Lithium ion conductivity of LiLaO<Subscript>2</Subscript>-Li<Subscript>2</Subscript>ZrO<Subscript>3</Subscript> solid solutions

The limits of the LiLaO₂-and Li₂ZrO₃-based solid solutions in the LiLaO₂-Li₂ZrO₃ system have been determined: 0–10 mol % Li₂ZrO₃ and 0–5 mol % LiLaO₂, respectively. We have studied the transport properties (electronic conductivity, temperature and composition dependences of conductivity and activation energy) of lithium lanthanate and the solid solutions in the LiLaO₂-Li₂ZrO₃ system. Conduction in LiLaO₂ is likely due to lithium ion transport through a polyhedral network.     

Change in the mechanism of conductivity in ZrO<Subscript>2</Subscript>-based crystals depending on the content of stabilizing Y<Subscript>2</Subscript>O<Subscript>3</Subscript> additive

The interrelationship between the structure, phase composition, and transport characteristics of solid electrolytes based on ZrO₂ has been studied as dependent on the content of stabilizing Y₂O₃ additive. It is established that twin boundaries do not lead to the appearance of additional mechanism of ionic conductivity acceleration in ZrO₂–Y₂O₃ crystals. The maximum conductivity has been observed in ZrO₂–(8–10) mol % Y₂O₃ crystals containing a t” phase, in which oxygen atoms are displaced from high-symmetry positions characteristic of the cubic phase.     

Structure of multilayer ZrO<Subscript>2</Subscript>/SrTiO<Subscript>3</Subscript>

Multilayered oxide heteroepitaxial systems, including that of a 1-nm-thick Y₂O₃-stabilised ZrO₂ (YSZ) sandwiched between layers of SrTiO₃ (STO) [1], have been a subject of much interest lately due to their significantly enhanced ionic conductivities as compared to the bulk materials. We aim to provide the foundation for understanding this increase in conductivity by considering the atomic configurations at the interfaces of such systems, specifically a ZrO₂/STO multilayer system. Possible stable lattice structures of pure ZrO₂ in the system are explored using a genetic algorithm in which the interatomic interactions are modelled by simple pair potentials. The energies of several of the more stable of these structures are then evaluated more accurately within density functional theory (DFT). We find that the fluorite ZrO₂ phase is unstable as a coherently strained epitaxial layer in the multilayer system. Instead, anatase-, columbite-, rutile-, and pyrite-like ZrO₂ epitaxies are found to be more stable, with the anatase-like epitaxy being the most stable structure over a wide range of chemical potential of the components. We also find a high energy metastable structure resembling the tetragonal fluorite structure which is predicted by DFT to be stabilised by SrO-terminated STO but not by TiO₂-terminated STO.     

Preparation of porous ZrO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> macrobeads from ion-exchange resin templates

In this work, we will report a method to prepare porous ZrO₂ and ZrO₂/Al₂O₃ macrobeads using cation-exchange resins with sulfonate groups as templates. The preparation process involves metal ion-loading, ammonia-precipitation, and calcination at an appropriate temperature. Several characterization methods, such as TGA, XRD, SEM with EDX, TEM and N₂ adsorption and desorption, were used to characterize the ZrO₂ and ZrO₂/Al₂O₃ macrobeads. The results showed that the porous structures of the resin templates were negatively duplicated in the two kinds of macrobeads. We found the following interesting results: (1) The ZrO₂/Al₂O₃ macrobeads are composed of tetragonal zirconia nanocrystals that are more technologically important, while the pure ZrO₂ macrobeads consist of a mixture of tetragonal and monoclinic zirconia. (2) In the ZrO₂/Al₂O₃ macrobeads, the size of ZrO₂ nanocrystals is about 5 nm smaller than that (about 19 nm) found in the pure ZrO₂ macrobeads. (3) The ZrO₂/Al₂O₃ macrobeads have more mesopores and, therefore, have a larger surface area than the pure ZrO₂ macrobeads. These oxide macrobeads will have potential applications in catalysis by taking advantage of their macrobeads shape and pores structure.     

