal structure of KNa<Subscript>3</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>5</Subscript>O<Subscript>6</Subscript>(SO<Subscript>4</Subscript>)]

The crystal structure of a previously unknown compound KNa₃[(UO₂)₅O₆(SO₄)] [space group Pbca, a = 13.2855(15), b = 13.7258(18), c = 19.712(2) Å, V = 3594.6(7) ų] was solved by direct methods and refined to R ₁ = 0.055 for 3022 reflections with |F _hkl | ≥ 4σ |F _hkl |. In the structure there are five sym-metrically nonequivalent uranyl cations. They are linked by cationcation (CC) interactions to form a pentamer whose central cation is U(2)O ₂ ²⁺ forming two three-centered CC bonds. All the uranyl ions are coordinated in the equatorial plane by five O atoms, which leads to the formation of pentagonal bipyramids sharing common edges to form layers parallel to the (100) plane. The sulfate tetrahedron links the uranyl layers into a 3D framework. The K⁺ and Na⁺ cations are arranged in framework voids. A brief review of CC interactions in U(VI) compounds is presented.     

Electric field effect on the short-range order in amorphous Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> films

The short-range order in thin amorphous Bi₂S₃ films grown under ordinary conditions and in an applied electric field of 3000 V/cm has been studied. The interatomic distances obtained are r ₁ = 0.23 nm, r ₂ = 0.345 nm, and r ₃ = 0.45 nm, and the corresponding coordination numbers are n ₁ = 4, n ₂ = 6, and n ₃ = 5.88. The coordination numbers and the ratios r ₃/r ₁ = 1.96 and r ₂/r ₁ = 1.5 indicate that the atoms in amorphous Bi₂S₃ are in tetrahedral and octahedral coordination. In the films grown in an electric field, the near neighbor distances are slightly shorter.