Effect of phosphate doping on electric properties and chemical stability of Ba<Subscript>4</Subscript>Ca<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>11</Subscript> protonic conductor

Conductivity of perovskite phosphate–substituted solid solutions of Ba₄Ca₂Nb_{2 –x} P _x O₁₁ (0.0 ≤ x ≤ 0.5) was studied as a function of temperature, partial pressure of oxygen and water vapors. It is proved that the studied systems are protonic conductors at the temperatures below 600°C in the atmosphere with elevated content of water vapors (pH₂O = 1.92 × 10^–2 atm). Introduction of the tetrahedral [PO₄] group in the complex oxide matrix of Ba₄Ca₂Nb₂O₁₁ results in an increase in the oxygen–ionic (dry air, pH₂O = 1.91 × 10^–4 atm) and protonic conductivities (wet air, pH₂O = 1.92 × 10^–2 atm). Is it found that the doping causes a considerable increase in chemical stability of phases with respect to carbon dioxide.     

Hydration and proton transport in solid solutions based on Ba<Subscript>2</Subscript>CaWO<Subscript>6</Subscript>

Hydrated alkaline-earth metal tungstates Ba₄Ca_{2 + x} W_{2 ? x} O_{12 ? 2x} with perovskite structure were studied by the thermogravimetry, ¹H NMR, IR, and Raman spectroscopy methods. Electrical conductivity and transfer numbers were measured with varying T, \(p_{O_2 } \) and \(p_{H_2 O} \). The solid solutions are capable of reversibly intercalating water and can exhibit high-temperature proton transport. The localization of protons on oxygen results in the appearance of energetically nonequivalent OH groups; a small fraction of protons are present in the form of H₂O and H₃O⁺.     

Synthesis,structure, and electric properties of oxygen-deficient perovskites Ba<Subscript>3</Subscript>In<Subscript>2</Subscript>ZrO<Subscript>8</Subscript> and Ba<Subscript>4</Subscript>In<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>11</Subscript>

Perovskite phases Ba₃In₂ZrO₈ and Ba₄In₂Zr₂O₁₁ with the nominal concentration of structural oxygen vacancies 1/9 and 1/12, respectively, were synthesized by solid-phase and solution methods. X-ray diffraction showed cubic symmetry of both phases with the unit cell parameter a = 0.4193(2) and 0.4204(3) nm, respectively. The absence of superstructural lines resulted in the conclusion on statistical arrangement of oxygen vacancies. Thermogravimetry and mass spectrometry proved that both phases can reversibly absorb water from gas phase (pH₂O = 2 × 10⁻² atm) with observed correlation between the concentration of oxygen vacancies and amount of absorbed water. The total water amount was up to 0.9 mol per formula unit or, if recalculated for perovskite unit ABO₃, 0.3 and 0.23 mol H₂O, respectively. The temperature curves of coductivity in the atmosphere with various partial water vapor pressures (pH₂O = 3 × 10⁻⁵ and 2 × 10⁻² atm) showed significantly higher conductivity and lower activation energy (0.52 eV) in humid atmosphere due to proton transfer. The proton conductivity is up to 5 × 10⁻⁴ Ohm⁻¹ cm⁻¹ at 300°C for Ba₃In₂ZrO₈ specimen. IR spectrometry showed that protons in the structure exist primarily in OH-groups.     

The synthesis and selected properties of Co<Subscript>2</Subscript>InV<Subscript>3</Subscript>O<Subscript>11</Subscript>

It has been demonstrated that Co₂V₂O₇ and InVO₄ react with each other forming a new compound of the Co₂InV₃O₁₁ formula, when their molar ratio is equal to 1:1, or among CoCO₃, In₂O₃ and V₂O₅, mixed at a molar ratio of 4:1:3. This compound melts incongruently at the temperature of 960±5°C, depositing crystals of InVO₄. It crystallizes in the triclinic system and the unit cell parameters amount to: a=0.6524(6) nm, b=0.6885(5) nm, c=1.0290(4) nm, α=96.5°, β=104.1°, γ=100.9°, Z=2. The phase equilibria being established in the Co₂V₂O₇–InVO₄ system over the whole components concentration range up to the solidus line were described.     

