Structure of Cs<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Rb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> solid solutions

Cs_{1 − x} Rb _x H₂PO₄ solid solutions have been synthesized for the first time in a broad composition range, x = 0.03–0.9. At room temperature, the Cs_{1 − x} Rb _x H₂PO₄ solid solutions are isostructural with the low-temperature phase of CsH₂PO₄ over the entire composition range studied. In the CsH₂PO₄-based solid-solution series, the unit-cell parameters and volume decrease with increasing Rb content. At high temperatures, the Cs_{1 − x} Rb _x H₂PO₄ solid solutions exist in the range x = 0–0.4, are isostructural with cubic CsH₂PO₄, and have a smaller unit-cell parameter.     

Structure and dielectric properties of (1 − <Emphasis Type="Italic">x</Emphasis>)BiFeO<Subscript>3</Subscript> · <Emphasis Type="Italic">x</Emphasis>(KBi)<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> perovskite solid solutions

(1 − x)BiFeO₃ · x(KBi)_1/2TiO₃ ceramics have been prepared by solid-state reactions. The system has been shown to contain a continuous series of perovskite solid solutions. In the composition ranges x < 0.4, 0.4 < x < 0.9, and x > 0.9, the solid solutions have rhombohedral, orthorhombic, and tetragonal structures, respectively. The observed compositional phase transitions are accompanied by sharp changes in unit-cell volume. We describe the dielectric properties of the orthorhombic solid solutions, which demonstrate that these materials exhibit relaxor behavior.     

Electrical conductivity and thermal stability of (1 ? x )CsH2PO4/ x SiP y O z ( x = 0.2–0.7) composites

The physicochemical properties of (1 − x)CsH₂PO₄/xSiP _y O _z (x = 0.2–0.7) composites containing fine-particle silicon phosphates as heterogeneous additives have been studied at different humidities. The introduction of silicon phosphates suppresses the superionic phase transition of CsH₂PO₄ and increases the low-temperature conductivity of the materials, which depends significantly on humidity. The CsH₂PO₄-SiP _y O _z materials offer high conductivity (∼3 × 10⁻³ to 10⁻² S/cm at ∼110–230°C) at low water vapor pressures (3 mol % H₂O). Amorphization of the CsH₂PO₄ in the composites markedly changes its thermodynamic properties. The effect of long-term isothermal holding (210°C, 3 mol % H₂O) on the conductivity of the composites has been studied. Original Russian Text ? V.G. Ponomareva, E.S. Shutova, G.V. Lavrova, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 9, pp. 1131–1136.     

Synthesis and properties of AgTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based NASICON-type phosphates doped with Nb<Superscript>5+</Superscript>, Zr<Superscript>4+</Superscript>, and Ga<Superscript>3+</Superscript>

We have synthesized materials based on a silver titanium phosphate with partial substitution of tri-, tetra-, or pentavalent cations for titanium: Ag_1±x Ti_2−x M _x (PO₄)₃ (M = Nb⁵⁺, Ga³⁺) and AgTi_2−x Zr _x (PO₄)₃. The materials have been characterized by X-ray diffraction and impedance spectroscopy and have been shown to have small thermal expansion coefficients. Their ionic conductivity has been determined. Silver ions in these materials are difficult to replace with protons.     

Preparation of Pb(Zr,Ti)O<Subscript>3</Subscript>–Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> piezoelectric ceramics by dry–dry method

Ternary perovskite ceramics of Pb[(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x]_0.98Nb_0.02O_3.01 (PZTMN, x = −0.075, −0.05, −0.025, 0, 0.025, 0.05, and 0.075 ), are synthesized via dry–dry method. B-site precursors of PZTMN ([(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x ]_0.98Nb_0.02O_2.01, ZTMN) can be synthesized via a two-step solid state reaction method. The first calcination temperature is 1,300 °C, and the second is not higher than 1,360 °C. Incorporation of magnesium and niobium ions promotes the formation of the single phase solid solution with ZrTiO₄ structure. Single phase perovskite PZTMN is formed at 780 °C, much lower than that in conventional process. Dense ceramics can be sintered at about 1,260 °C with dielectric and piezoelectric properties comparable to that of wet–dry method and higher than that of conventional method. It seems that B-site precursor method is cost effective in preparation of ternary piezoelectric ceramics.     

