Synthesis and high-temperature electrical conductivity of Ln<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> and LnYTi<Subscript>2</Subscript>O<Subscript>7</Subscript> (Ln = Dy,Ho)

Ho₂Ti₂O₇ and LnYTi₂O₇ (Ln = Dy, Ho) pyrochlores have been synthesized using hydroxide coprecipitation, mechanical activation, and firing at 1600°C. The bulk and grain-boundary components of their conductivity have been determined for the first time by impedance spectroscopy. The 740°C bulk conductivity of Ho₂Ti₂O₇ is 4 × 10^?4 S/cm, and that of HoYTi₂O₇ is 1 × 10^?3 S/cm, with activation energies E _a = 1.01 and 1.17 eV, respectively, suggesting that these materials are new oxygen-ion conductors. The bulk conductivity of DyYTi₂O₇ (3 × 10^?4 S/cm at 740°C, E _a = 1.09 eV) is almost one order of magnitude lower than that of HoYTi₂O₇ (1 × 10^?3 S/cm at 740°C, E _a = 1.17 eV).     

Synthesis and electrical properties of Gd<Subscript>2</Subscript>MO<Subscript>5</Subscript> (M = Zr,Hf)

Polycrystalline Gd₂ZrO and Gd₂HfO₅ have been prepared by heat-treating coprecipitated oxide mixtures, and their order-disorder phase transitions have been studied in the range 20–1600°C. The materials have been shown to consist of nanostructured grains with a nanodomain size of ∼40 nm. Their electrical conductivity has been determined by impedance spectroscopy in air between 300 and 1000°C. The 1000°C conductivities of Gd₂ZrO₅ and Gd₂HfO₅ are 3.7 × 10⁻³ and 1.8 × 10⁻³ S/cm, and the respective effective activation energies are 1.37 and 1.56 eV.     

Mechanism of structure formation in samarium and holmium titanates prepared from mechanically activated oxides

We have studied the formation mechanism and phase transitions of samarium and holmium titanates prepared from mechanically activated oxide mixtures with the overall compositions Sm₂(Ho₂)Ti₂O₇ and Sm₂TiO₅. Mechanical activation of oxide mixtures leads to the formation of amorphous solid phases which crystallize in a distorted pyrochlore-like structure and contain OH groups on the oxygen site and structural vacancies up to 1000°C. In the range 800–1000°C, Sm_2?x Ti_1?y O_5?δ (OH) _n (x < 0.02; y < 0.08; δ, n < 0.19) converts to a distorted orthorhombic phase as a result of the relaxation of internal stress and removal of OH groups. Above 1000°C, the phases studied have the compositions Sm₂(Ho₂)Ti₂O₇ and Sm₂TiO₅ and ordered pyrochlore-like and orthorhombic structures, respectively. The lattice parameters of the titanates have been measured in the range 800–1350°C. The internal stress produced by mechanical activation in the phases studied here fully relaxes by ～1300°C.     

Synthesis,X-ray structure analysis,and Raman spectroscopy of R<Subscript>2</Subscript>TiO<Subscript>5</Subscript>-based (R = Sc,Y) solid solutions

Order–disorder transitions in xR₂O₃ · (1 ? x)TiO₂ (R = Sc, 0.4 ≤ x ≤ 0.5; R = Y, 0.5 ≤ x ≤ 0.6) solid solutions with highly imperfect fluorite-derived structures have been studied using monochromatic synchrotron X-ray diffraction and Raman spectroscopy. The results demonstrate that the synthesis process leads to the formation of a fluorite-like (Fm3m) disordered phase and a nanoscale (~10–100 nm) pyrochlore-like (Fd3m) ordered phase of the same composition, coherent with the disordered phase. We have determined their lattice parameters. The Raman spectra of Sc₂TiO₅ (Y₂TiO₅) contain broad lines in low- and high-frequency regions: at 190, 350, and 775 (134, 188, 365, 404, and 727) cm^?1. These lines are characteristic of a pyrochlore-like phase with a varying degree of order and a disordered fluorite-like phase, respectively. The pyrochlore-like phase Y₂Ti₂O₇ has two strong Raman peaks in the low-frequency region: at 312 and 527 cm^?1. The formation of nanodomains with different degrees of order is caused by the internal stress that arises from the high density of structural defects in the unit cells of the solid solutions.     