Specific heat on Sr<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>7</Subscript> and Sr<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>7</Subscript>

Summary Specific heats on the single crystals of Sr₂Nb₂O₇, Sr₂Ta₂O₇ and (Sr_1-xBa_x)₂Nb₂O₇ were measured in a wide temperature range of 2-600 K. Heat anomalies of a λ-type were observed at the incommensurate phase transition of T_INC (=495 K) on Sr₂Nb₂O₇ and at the super-lattice phase transition of T_SL (=443 K) on Sr₂Ta₂O₇; the transition enthalpies and the transition entropies were estimated. Furthermore, a small heat anomaly was observed at the low temperature ferroelectric phase transition of T_LOW (=95 K) on Sr₂Nb₂O₇. The transition temperature T_LOW decreases with increasing Ba content x and it vanishes for samples of x>2%.     

Structure and real composition of undoped and Cr- and Ni-doped Sr<Subscript>0.61</Subscript>Ba<Subscript>0.39</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> single crystals

Strontium barium niobate crystals with congruent melting composition Sr_0.61Ba_0.39Nb₂O₆ (SBN-61), both nominally pure and doped with Cr³⁺ и Ni³⁺ ions, have been investigated by neutron diffraction. Different strontium and barium contents as well as their different distribution over the Sr1, of Sr2 and Ba2 crystallographic sites of SBN-61 structure, caused by introduction of dopants, have been revealed. Coordination polyhedra of cations have been established based on the analysis of cation–anion internuclear distances together with the calculation of bond-valence sums for cations, which are equal to their formal charge. It was found that the Nb1 and Nb2 atoms are located in distorted octahedra with quadfurcated (the Nb1O₆ polyhedron) or bifurcated (the Nb2O₆ polyhedron) vertices, and the Sr1 atoms are located in a cuboctahedron with bifurcated vertices in the base plane. Different polyhedra have been revealed for the Sr2 and Ba2 atoms: Sr2 atoms are coordinated by 15 oxygen atoms to form a highly distorted five-capped pentagonal prism, whereas Ba2 atoms are located in a highly distorted three-capped trigonal prism with a coordination number 9. Comparison of interatomic and internuclear distances, determined by X-ray and neutron diffraction analyses, respectively, allowed to reveal a highly pronounced shift of electron density in Nb1 and Sr2 polyhedra, responsible for the covalent bond and properties of crystals. Location of Cr³⁺ и Ni³⁺ dopant ions in the SBN-61 structure as well as their formal charges has been discussed.     

Synthesis processes and transport properties of solid solutions in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-V<Subscript>2</Subscript>O<Subscript>5</Subscript> system

The results of studies of solid solutions with the overall composition of Bi₄V_{2 ? x} Ge _x O_{11 ? δ} and Bi₄Ge_{3 ? x} V _x O_{12 + δ} are presented. The process of phase formation are studied during the synthesis of solid solution using the ceramic method and through liquid precursors. Crystallochemical parameters of the obtained compounds are determined. The size distribution of the particles is studied. Conductivity of annealed of polycrystalline samples as a function of temperature and composition is studied using the impedance spectroscopy method. The shape of impedance complex plane plots of the samples obtained in different ways is studied and analyzed.     

Effect of the modifier ion on the properties of MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript> and ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> pigments

Magnesium and zinc ferrites have been prepared by the polymeric precursor method. The organic material decomposition was studied by thermogravimetry (TG) and differential thermal analysis (DTA). The variation of crystalline phases and particle morphology with calcination temperature were investigated using X-ray diffraction (XRD) and scanning electronic microscopy (SEM), respectively. The colors of the ferrites were evaluated using colorimetry. Magnesium ferrite crystallizes above 800°C, presenting a yellow- orange color with a reflectance peak at the 600–650 nm range, while zinc ferrite crystallizes at 600°C, with a reflectance peak between 650–700 nm, corresponding to the red-brick color.     

