Mechanism of formation of the complex oxide Na<Subscript>2</Subscript>Nd<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>10</Subscript>

The processes of phase formation in the Nd₂O₃-TiO₂-Na₂CO₃ system have been investigated in the temperature range 500–1100°C. The mechanism of the high-temperature solid-phase reaction of formation of the complex oxide Na₂Nd₂Ti₃O₁₀ has been studied. It has been established that the Na₂Nd₂Ti₃O₁₀ compound is formed from the intermediate product Na_0.5Nd_0.5TiO₃ with a perovskite structure in the temperature range 830–890°C and from the NaNdTiO₄ oxide with a perovskite-like layered structure in the temperature range 960–1100°C.     

Synthesis of Heterogeneous Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> Nanostructured Anodes with Long-Term Cycle Stability

The 0D-1D Lithium titanate (Li₄Ti₅O₁₂) heterogeneous nanostructures were synthesized through the solvothermal reaction using lithium hydroxide monohydrate (Li(OH)·H₂O) and protonated trititanate (H₂Ti₃O₇) nanowires as the templates in an ethanol/water mixed solvent with subsequent heat treatment. A scanning electron microscope (SEM) and a high resolution transmission electron microscope (HRTEM) were used to reveal that the Li₄Ti₅O₁₂ powders had 0D-1D heterogeneous nanostructures with nanoparticles (0D) on the surface of wires (1D). The composition of the mixed solvents and the volume ratio of ethanol modulated the primary particle size of the Li₄Ti₅O₁₂ nanoparticles. The Li₄Ti₅O₁₂ heterogeneous nanostructures exhibited good capacity retention of 125 mAh/g after 500 cycles at 1C and a superior high-rate performance of 114 mAh/g at 20C.     

Investigation into the formation of phases with a Ba<Subscript>2</Subscript>Ti<Subscript>9</Subscript>O<Subscript>20</Subscript>-type structure in the BaO-TiO<Subscript>2</Subscript> and BaO-SrO-TiO<Subscript>2</Subscript> systems

The mechanism of formation of barium titanate Ba₂Ti₉O₂₀ in the BaO-TiO₂ and BaO-SrO-TiO₂ systems is investigated using initial mixtures prepared by three methods, namely, mechanical grinding of the initial reactants, coprecipitation from aqueous solutions of salts, and the sol-gel technique. It is established that, irrespective of the preparation procedure, the formation of Ba₂Ti₉O₂₀ proceeds through the formation of the intermediate phases BaTi₄O₉ and BaTi₅O₁₁. The nature of the intermediate phases is determined by the homogeneity and dispersion of the initial mixture, as well as by the stability of the intermediate phase. The most optimum conditions for the synthesis of Ba₂Ti₉O₂₀ are provided by the formation of BaTi₅O₁₁ as an intermediate phase upon heat treatment of the coprecipitation products in the nanocrystalline state. The metastability and structural defects in the BaTi₅O₁₁ intermediate phase encourage a decrease in the temperature of the final heat treatment by 100–150°C in the course of the preparation of Ba₂Ti₉O₂₀ single-phase ceramics.     

Formation of La<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> crystals from amorphous La<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> powders synthesized by the polymerized complex method

Amorphous La₂O-TiO₂ powders were synthesized by the polymerized complex (PC) method. The activation energies for crystallization and grain growth of La₂Ti₂O₇ from these precursors were determined from results of XRD and DTA and compared with those for La₂Ti₂O₇ precursors by the conventional solid-state reaction (SSR). Activation energy of grain growth of La₂Ti₂O₇ in PC-sample was determined to be 7.1 kJ/mol while that of SSR sample was 14.8 kJ/mol. The energy required for the phase transformation from amorphous PC sample to layered perovskite was 432 kJ/mol, while the SSR sample did not show this transition below 900‡C. It was clearly demonstrated that the La₂Ti₂O₇ crystals were formed at a lower temperature and they grew in size faster in the sample prepared by the PC method relative to the sample prepared by the SSR method. Mixing of elements in molecular level in PC preparation appeared responsible for these differences.     