Synthesis of WO<Subscript>3</Subscript>/mesoporous ZrO<Subscript>2</Subscript> catalyst as a high-efficiency catalyst for catalytic oxidation of dibenzothiophene in diesel

The catalyst of WO₃ highly dispersed on mesoporous ZrO₂ was prepared by hydrothermal treatment and calcination. Ionic liquid templates with different cations and various calcination temperatures were taken into account to investigate factors that affect the structure of the catalysts. Wide-angle XRD, Raman, low-angle XRD, N₂ adsorption–desorption, SEM, EDS-mapping and TEM analyses were employed to characterize the composition, morphology and the dispersion of WO₃. It was found that [C₁₆H₃₃N(CH₃)₃]₄SiW₁₂O₄₀ and 700 °C were the optimal ionic liquid template and calcination temperature; the obtained catalyst, expressed as 700-C₁₆-WO₃/ZrO₂, exhibited the best catalytic activity in oxidation desulfurization. Dibenzothiophene (DBT) in the model oil could be oxidized to DBT sulfone (DBTO₂) completely, certified by GC-MS analysis, under optimum conditions. The oxidative desulfurization efficiencies of different substrates catalyze by 700-C₁₆-WO₃/ZrO₂, and the cycle performance on the oxidation of DBT were studied.     

A novel method for producing open-cell Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> ceramic foams with controlled cell structure

A novel method was introduced to prepare open-cell Al₂O₃–ZrO₂ ceramic foams with controlled cell structure. This method used epispastic polystyrene (EPS) spheres to array ordered templates and centrifugal slip casting in the interstitial spaces of the EPS template to obtain cell struts with high packing density. Aqueous Al₂O₃–ZrO₂ slurries with up to 50 vol.% solid contents were prepared and centrifuged at acceleration of 2,860g. The effect of the solid contents of slurries on segregation phenomena of different particles and green compact uniformity were investigated. In multiphase system, the settling velocities of Al₂O₃ and ZrO₂ particles were calculated. Theory analysis and calculated results both indicated segregation phenomenon was hindered for slurries with 50 vol.% solid content. The cell struts of sintered products had high green density (61.5%TD), sintered density (99.1%TD) and homogeneous microstructures after sintered at 1,550 °C for 2 h. The cell size and porosity of Al₂O₃–ZrO₂ ceramic foams can be adjusted by changing the size of EPS spheres and the load applied on them during packing, respectively. When the porosity increased from 75.3% to 83.1%, the compressive strength decreases from 3.82 to 2.07 MPa.     

Behavior of Np(VI) and Np(V) Ions in NaHCO<Subscript>3</Subscript> Solutions Containing H<Subscript>2</Subscript>O<Subscript>2</Subscript>

The behavior of Np(VI) and Np(V) in NaHCO₃ and NaHCO₃ + Na₂CO₃ solutions containing H₂O₂ was studied spectrophotometrically. In 0.75–1.0 M NaHCO₃, hydrogen peroxide oxidizes Np(V) to Np(VI). The kinetics curves of Np(V) oxidation into Np(VI) have a complex shape and are characterized either by an induction period of up to tens of minutes or by a period of steady-state Np(VI) concentration, followed by an increase in the Np(VI) concentration. When Np(VI) initially exists in the solution, the induction period is lacking. The process character changes when the bicarbonate concentration decreases, or when Na₂CO₃ is added. In 1.0 M Na₂CO₃, 0.5 M NaHCO₃ + 0.5 M Na₂CO₃, or 0.01–0.5 M NaHCO₃, hydrogen peroxide completely reduces Np(VI) into Np(V). The probable mechanisms of this process were discussed. Accumulation of Np(VI) in NaHCO₃ solutions can be accounted for by assuming that Np(VI) itself participates in the transformations. Initially, the reaction of Np(VI) with H₂O₂ yields the excited *Np(V) ion. Then it reacts with another H₂O₂ molecule and forms a carbonate-peroxide complex. In the collision of the latter with unexcited Np(V), two electrons from two Np(V) ions are transferred onto the O ₂ ^2? ligand with formation of two Np(VI) ions.     

Synthesis and properties of complexes of hexavalent actinides with dimethyl sulfoxide [AnO<Subscript>2</Subscript>(DMSO)<Subscript>5</Subscript>](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript> (An = U,Np, Pu)

The complexes [NpO₂(DMSO)₅](ClO₄)₂ (1) and [PuO₂(DMSO)₅](ClO₄)₂ (2), isostructural to the known uranyl complex, were synthesized in the form of single crystals. Their crystallographic characteristics were determined by single crystal X-ray diffraction. The IR and electronic absorption spectra of the crystalline U(VI), Np(VI), and Pu(VI) complexes were measured and analyzed.     

Thermodynamic properties of Dy<Subscript>2</Subscript>O<Subscript>3</Subscript> · 2ZrO<Subscript>2</Subscript> and Ho<Subscript>2</Subscript>O<Subscript>3</Subscript> · 2ZrO<Subscript>2</Subscript> in the range 10–340 K

The low-temperature heat capacity of Dy₂O₃ · 2ZrO₂ and Ho₂O₃ · 2ZrO₂ has been determined by adiabatic calorimetry in the temperature range 10–340 K. The results have been used to calculate the entropy, enthalpy increment, and reduced Gibbs energy of the zirconates without taking into account their low-temperature magnetic transformations.     