Thermodynamic properties of silicate glasses and melts: V. Systems CaB<Subscript>2</Subscript>O<Subscript>4</Subscript>-CaSiO<Subscript>3</Subscript> and Ca<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>5</Subscript>-CaSiO<Subscript>3</Subscript>

Thermodynamic properties of melts of the CaB₂O₄-CaSiO₃ and Ca₂B₂O₅-CaSiO₃ systems were determined by the method of high-temperature mass-spectrometry. The melts of these systems are characterized by negative deviations from the ideal behavior at 1800 K.     

Physicochemical properties of KOH-H<Subscript>2</Subscript>O<Subscript>2</Subscript>-H<Subscript>2</Subscript>O solutions

Density, viscosity, and surface tension of KOH-H₂O₂-H₂O solutions used to synthesize potassium superoxide in sprayer apparatus were studied with various relative amounts of the components in the temperature range 0–30°C. Analytical dependences of the above-mentioned quantities on temperature and solvent (water) content of the system were found.     

Subsolidus phase relations in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Li<Subscript>2</Subscript>O-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> (Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>) systems

The phase composition has been studied and an equilibrium phase diagram has been designed for the Al₂O₃-Li₂O-R₂O₅ (R = Ta or Nb) systems in the subsolidus region up to 1000°C and 85 mol % Li₂O. New phases with the composition Li_1+x Al_1?x O_2?x , where x = 0–0.67, have been found.     

Mechanism and kinetics of formation of La<Subscript>2</Subscript>SrFe<Subscript>2</Subscript>O<Subscript>7</Subscript> and Nb<Subscript>2</Subscript>SrFe<Subscript>2</Subscript>O<Subscript>7</Subscript>

Phase formation processes in the systems Ln₂O₃-SrO-Fe₂O₃ (Ln = La, Nd) in air in the temperature range 1200–1500°C were studied. The synthesis of the complex ferrites La₂SrFe₂O₇ and Nb₂SrFe₂O₇ involves the formation of the intermediate compounds LnFeO₃ and LnSrFeO₄ and occurs by the same mechanism as the synthesis of the corresponding aluminates, but much faster.     

Whitlockite solid solutions in the Ca<Subscript>3</Subscript>(VO<Subscript>4</Subscript>)<Subscript>2</Subscript>-K<Subscript>3</Subscript>VO<Subscript>4</Subscript>-NdVO<Subscript>4</Subscript> system

Phase equilibria in the Ca₃(VO₄)₂-K₃VO₄-NdVO₄ system have been studied. An extensive calcium orthovanadate-based solid solution was found to form with the boundary compositions as follows: Ca₃(VO₄)₂-Ca₉Nd(VO₄)₇-Ca_9.33K_2.33(VO₄)₇-Ca_7.88K_2.63Nd_0.87(VO₄)₇. The unit cell parameters of the whit-lockite vanadates synthesized increase as the potassium and neodymium contents increase. Phase transitions from the low-temperature β phase to the β′ centrosymmetrical structure in Ca_{9.33 − 5z} K_{2.33 + z} Nd_3z (VO₄)₇ vanadates have been studied dilatometrically. The increase in the β ai β′ transition temperature caused by potassium is interpreted as arising from the filling in of vacant cation positions M(4) and M(6).     

Electrochemical properties of solid electrolytes based on BaSm<Subscript>2</Subscript>S<Subscript>4</Subscript>

Solid solutions based on BaSm₂S_{4 ? x} mol % BaS (Sm₂S₃) are obtained. Oxide intermediates were homogenized using chemical and mechanical mixing methods. The solid solution region is determined. Complex conductivity is studied and conductivity activation energy is calculated for samples with different history. Electrolytic properties of phases based on barium thiosamarate are studied. Vacancy mechanism of defect formation is suggested.     