Sintering and electrical properties of Ce<Subscript>0.8</Subscript>Sm<Subscript>0.2</Subscript>O<Subscript>1.9</Subscript> film prepared by spray pyrolysis and tape casting

Ce_0.8Sm_0.2O_1.9 (SDC) powder was synthesized by spray pyrolysis at 650 °C. XRD results showed that phase-pure SDC powder with an average crystallite size of 11 nm was synthesized. SDC electrolyte film was prepared by tape casting and sintered at different temperatures of 1,300, 1,400 and 1,500 °C for 2 h, respectively. The SDC electrolyte film was relatively denser and showed finer microstructure at relatively lower temperature of 1,400 °C, which might be due to the high sintering activity of the spray pyrolysis SDC powder. The ionic conductivity of the SDC electrolyte film sintered at 1,400 °C reached a maximum value of 9.5 × 10⁻³ S cm⁻¹ (tested at 600 °C) with an activation energy for conduction of 0.90 eV.     

High-performance flexible supercapacitors based on C/Na<Subscript>2</Subscript>Ti<Subscript>5</Subscript>O<Subscript>11</Subscript> nanocomposite electrode materials

A new solution method to synthesize Na₂Ti₅O₁₁ with titanium powder is presented, and the C/Na₂Ti₅O₁₁ nanocomposite with high specific surface area and tunnel structure as the electrode material has excellent electrochemical performance. The single electrode composed of the C/Na₂Ti₅O₁₁ nanocomposite based on carbon fiber fabric (CFF) has the highest area capacitance of 1066 mF cm^?2 at a current density of 2 mA cm^?2, which is superior to other titanates and Na-ion materials for supercapacitors (SCs). By scan-rate dependence cyclic voltammetry analysis, the capacity value shows both capacitive and faradaic intercalation processes, and the intercalation process contributed 81.7% of the total charge storage at the scan rate of 5 mV s^?1. The flexible symmetric solid-state SCs (C/Na₂Ti₅O₁₁/CFF//C/Na₂Ti₅O₁₁/CFF) based on different C/Na₂Ti₅O₁₁ mass were fabricated, and 7 mg SCs show the best supercapacitive characteristics with an area capacitance of 309 mF cm^?2 and a specific capacitance of 441 F g^?1, it has a maximum energy density of 22 Wh kg^?1 and power density of 1286 W kg^?1. As for practical application, three SCs in series can power 100 green light-emitting diodes (LEDs) to light up for 18 min, which is much longer than our previous work by Wang et al. lighting 100 LEDs for 8 min. Thus, the C/Na₂Ti₅O₁₁ nanocomposite has promising potential application in energy storage devices.     

Ionic conductivities of Na2Ti3O7, K2Ti4O9 and their related materials

Ionic conductivities were measured on the polycrystalline samples of layered titanates, Na₂Ti₃O₇ and K₂Ti₄O₉, and their derivatives. The activation energies and the prefactors of the conductions were 0.70 eV and 7.9 × 10 (Ωcm)^?1K for Na₂Ti₃O₇ and 0.81 eB and 1.1 × 10³ (Ωcm)^?1K for K₂Ti₄O₉. A small amount of Nb₂O₅ was doped to these titanates substituting TiO₂. Remarkable enhancements of ionic conductivities were observed with the doping. A new metastable phase, Li₂Ti₃O₇, was prepared by ion-exchange of Na₂Ti₃O₇ and its ionic conductivity was measured.     

Effect of calcination temperature on structure and thermoelectric properties of CuAlO<Subscript>2</Subscript> powders