Synthesis of polyaniline/ZrO<Subscript>2</Subscript> nanocomposites and their performance in AC conductivity and electrochemical supercapacitance

Polyaniline/zirconium oxide (PANI/ZrO₂) nanocomposites have been synthesized by incorporating ZrO₂ nanoparticles into the PANI matrix via liquid–liquid interfacial polymerization method. The composite formation and structural changes in PANI/ZrO₂ nanocomposites were investigated by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). PXRD pattern of PANI/ZrO₂ nanocomposites exhibited sharp and well-defined peaks of monoclinic phase of ZrO₂ in PANI matrix. SEM images of the composites showed that ZrO₂ nanoparticles were dispersed in the PANI matrix. The FT-IR analysis revealed that there was strong interaction between PANI and ZrO₂. AC conductivity and dielectric properties of the nanocomposites were studied in the frequency range, 50–10⁶ Hz. AC conductivity of the nanocomposites obeyed the power law indicating the universal behaviour of disordered media. The nanocomposites showed high dielectric constant in the order of 10⁴, which could be related to dielectric relaxation phenomenon. Further, the materials were checked for their supercapacitance performance by using cyclic voltammetry (CV), chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS). Among the synthesized nanocomposites, PANI/ZrO₂-25 wt.% showed a higher specific capacitance of 341 F g^?1 at 2 m Vs^?1 and good cyclic stability with capacitance retention of about 88% even after 500 charge–discharge cycles.     

Properties of nanocrystalline ZrO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>-CoO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powders

We have studied the properties of nanocrystalline ZrO₂-Y₂O₃-CeO₂-CoO-Al₂O₃ powders prepared via hydrothermal treatment of a mixture of coprecipitated hydroxides at 210°C. A number of general trends are identified in the variation of the properties of the synthesized powders during heat treatment at temperatures from 500 to 1200°C. Our results demonstrate that the addition of 0.3 mol % CoO to nanocrystalline ZrO₂-based powders containing 1 to 5 mol % Al₂O₃ allows one to obtain composites with good sinterability at a reduced temperature (1200°C).     

Influences of ZrO<Subscript>2</Subscript> nanoparticles on the microstructure and mechanical behavior of Ce-TZP/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposites

Influences of ZrO₂ nanoparticles on the mechanical properties and microstructure of hot-pressing Ce-TZP/Al₂O₃ ceramics were investigated. Meanwhile, t-ZrO₂ to m-ZrO₂ transformation toughening mechanism was investigated by X-ray diffractometry (XRD) method, and deflection of samples under applied stress were recorded too. The results show that when the percentage of ZrO₂ was 20%, the mechanical properties and microstructures of materials are optimum. Moreover, TEM observation show dislocation structures formation both in the Al₂O₃ and on the grain boundary. Because the dislocation agglomeration and fixation by ZrO₂ nanoparticles could deflect cracking or stop cracking development, a strengthening and toughening effect could be achieved.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> on the properties of nanocrystalline ZrO<Subscript>2</Subscript> + 3 mol % Y<Subscript>2</Subscript>O<Subscript>3</Subscript> powder

We have studied the properties of nanocrystalline ZrO₂〈3 mol % Y₂O₃〉 and 90 wt % ZrO₂〈3 mol % Y₂O₃〉-10 wt % Al₂O₃ powders prepared via hydrothermal treatment of coprecipitated hydroxides at 210°C. The results demonstrate that Al₂O₃ doping raises the phase transition temperatures of the metastable low-temperature ZrO₂ polymorphs and that the structural transformations of the ZrO₂ and Al₂O₃ in the doped material inhibit each other.     

Structure and microwave dielectric properties of ZnTa<Subscript>2</Subscript>O<Subscript>6</Subscript> ceramics with TiO<Subscript>2</Subscript> and ZrO<Subscript>2</Subscript> additions

Ceramic samples based on ZnTa2O₆ and ZnTa₂O₆–MO₂ (M = Ti, Zr) systems have been obtained by the solid state ceramic route. The phase composition and microstructure of samples were investigated. The effect of the aliovalent substitution of ions Zn²⁺ and Ta⁵⁺ by M⁴⁺ (M = Ti, Zr) in the structure of ZnTa₂O₆ on microwave dielectric properties of ceramics was studied. The way of the compensation of the positive temperature coefficient of resonant frequency of dielectric resonators based on ZnTa₂O₆ ceramics with using the aliovalent substitution of cations was proposed. Dielectric resonators with the high temperature stability of the resonant frequency and high dielectric properties in the microwave range based on the ZnTa₂O₆–ZrO₂ system were obtained for application in electronics.     