Synthesis and Spectral Properties of Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>-Doped Sodium Silicophosphate Glass

Combined UV-visible and FTIR spectral studies of undoped and Nd₂O₃ –doped sodium silicophosphate glasses were carried out to characterize the optical and structural properties of such glasses. The base undoped silicophosphate glass exhibits strong UV absorption which is due to the presence of unavoidable trace iron impurities (mainly Fe³⁺ ions) present contaminated within the raw materials used for the preparation of such glasses. Nd₂O₃ –doped glasses show characteristic absorption bands extending in the entire visible region which are attributed to the contribution of Nd³⁺ ions with distinct peaks which are almost constant with the increase of dopant. This comes from the combined compact glass structure containing two glass forming units and the shielding of the rare-earth ions. Infrared absorption spectra of the studied glasses reveal characteristic IR bands due to the combination of both silicate and phosphate groups. The introduction of Nd₂O₃ within the dopant level (2 %) produces no variations in the IR vibrational bands due to the presence of the two structural silicate and phosphate groups giving compactness of the network structure. The deconvoluted spectra reveal the presence of phosphate groups in a slightly high ratio due to the high content of P₂O₅ in the composition.     

Crystal structure of new compound (Rb,K)<Subscript>2</Subscript>Cu<Subscript>3</Subscript>(P<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>2</Subscript>

A new compound of (Rb,K)₂Cu₃(P₂O₇)₂ is obtained by high-temperature reactions from a mixture of RbNO₃, KNO₃, Cu(NO₃)₂, and (NH₄)₄P₂O₇. The crystal structure was solved by direct methods and refined to R ₁ = 0.056 for 5022 independent reflections. The compound belongs to a rhombic crystal system, P2₁2₁2₁, Z = 8, a = 9.9410(7) Å, b = 13.4754(6) Å, c = 18.6353 (3) Å, and R = 0.056. The basis of the structure is a complex copper-phosphate skeleton of the composition of [Cu₃(P₂O₇)₂]^2–, which can be regarded as consisting of two types of heteropolyhedral layers parallel to the (001) plane. The layers are alternated with each other, forming a frame, in the cavities of which the positions of alkali cations are located, statistically populated with K⁺ and Rb⁺ ions. Based on the refined populations of the positions of alkali cations, an exact chemical formula of the compound can be written as Rb_1.28K_0.72Cu₃(P₂O₇)₂. The compound is the most complex among those known to this day of the composition of A₂ ^IB₃ ^II(P₂O₇)₂ (A = Li, Na, K, Rb, or Cs; B = Ni, Cu, or Zn).     

Phase Equilibria in the Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>-SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript> System

The phase equilibria are investigated and the phase diagram is constructed for the Gd₂O₃-SrAl₂O₄ pseudobinary join of the Gd₂O₃-SrO-Al₂O₃ ternary oxide system. One ternary compound, namely, Gd₂SrAl₂O₇, is revealed in the Gd₂O₃-SrAl₂O₄ join. It is found that this compound undergoes congruent melting.     

Dependence of the optical properties of the 30.5K<Subscript>2</Subscript>O · 8.3Al<Subscript>2</Subscript>O<Subscript>3</Subscript> · 3.6SiO<Subscript>2</Subscript> · 57.6P<Subscript>2</Subscript>O<Subscript>5</Subscript> glass on the trivalent titanium content

An optical material, namely, the potassium aluminosilicophosphate glass activated with trivalent titanium ions, is synthesized and studied. The optimum concentration range (0.2–10.0 wt % Ti₂O₃) that provides the best physical, luminescent, and kinetic properties of glasses is determined. This makes it possible to use the sensitizing properties of Ti³⁺ ions to the greatest extent.Original Russian Text Copyright © 2004 by Fizika i Khimiya Stekla, Batyaev, Leonov.     

Facile synthesis of nano-Li<Subscript>4</Subscript> Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> for high-rate Li-ion battery anodes

One of the most promising anode materials for Li-ion batteries, Li₄Ti₅O₁₂, has attracted attention because it is a zero-strain Li insertion host having a stable insertion potential. In this study, we suggest two different synthetic processes to prepare Li₄Ti₅O₁₂ using anatase TiO₂ nanoprecursors. TiO₂ powders, which have extraordinarily large surface areas of more than 250 m² g^-1, were initially prepared through the urea-forced hydrolysis/precipitation route below 100°C. For the synthesis of Li₄Ti₅O₁₂, LiOH and Li₂CO₃ were added to TiO₂ solutions prepared in water and ethanol media, respectively. The powders were subsequently dried and calcined at various temperatures. The phase and morphological transitions from TiO₂ to Li₄Ti₅O₁₂ were characterized using X-ray powder diffraction and transmission electron microscopy. The electrochemical performance of nanosized Li₄Ti₅O₁₂ was evaluated in detail by cyclic voltammetry and galvanostatic cycling. Furthermore, the high-rate performance and long-term cycle stability of Li₄Ti₅O₁₂ anodes for use in Li-ion batteries were discussed.     