Dielectric properties of (1 − <Emphasis Type="Italic">x</Emphasis>)KNbO3 · <Emphasis Type="Italic">x</Emphasis>BiMg<Subscript>2/3</Subscript>Nb<Subscript>1/3</Subscript>O<Subscript>3</Subscript> perovskite solid solutions

(1 − x) KNbO₃ · xBiMg_2/3Nb_1/3O₃ ceramic materials have been prepared by solid-state reactions. The materials with x < 0.3 have been shown to be perovskite solid solutions. Their average lattice parameter increases linearly with x. Like undoped KNbO₃, the solid solutions undergo a low-temperature (rhombohedral → orthorhombic) ferroelectric phase transition. The transition temperature increases almost linearly with x. The dc electrical conductivity of the ceramics exhibits Arrhenius behavior. The activation energy for conduction rises sharply near the phase transition temperature.     

Synthesis and luminescence properties of Eu<Superscript>2+</Superscript>-doped Li<Subscript>2</Subscript>SrSiO<Subscript>4</Subscript>

We have studied the luminescence spectra of Li₂Sr_{1 − x} Eu _x SiO₄ (x = 0.0001–0.01) solid solutions prepared by solid-state reactions and a sol-gel process in a reducing atmosphere. The spectra show a broad band in the range 500–700 nm, centered at 578 nm, which is due to the 4f ⁶5d → 4f ⁷ transition. The luminescence excitation spectrum shows, in addition to bands due to Eu²⁺ 4f ⁷ → 4f ⁶5d transitions, a strong band centered at 174 nm, attributable to absorption in the SiO₄⁴⁻ group.     

Phonons in mixed superionic fluorites (BaF<Subscript>2</Subscript>)<Subscript>1-x</Subscript>(LaF<Subscript>3</Subscript>)<Subscript>x</Subscript>

In recent years, the fluorite-structured solid solutions with the general formula, (MF₂)_1-x(RF₃)_x (M = Ca, Sr, Ba, Pb and R is a rare-earth element or Y), have been the subject of numerous experimental studies focussed on their superionic properties. The overall cubic crystal symmetry (space group Fm3m) is conserved up to x ≶ x_max, where x_max ⊁ 0.4-0.5 depending on M and R. The zone centre phonons and phonon dispersion along three symmetry directions of the mixed superionic compound (BaF₂)_1-x(LaF₃)_x have been investigated by applying de Launey angular force model for x ≶ x_max. The calculated results are compared and explained with available experimental results.     

Citrate–nitrate combustion route to the synthesis of (1−<Emphasis Type="Italic">x</Emphasis>)LaCrO<Subscript>3</Subscript>–<Emphasis Type="Italic">x</Emphasis>BiCrO<Subscript>3</Subscript> solid solution

Solid solution of (1−x)LaCrO₃–xBiCrO₃ (x = 0, 0.10, 0.15, 0.20 and 0.25) was prepared via the citrate–nitrate combustion synthesis. Pure perovskite phase was obtained at 800 °C, a much lower synthesis temperature than that needed in the solid-state reactions. The thermodynamics of phase formation and the ceramic sintering mechanism were investigated. The substitution of Bi³⁺ for La³⁺ was found to give a separate exothermic decomposition event in the gels and the precursor did not produce a transient liquid phase while heating to 1200 °C, as was found in ceramics prepared by solid state reaction. This finding shows that the role of Bi₂O₃ in the sintering of the La_1−x Bi _x CrO₃ ceramics depends on the processing method.     

Study of structure and properties of ZnO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Glasses of the ternary system ZnO–Bi₂O₃–P₂O₅ were prepared and studied in two compositional series 50ZnO–xBi₂O₃–(50 − x)P₂O₅ and (50 − y)ZnO–yBi₂O₃–50P₂O₅. Two distinct glass-forming regions were found in the 50ZnO–xBi₂O₃–(50 − x)P₂O₅ glass series with x = 0–10 and 20–35 mol.% Bi₂O₃. All prepared Bi₂O₃-containing glasses reveal a high chemical durability. Small additions of Bi₂O₃ (∼5 mol.%) improve thermal stability of glasses. All glasses crystallize on heating within the temperature range of 505–583 °C. Structural studies by Raman and ³¹P MAS NMR spectroscopies showed the rapid depolymerisation of phosphate chains within the first region with x = 0–15 and the presence of isolated Q⁰ phosphate units within the second region with x = 20–35. Raman studies showed that bismuth is incorporated in the glass structure in BiO₆ units and their vibrational bands were observed within the spectral region of 350–700 cm⁻¹. The evolution of properties and the spectroscopic data are both in accordance with a network former effect of Bi₂O₃.     