Sorption properties of silicate materials based on Ca<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

Sorption studies showed that a silicate material formed in the course of metallurgical slag reprocessing, containing dicalcium silicate as the major component, exhibits high affinity (logK _d [ml g⁻¹] > 4) for U(VI), Pu(IV), REE(III), and Th(IV) cations and for simple anions and appreciable affinity (logK _d [ml g⁻¹] > 2) for Cs(I) and Sr(II) cations in their sorption from river water. The sorbent can be of practical interest for separation, preconcentration, neutralization, and recovery of harmful chemical elements and radioactive substances from aqueous solutions, followed by their cementation (solidification) and safe disposal.     

Behavior of Am(V) in concentrated HNO<Subscript>3</Subscript> solutions containing potassium phosphotungstate K<Subscript>10</Subscript>P<Subscript>2</Subscript>W<Subscript>17</Subscript>O<Subscript>61</Subscript>

The Am(V) disproportionation in (2–10) × 10^?3 M K₁₀P₂W₁₇O₆₁ (KPW) solutions in 1–7 M HNO₃ was studied spectrophotometrically. Under the experimental conditions, Am(VI) and Am(III) are the final products of Am(V) transformation; the process is described by the rate equation of a reversible reaction. The direct reaction follows the first-order rate equation with respect to Am(V) concentration, and the reverse reaction, the zero-order equation.     

Effect of V<Subscript>2</Subscript>O<Subscript>5</Subscript> content on the optical,structural and electrochromic properties of TiO<Subscript>2</Subscript> and ZrO<Subscript>2</Subscript> thin films

Vanadium oxide (V₂O₅) mixed titanium oxide (TiO₂) and zirconium oxide (ZrO₂) thin films were fabricated on glass substrates (corning 2947) and on indium tin oxide (ITO) coated glass substrates by sol gel spin coating process. Their optical, structural and electrochromic properties were investigated. The results were compared with pure TiO₂ and ZrO₂ thin films. Mixture of V₂O₅ with both types of film reduces the transmittance at the higher wavelengths. The refractive index of the V₂O₅ mixed TiO₂ and ZrO₂ films increases when compared with pure TiO₂ and ZrO₂ films. AFM images demonstrate no significant topographical changes for V₂O₅ mixed TiO₂ whereas for V₂O₅ mixed ZrO₂ films a topographical change is observed. V₂O₅ mixed TiO₂ showed slight increase in their charge capacity.     

Preparation and properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> partially stabilized ZrO<Subscript>2</Subscript> crystals

We have studied the effect of composition and growth conditions on the structure and properties of 2.5–5 mol % Y₂O₃ partially stabilized ZrO₂ crystals grown by directional solidification in a cold-wall crucible. The phase composition and density of the crystals have been determined. The crystals are shown to be uniform in composition, with local changes in Y₂O₃ content within ±0.5 mol %. The dimensions and quality of the single crystals are influenced by the growth conditions.     

Phase analysis of the ZrO<Subscript>2</Subscript>-GeO<Subscript>2</Subscript> system

This paper presents a physicochemical study of poorly explored compounds in the zirconia-germania system. Reactions between these oxides were investigated by differential scanning calorimetry and thermogravimetry. The morphology of the reaction products was studied by scanning electron microscopy. The reaction products of ZrO₂ and GeO₂ powders were characterized by quantitative phase analysis. X-ray diffraction and Raman spectroscopy data indicate the formation of the germanates Zr₃GeO₈ and ZrGeO₄. These compounds are shown to be substitutional solid solutions, and their homogeneity ranges are determined. GeO₂ dissolution in ZrO₂ stabilizes its tetragonal structure.     

Kinetics of Np(V) transformation in concentrated HNO<Subscript>3</Subscript> solutions containing potassium phosphotungstate K<Subscript>10</Subscript>P<Subscript>2</Subscript>W<Subscript>17</Subscript>O<Subscript>61</Subscript>

The behavior of Np(V) in concentrated HNO₃ solutions containing potassium phosphotungstate K₁₀P₂W₁₇O₆₁ (KPW) at various concentrations of HNO₃ (1.0–3.0 M) and KPW [(1–5) × 10^?3 M] was studied. Under the examined experimental conditions, the final products of Np(V) transformation are Np(IV) and Np(VI). The reaction follows a first-order rate equation with respect to the Np(V) concentration.