Optoelectronic Properties of Al/n-Si/ Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript>/Au Photosensor

We have fabricated an Al/n-Si/Bi₄Ti₃O₁₂/Au photodiode by the sol-gel method. The photoelectrical response of the diode was measured under dark and various light intensity conditions. The photocurrent of the diode increases with increase in light intensity. The light sensitivity value of the photosensor was measured and observed to increase from 5.06 × 10^?8 (under dark) to 2.34 × 10^?4 A (under 100 mW/cm²). Furthermore, other parameters for instance, ideality factor and barrier height of the photosensors were calculated. The ideality factor and barrier height of the Al/n-Si/Bi₄Ti₃O₁₂/Au photosensor were found to be 3.01 and 0.86 eV respectively. Also capacitance-voltage (C-V) characteristics were measured. The C-V graph indicates changeable behavior with the varying frequency. The value of capacitance and the interface state density D_it value decrease with increase in frequency. Thus, the obtained results indicate that the Al/n-Si/Bi₄Ti₃O₁₂/Au photosensor can be used as a photosensor in optoelectronic applications.     

Viscosity of glass melts in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The temperature dependences of the viscosity are investigated for three series of glass melts in the SrO-B₂O₃-SiO₂ system with a constant strontium oxide content equal to 35, 40, or 45 mol % in the viscosity range from 10¹⁰ to 10¹³ P.     

Phase Transformations in Stabilized ZrO<Subscript>2</Subscript> - Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> Compositions

Data on interactions in the ZrO₂ - Fe₂O₃ system stabilized by oxides in a high-temperature form at 1750°C are obtained. Of all zirconia-based compositions, only magnesium-zirconium cubic solid solution enters into an active reaction with Fe₂O₃ to yield MgFe₂O₄. The solid solutions formed by ZrO₂ with oxides of yttrium, neodymium, and calcium resist degradation by attack from Fe₂O₃; part of iron oxide undergoes dissolution in cubic ZrO₂. __________ Translated from Novye Ogneupory, No. 9, pp. 40 – 43, September, 2005.     

Improvement in dielectric and mechanical performance of CaCu<Subscript>3.1</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12.1</Subscript> by addition of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

The properties of CaCu_3.1Ti₄O_12.1 [CC3.1TO] ceramics with the addition of Al₂O₃ nanoparticles, prepared via a solid-state reaction technique, were investigated. The nanoparticle additive was found to inhibit grain growth with the average grain size decreasing from approximately 7.5 μm for CC3.1TO to approximately 2.0 μm for the unmodified samples, while the Knoop hardness value was found to improve with a maximum value of 9.8 GPa for the 1 vol.% Al₂O₃ sample. A very high dielectric constant > 60,000 with a low loss tangent (approximately 0.09) was observed for the 0.5 vol.% Al₂O₃ sample at 1 kHz and at room temperature. These data suggest that nanocomposites have a great potential for dielectric applications.     

Structure and crystallization of ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Structure and crystalline behavior of the ternary system ZnO-B₂O₃-P₂O₅ glasses were investigated by means of X-ray diffraction (XRD) and infrared Raman spectra. The research showed that number of the planar [BO₃] units increases with the increase of B₂O₃ content. When the B₂O₃ content is above ≥10 mol %, the relative content of planar [BO₃] units increases rapidly and causes weakening of the glass structure and decrease in the chemical stability. In the crystallized glasses the predominant crystal phase Zn₂P₂O₇ decreases with the increase of B₂O₃ content, while the crystal phase BPO₄ increases with it, which cause the declining of chemical stability and the decrease of thermal coefficients of expansion.     

Synthesis and Thermoelectric Properties of Ceramics Based on Bi<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Co<Subscript>1.7</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Oxide

Layered ceramics based on bismuth–calcium cobaltite with varied cobalt oxide contents is synthesized by the solid-phase method, the ceramics phase composition is determined, and the microstructure, thermal expansion, electroconductivity, and thermal electromotive force are investigated. The formation of just one compound, ternary oxide composed of Bi₂Ca₂Co_1.7O _y , is established within the quasi-binary Bi₂Ca₂O₅–CoO _z system. The effect of the cobalt oxide content on the Bi₂Ca₂Co _x O _y ceramics’ microstructure and physicochemical properties is analyzed. The single-phased ceramic sample Bi₂Ca₂Co_1.7O _y demonstrated the highest power factor value among all the investigated samples—26.0 μW/(m K²) at a temperature of 300 K. This sample showed the lowest value of the thermal linear expansion coefficient of 9.72 × 10^–6 K^–1.     