Properties of Mg(Fe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>O<Subscript>4 + δ</Subscript> solid solutions in stable and metastable states

Using pyrohydrolytic synthesis, we have obtained a continuous series of Mg(Fe_{1 − x} Ga _x )₂O_{4 + δ} solid solutions, as checked by X-ray diffraction. The magnetization and coercivity of the samples have been determined from field dependences in applied magnetic fields of ±5 T, and their conductivity has been assessed using current-voltage measurements at 300 K in electric fields from −200 to +200 V. The effective band gap of the solid solutions has been evaluated from their absorption spectra obtained by diffuse reflectance measurements. The optimal composition for spintronic applications is Mg(Fe_0.8Ga_0.2)₂O_{4 + δ}.     

Enhanced Superconducting Properties of Air-Processed GdBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-δ</Subscript> Single Domains with BaCO<Subscript>3</Subscript>/BaCuO<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript> Addition

Single domain GdBa₂Cu_7-δ (Gd123) bulk superconductors were fabricated in air by top-seeding melt-texture growth. Performance of the air-processed Gd123 was successfully enhanced by addition of both BaCO₃ and BaCuO_2−x , which suppress the formation of Gd_1+x Ba_2−x Cu₃O_7-δ solid solutions. The optimum doping amount ranges from 0.05 to 0.15, M BaCO₃ and 0.05 to 0.1, M BaCuO_2−x per molar Gd123. The distribution of the second phase particles was observed by scanning electron microscopy. A narrow band formed by Gd₂BaCuO₅ particle concentration appeared around the seeding zone in both a–b plane and c-growth sector in Gd123 single grain. Trapped magnetic field density reached 0.67, T for sample with 24 mm in diameter and 8, mm in thickness and a high critical current density J _c up to 91,200, A/cm² was achieved at 77, K under self-field.     

Investigation of Cs(H2PO4)1 − x (HSO4) x (x = 0.15–0.3) superprotonic phase stability

A detailed investigation of the highly conductive Cs(H₂PO₄)_1?x (HSO₄) _x (x = 0.15–0.3) proton electrolyte, its structural properties, and ageing behavior was carried out using X-ray diffraction, DSC, and impedance and NMR spectroscopy. The high conductivity of electrolytes (～2 × 10^?2 S/cm) remains stable during long-term ageing at 180–200°C due to stabilization of the high temperature phase to lower temperatures. The room temperature ¹H MAS NMR spectrum of (CsH₂PO₄)_1?x (CsHSO₄) _x demonstrates the predominantly highly mobile protons present in these materials with the residual low-mobile protons, which agrees with the XRD data. According to XRD and ¹H NMR data, the cubic phase of Cs(H₂PO₄)_{1 ? x} (HSO₄) _x (x = 0.15–0.3) that stabilizes at room temperature gradually transforms to a low-temperature monoclinic one. The kinetics of the phase transformation for mixed salt depends markedly on the relative air humidity. A possible stabilization mechanism of the Cs(H₂PO₄)_{1 ? x} (HSO₄) _x superionic phase with high proton mobility at low temperatures is discussed.     

Multifunctional anti-stokes Y<Subscript>2</Subscript>O<Subscript>2</Subscript>S-based white phosphors

We have established the key trends in the variation of the intensity of the visible and IR luminescence of (Y_{1 − x − y − z} Yb _x Tm _y Er _z )₂O₂S solid solutions in relation to their composition under laser excitation at λ = 0.940 μm. The results obtained have been used to develop multifunctional anti-Stokes white phosphors with various tinges and a predetermined relative intensities of visible and IR emission bands.     

Thermoelectric power factor of Ti<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>V<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>NiSn alloys

Ti_{1 − x} V _x NiSn (x = 0–0.10) substitutional solid solutions have been prepared by doping the intermetallic semiconductor n-TiNiSn (half-Heusler phase) with vanadium, a donor impurity, and their resistivity and thermopower have been measured at temperatures from 80 to 380 K. The results demonstrate that, when doping of TiNiSn causes no type inversion, the thermoelectric power factor of the solid solution markedly exceeds that of the undoped ternary compound.     