Preparation of Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript> by polyacrylamide gel processing and its thermoelectric properties

Ca₃Co₄O₉ powder was prepared by a polyacrylamide gel route in this paper. The effect of the processing on microstructure and thermoelectric properties of Ca₃Co₄O₉ ceramics via spark plasma sintering were investigated. Electrical measurement shows that the Seebeck coefficient and conductivity are 170 μV/K and 128 S/cm, respectively, at 700 °C, yielding a power factor value of 3.70 × 10⁻⁴ W m⁻¹ K⁻² at 700 °C, which is larger than that of Ca₃Co₄O₉ ceramics via solid-state reaction processing. The polyacrylamide gel processing is a fast, cheap, reproducible and easily scaled up chemical route to improve the thermoelectric properties of Ca₃Co₄O₉ ceramics by preparing the homogeneous and pure Ca₃Co₄O₉ phase.     

Oxygen redistribution during crystal growth of ZrO<Subscript>2</Subscript>-R<Subscript>2</Subscript>O<Subscript>3</Subscript> solid solutions

This paper presents the results of our experimental studies of quantitative redistribution and isotope fractionation of oxygen during the crystal growth of cubic solid solutions based on ZrO₂. The single crystals were grown by directional crystallization of a melt in a cold container. As stabilizing oxides, we used Y₂O₃, Gd₂O₃, and Yb₂O₃ in concentrations of 8–40 mol %. The results showed that the oxygen isotopic growth effects changed depending on the type and content of the stabilizer in the crystals of ZrO₂-R₂O₃ solid solutions.     

Effect of protonation and deprotonation on surface charge density of Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>

The protonation and deprotonation of the Nb₂O₅ surface has been followed in order to understand the reactions of surface of this catalyst. The simultaneous potentiometric and conductometric titrations had been carried by using 50 mL of water suspension of Nb₂O₅ 40 g L⁻¹. The oxide was entirely deprotonated when adding 0.4 mL NaOH 1 mol L⁻¹, and later titrated with 0.1 mol L⁻¹. The titration had supplied K ₁ and K ₂ and the obtained values were 3.24 × 10⁻³ and 4.17 × 10⁻⁸, respectively. The zero point charge was pH_pcz = 4.94. The thermodynamic studies were carried out by using 50 mL of a 40 g/L Nb₂O₅ aqueous suspension with the pH adjusted to pH_PZC value. The suspension was titrated with 0.5 mol/L of HNO₃ or NaOH for protonation or deprotonation studies, respectively, in an isoperibol calorimeter CSC ISC-4300. Thus, the obtained thermodynamic values of the protonation and deprotonation of Nb₂O₅ were Δ_dp G = −37.60 kJ/mol, Δ_dp H = −23.72 kJ/mol and Δ_dpS = 47 J/(mol K).     

Thermal oxide synthesis and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

Fe₃O₄ nanorods and Fe₂O₃ nanowires have been synthesized through a simple thermal oxide reaction of Fe with C₂H₂O₄ solution at 200–600°C for 1 h in the air. The morphology and structure of Fe₃O₄ nanorods and Fe₂O₃ nanowires were detected with powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The influence of temperature on the morphology development was experimentally investigated. The results show that the polycrystals Fe₃O₄ nanorods with cubic structure and the average diameter of 0.5–0.8 μm grow after reaction at 200–500°C for 1 h in the air. When the temperature was 600°C, the samples completely became Fe₂O₃ nanowires with hexagonal structure. It was found that C₂H₂O₄ molecules had a significant effect on the formation of Fe₃O₄ nanorods. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ nanorods. Supported by the Fund of Weinan Teacher’s University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and the Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)