Copper aluminum oxide (CuAlO₂) with delafossite phase was synthesized by the Pechini method using different calcination temperatures to evaluate its influence on the structure and thermoelectric material properties. X-ray diffraction and Raman spectroscopy confirm that delafossite phase was formed at 1100 °C with the presence of 2H-CuAlO₂ and Al₂O₃ impurities, while at lower calcination temperatures (900 and 1000 °C), a mixture of CuO + CuAl₂O₄ (spinel phase) was observed. Energy-dispersive X-ray elemental maps display an even distribution of copper, aluminum and oxygen in the sample calcined at 1100 °C. Direct optical band gap, E _g = 3.6 eV, was calculated from reflectance diffuse spectra by Kubelka–Munk and Tauc methods. An absorption band at 1.7 eV accounts for defect levels, masking the characteristic indirect transition. The thermoelectric properties, such as Seebeck coefficient, and thermal and electrical conductivities of the sample calcined at 1100 °C were measured at different temperatures. Hall voltage and positive values of the Seebeck coefficient (425.8–434.4 µV K^?1) confirm the material’s p-type character. The independence of the Seebeck coefficient on the operation temperature indicates a small polaron electrical conduction mechanism. Thermal conductivity decreases exponentially with the temperature from 43.45 to 23.9 W m^?1 K^?1, where the principal contribution is due to phonons. Figure of merit ZT of sample calcined at 1100 °C between 100 and 800 °C increases from 1.42 × 10^?8 to 4.94 × 10^?4 in the order of the literature reports. From the Arrhenius plot ln(σT) versus 1000/T, an activation energy E _a = 0.32 eV for the electrical conductivity was calculated.     

The synthesis and the magnetic properties of Sm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>BiY<Subscript>2–<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>5</Subscript>O<Subscript>12 </Subscript>nanoparticles

Sm _x BiY_2–x Fe₅O₁₂ (x = 0, 0.1, 0.2, 0.4, 0.6, 0.8) nanocrystals were fabricated by sol–gel method. Samples were characterized by powder X-ray diffraction (XRD), thermal gravity analysis (TGA) and differential thermal analysis (DTA), transmission electron microscopy (TEM), vibrating sample magnetometer(VSM). The samples were calcined at 850 °C and 1000 °C and the average size of the particles were determined by Scherrer’s formula . In this paper, we discussed the effect of Sm³⁺ substitution for Y³⁺ on magnetic properties of BiY₂Fe₅O₁₂. The magnetic properties of Sm _x BiY_2−x Fe₅O₁₂ are decreased with increasing content of Sm ion.     

Electrical conductivity of nanostructured fluorite-like Sc<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript>

Single-crystal and polycrystalline samples of Sc₄Ti₃O₁₂ have been shown to contain nanodomains (10–50 nm) with different degrees of ordering, coherent with the fluorite-like matrix. The oxygen-ion conductivity of this compound has been determined in the range 300–1000°C in air using impedance spectroscopy. The nanostructured single-crystal and polycrystalline samples are close in the activation energy for bulk conduction at both low and high temperatures: ?1.26 and 1.29 eV in the range 300–775°C, ?1.98 and 2.07 eV in the range 775–1000°C.     

Luminescence properties and electronic structure of Sm<Superscript>3+</Superscript>-doped YAl<Subscript>3</Subscript>B<Subscript>4</Subscript>O<Subscript>12</Subscript>

The luminescence properties of Sm³⁺ ions in YAl₃B₄O₁₂ were studied upon synchrotron excitation in the 3.8–11 eV region. In addition to the 4f → 4f excitation bands, the excitation spectra of the Sm³⁺ emission contain broad bands at 6.1 and ~7.0 eV. These bands are attributed to charge transfer transition in Sm³⁺–O²⁻ complexes and 4f → 5d transition of Sm³⁺ ions, respectively. The optical absorption edge of YAl₃B₄O₁₂ was determined at 7.3 eV. A comparison with the results of electronic structure calculations on YAl₃B₄O₁₂ is also made.     

The ZrO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> phase diagram

The ZrO₂-TiO₂ phase diagram was determined experimentally between 800 and 1200°C, 1 atm, extending our knowledge of this system to temperatures previously inaccessible for equilibrium experiments due to sluggish kinetics. The crystallization of the ordered (Zr,Ti)₂O₄ phase from the oxides was facilitated by the addition of flux (CuO or Li₂MoO₄/MoO₃), and seeds. Two ordered (Zr,Ti)₂O₄ phases with different compositions were identified, and their phase relationships with TiO₂ and ZrO₂ solid solutions investigated. Structure data, superstructure reflections and composition were used to locate the ordering phase transition of (Zr,Ti)₂O₄ in equilibrium with ZrO₂ and TiO₂. At the onset of ordering between 1130 and 1080°C, (Zr,Ti)₂O₄ is of composition X_Ti = 0.495 ± 0.02, and displays a dramatic change in b-dimension. At 1060°C and below, the composition of (Zr,Ti)₂O₄ is significantly more Ti-rich and dependent on temperature, ranging from X_Ti = 0.576 at 1060°C to 0.658 at 800°C. This variability in composition of the ordered phase contrasts with previous studies that suggested the composition to be constant at either X_Ti = 0.667 [ZrTi₂O₆] or 0.583 [Zr₅Ti₇O₂₄]. When grown at low temperatures and with lithium molybdate, the crystals of ordered (Zr,Ti)₂O₄ are acicular to needle shape, and develop distinct square cross-sections and end facets.     