Spectroscopic studies of TeO<Subscript>2</Subscript>–ZnO–Er<Subscript>2</Subscript>O<Subscript>3</Subscript> glass system

Series of glass based on the (80 − x)TeO₂–20ZnO–(x)Er₂O₃ system (0.5 mol% ≤ x ≤ 2.5 mol%) has successfully been made by melt quenching technique. The optical properties of glass have been investigated by means of IR and Raman spectroscopy. It is observed that as the Er₂O₃ content is being increased, the sharp IR absorption peaks are consistently shifted from 650 to 672 cm⁻¹ while the Raman shift intensity around 640–670 cm⁻¹ is decreases but increases around 720–740 cm⁻¹. It is found out that both phenomenons are related to the structural changes between the stretching vibration mode of TeO₄ tbp and TeO₃ tp, and bending vibration mode of Te–O bonds in the glass linkages.     

Structural and thermoelectric properties of Zr<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Er<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>NiSn solid solutions

We have studied the electronic and crystal structures and temperature-dependent resistivity and thermopower of Zr_{1 − x} Er _x NiSn (x = 0–0.20) substitutional semiconductor solid solutions (so-called half-Heusler alloys) in the temperature range 80–380 K. Heavily erbium doped semiconductors with the MgAgAs structure are described in terms of an amorphous semiconductor model. The erbium atoms in Zr_{1 − x} Er _x NiSn are shown to act as acceptors. Density of states calculation results for the Zr_{1 − x} Er _x NiSn alloys are consistent with experimental data.     

Influence of Sm substitution on the phase,microstructure and microwave dielectric properties of SrLa<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>17</Subscript>

New dielectric ceramics in the SrLa_4−xSm_xTi₅O₁₇ (0 ≤ x ≤ 4) composition series were prepared through a solid state mixed oxide route to investigate the effect of Sm⁺³ substitution for La⁺³ on the phase, microstructure and microwave dielectric properties. At x = 0–3, all the compositions formed single phase ceramics within the detection limit of in-house X-ray diffraction when sintered in the temperature range 1500–1580 °C. At x = 4, a mixture of Sm₂Ti₂O₇ and SrTiO₃ formed. The maximum Sm⁺³-containing single phase ceramics, SrLaSm₃Ti₅O₁₇, exhibited relative permittivity (ε_r) = 42.6, temperature coefficient of resonant frequency (τ _f ) = −96 ppm/^oC and quality factor (Q _u f _o ) = 7332 GHz. An analysis of results presented here indicates that SrLa_4−xSm_xTi₅O₁₇ ceramics, exhibiting τ _f  ~ 0 and ε_r ~ 53 could be achieved at x ~ 1.4 but at the cost of decrease in Q _u f _o .     

Synthesis and structural studies of Na<Subscript>2</Subscript>O-ZnO-ZnF<Subscript>2</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> oxyfluoride glasses

This paper describes the synthesis and spectroscopic studies of the glass system, 20Na₂O-(20-x) ZnO-xZnF₂-60B₂O₃(x = 0, 5, 10, 15, 20), prepared by melt quenching method. The analyses of DSC and XRD did not show the crystallinity of the glass sample. ¹¹B MAS-NMR shows the presence of sharp peak around −14 ppm. From the IR studies, the broadening of the peak around 1200–1400 and 800–1100 cm⁻¹ shows the presence of mixed linkages like B-O-B, B-O-Zn in the network.     

Effect of Pr<Superscript>3+</Superscript> on the stokes luminescence of YPO<Subscript>4</Subscript>:Nd<Superscript>3+</Superscript> under IR excitation

We have identified general relationships between the spectral and kinetic properties of the IR Stokes luminescence bands of Y_{1 − x − y} Nd _x Pr _y PO₄ solid solutions in the spectral range 0.86–1.40 μm under 0.810-μm laser excitation. The results have been used to formulate technical requirements for the purity of rare-earth oxides for the fabrication of efficient YPO₄:Nd³⁺ IR phosphors and to develop a fast YPO₄:Nd³⁺, Pr³⁺ IR phosphor that allows the decay time of the Nd³⁺ IR Stokes luminescence bands in the range 0.86–1.40 μm to be tuned from 50 to 170 μs by varying the ratio of the Nd³⁺ and Pr³⁺ concentrations.