High-temperature oxidation behaviour of Ti<Subscript>3</Subscript>Si<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>C<Subscript>2</Subscript> in air

The oxidation behaviours of bulk Ti₃Si_(1−x)Al _x C₂ prepared by hot pressing were investigated. The results showed that the isothermal oxidation behaviour of Ti₃SiC₂ obeyed a parabolic law between 900 and 1100°C, and followed a two-step parabolic rate law between 1200°C and 1300°C. The cyclic oxidation behaviour of material is assumed to obey a three-step parabolic rate law at 1100°C and 1200°C. The calculated activation energy of isothermal oxidation is 101·43 kJ·mol⁻¹. The oxide layers consisted of a mass of α-Al₂O₃ and little TiO₂ and SiO₂ are observed on Ti₃SiC₂ as a dense and adhesive protect scale. The oxidation mechanism varies with the additive aluminum that greatly improves the oxidation resistance of Ti₃SiC₂.     

Crystal structure,microstructure and microwave dielectric properties of novel MgAl<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>10</Subscript> ceramic

In the present work, a novel MgAl₂Ti₃O₁₀ ceramic was obtained using a traditional solid-state reaction method. X-ray diffraction and energy dispersive spectrometer showed that the main MgAl₂Ti₃O₁₀ phase was formed after sintered at 1300–1450 °C. With rising the sintering temperature from 1300 to 1450 °C, the bulk density (ρ), relative permittivity (ε _r ) and Q?×?f value firstly increased, reached the maximum values (3.61 g/cm³, 14.9, and 26,450 GHz) and then decreased. The temperature coefficient of resonator frequency (τ _f ) showed a slight change at a negative range of ??94.6 to ??83.7 ppm/°C. When the sintering temperature was 1400 °C, MgAl₂Ti₃O₁₀ ceramics exhibited the best microwave dielectric properties with Q?×?f?=?26,450 GHz, ε _r ?=?14.9 and τ _f ?=???83.7 ppm/°C.     

Investigation of Li<Subscript>2</Subscript>Zn<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript>-based temperature stable dielectric ceramics for LTCC applications

A low temperature co-fired ceramic (LTCC) was fabricated at 910 °C /2 h from the powder mixture of Li₂Zn₃Ti₄O₁₂, TiO₂ and a B₂O₃–La₂O₃–MgO–TiO₂ glass (BLMT), and the influence of TiO₂ on microstructure and dielectric properties of the composite was investigated in the composition range (wt%) of 20BLMT–(80???x)Li₂Zn₃Ti₄O₁₂–xTiO₂ (x?=?0, 2.5, 5, 7.5, 9 and 10). The results showed that all samples consisted of Li₂Zn₃Ti₄O₁₂, TiO₂, LaBO₃ and LaMgB₅O₁₀ phase. And LaBO₃, LaMgB₅O₁₀ and a small amounts of TiO₂ were crystallized from BLMT glass during sintering process. As x increases, dielectric constant and temperature coefficient of resonance frequency of the composites demonstrated gradually increase, whereas the quality factor of the sample of x?=?0 wt% was about 41,500 GHz and the ones maintained stable at a high level of 49,000–51,000 GHz for other samples. The composite with x?=?9 wt% had an optimal microwave dielectric properties with the dielectric constant of 20.2, quality factor of 50,000 GHz and temperature coefficient of resonant frequency of ??0.33 ppm/°C.     

Synthesis and High-Temperature Heat Capacity of Sm<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Eu<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Sm₂Ge₂O₇ and Eu₂Ge₂O₇ germanates have been prepared by solid-state reactions via multistep firing of stoichiometric mixtures of Sm₂O₃ (Eu₂O₃) and GeO₂ in air at temperatures from 1273 to 1473 K. The molar heat capacity of the samarium and europium germanates has been determined by differential scanning calorimetry in the range 350–1000 K and the C _p (T) data have been used to evaluate their thermodynamic properties.     

Plutonium dioxide catalyzed reaction between H<Subscript>2</Subscript> and O<Subscript>2</Subscript>

The kinetic characteristics of the reaction between H₂ and O₂ were calculated to more adequately simulate the radiolysis of water adsorbed on PuO₂. The rate constants of this reaction were determined via comparison of the calculated results with the published experimental data. It was found that, with the amount of the adsorbed water increasing from 2 × 10^?4 to 5 × 10^?3%, the rate constant of the reaction decreases from 6.0 × 10^?4 to 1.7 × 10^?5 mol^?1 s^?1. At the water content over 5 × 10^?3%, the rate constant is ≤1 × 10^?5 mol^?1 s^?1. A new mathematical model of the radiation-chemical and physicochemical processes occurring in the PuO₂-H₂O system was presented; the amounts of hydrogen and oxygen yielded by α-radiolysis of the adsorbed water were calculated, taking into account the reaction between H₂ and O₂.     

Synthesis of nanocomposites based on MO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> (M = Ca,Sr, Ba) glasses

This work examines the effect of KBF₄ additions on the crystallization behavior of glasses based on the multicomponent systems MO-Bi₂O₃-B₂O₃ with M = Ca, Sr, and Ba. The glass-ceramic composites obtained contain a δ-Bi₂O₃-based crystalline phase with a crystallite size of ≃7 nm, evenly distributed over the glass matrix. The 400°C electrical conductivity of the nanocomposites reaches 2 × 10⁻⁴ S/cm, and the activation energy is 1.1 eV, typical of anion conduction. These values are comparable to those reported for δ-Bi₂O₃ ceramics.     

Effects of rare-earth Sm<Subscript>2</Subscript>O<Subscript>3</Subscript> addition on relaxation behavior and electric properties of 0.5PNN-0.5PZT ceramics

Rare-earth Sm₂O₃-doped Pb(Ni_1/3Nb_2/3)_0.5(Zr_0.3Ti_0.7)_0.5O₃ (0.5PNN-0.5PZT + xSm) piezoelectric ceramics were prepared by a two-step solid-state reaction method. The effects of Sm₂O₃ doping on phase structure, electric properties and dielectric relaxation of 0.5PNN-0.5PZT ceramics were investigated. The results showed that Sm³⁺ tended to occupy the B-site of Zr⁴⁺. The XRD patterns showed that all ceramics had a pure perovskite phase structure. With the increasing of Sm₂O₃ addition, Curie temperature moved towards low temperatures obviously and dispersion coefficient γ first increased and then decreased gradually. When x = 0.2 wt%, the γ reaches at maximum (1.998), it was indicated that a nearly complete diffuse phase transition existed and relaxation behaviors enhanced. But the ceramics with x = 0.2 wt% exhibited terrible electric properties: d₃₃ = 605 pC/N, k_p = 0.55, ε_r ~ 5020, tanδ ~ 2.20 %. It showed that the relaxation behaviors have relationships with electric properties to some extent.     

Giant dielectric and electrical properties of sodium yttrium copper titanate: Na<Subscript>1/2</Subscript>Y<Subscript>1/2</Subscript>Cu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript>

The electrical properties and dielectric response in Na_1/2Y_1/2Cu₃Ti₄O₁₂ ceramic prepared by conventional solid-state reaction method and sintered at 1,090 °C for 5 h were investigated as functions of frequency and temperature. Main phase of Na_1/2Y_1/2Cu₃Ti₄O₁₂ with CaCu₃Ti₄O₁₂-like crystallographic structure and CuO secondary phase were observed in the X-ray diffraction pattern. Abnormal grain growth was observed just as observed in CaCu₃Ti₄O₁₂ ceramics. The Na_1/2Y_1/2Cu₃Ti₄O₁₂ ceramic exhibits a high ε′ of ~2.04 × 10⁴ at 20 °C and 1 kHz and low tan δ (with the minimum 0.080 at 5 kHz). Impedance spectroscopy analysis reveals that Na_1/2Y_1/2Cu₃Ti₄O₁₂ ceramic is electrically heterogeneous, consisting of semiconducting grains and insulating grain boundaries. Giant ε′ response in Na_1/2Y_1/2Cu₃Ti₄O₁₂ ceramic is therefore attributed to an internal barrier layer capacitor effect.