Formation of the complex oxide NaNdTiO<Subscript>4</Subscript>

The processes of phase formation in the Na₂CO₃-TiO₂ and Na₂CO₃-TiO₂-Nd₂O₃ systems are investigated in the temperature range 600–900°C. The high-temperature solid-phase reactions underlying the process of formation of complex oxide NaNdTiO4 are studied. It is established that the synthesis of the NaNdTiO₄ compound occurs through the reaction of the intermediate product Na₈Ti₅O₁₄ with neodymium oxide in the temperature range 720–780°C. The optimum method is proposed for synthesizing NaNdTiO₄, which makes it possible to reduce the temperature of the synthesis, to avoid the formation of impurities, and to obtain the product in a finely dispersed state.     

Synthesis of Titanates with a Ramsdellite-Type Tunnel Structure Crystallizing in the Li<Subscript>2</Subscript>O-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> System in Different Gaseous Media

The ramsdellite-type phases crystallizing in the Li₂O-Fe₂O₃-TiO₂ system in the course of synthesis in gaseous media at different oxygen partial pressures are studied. Solid solutions based on the ramsdellite structure with the composition Li₂Ti_3?xFe _x O_{7 ? δ} (0 ≤ x ≤ 0.7) are prepared in an oxidizing medium (P_O2 = 1 atm) for the first time. Analysis of the results obtained by electron paramagnetic resonance and Mossbauer spectroscopy revealed that, in these solid solutions, all iron ions are in the oxidation state Fe⁺³.     

Chemical and electrochemical characterization of TiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> atomic layer depositions on AZ-31 magnesium alloy

In this study, innovative TiO₂/Al₂O₃ mono/multilayers were applied by atomic layer depositions (ALD) on ASTM-AZ-31 magnesium/aluminum alloy to enhance its well-known scarce corrosion resistance. Four different configurations of ALD layers were tested: single TiO₂ layer, single Al₂O₃ layer, Al₂O₃/TiO₂ bilayer and Al₂O₃/TiO₂/Al₂O₃/TiO₂ multilayer deposited using Al[(CH₃)]₃ (trimethylaluminum, TMA), and TiCl₄ and H₂O precursors. All depositions were performed at 120°C to obtain an amorphous-like structure of both oxide layers. The four coatings were then investigated using different techniques, such as scanning electron microscope (SEM), stylus profilometer, glow discharge optical emission spectrometry (GDOES) and polarization curves in 0.05-M NaCl solution. The thickness of all the coatings was around 100 nm. The layers compositions were successfully investigated by the GDOES technique, although obtained data seem to be affected by substrate roughness and differences in sputtering rates between ceramic oxides and metallic magnesium alloy. Corrosion resistance showed to be strongly enhanced by the nanometric coatings, giving lower corrosion current densities in 0.05-M NaCl media with respect to the uncoated substrate (from 10⁻⁴ to 10⁻⁶ A/cm² for the single layers and from 10⁻⁴ to 10⁻⁸ A/cm² for the bi- and multilayers). All polarization curves on coated samples also showed a passive region, wider for the bi-layer (from −0.58 to −0.43 V with respect to Ag/AgCl) and multilayer (from −0.53 to −0.38 V with respect to Ag/AgCl) structures.     

Electrical conductivity and the nature of charge carriers in glasses of the Tl<Subscript>2</Subscript>O-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The concentration dependence of the electrical conductivity of glasses in the Tl₂O-B₂O₃ system is studied. The nature of charge carriers in this system is experimentally investigated for the first time. It is demonstrated using the Hittorf, Tubandt, and Hebb-Liang-Wagner techniques and the Faraday law that neither Tl⁺ ions nor electrons are involved in the electricity transport. The verification of the Faraday law does not reveal the presence of thallium in the amalgam of the cathode or a change in the sample weight after electrolysis, to within the experimental error. This allows one to make the inference that protons can be charge carriers in glasses of the Tl₂O-B₂O₃ system. It is shown using extended X-ray absorption fine structure (EXAFS) spectroscopy that Tl³⁺ ions and thallium Tl⁰ reduced to the metallic state are absent in the structure of the glasses under investigation. This means that thallium in glasses of the Tl₂O-B₂O₃ system occurs only in the form of Tl⁺ ions. The analysis of the IR spectroscopic data leads to only a qualitative conclusion that the water content in the glasses insignificantly increases with an increase in the thallium oxide content. An increase in the electrical conductivity of glasses in the Tl₂O-B₂O₃ system with an increase in the thallium oxide content is explained by the increase in the number of protons formed upon dissociation of H⁺[BO_4/2]^? structural-chemical units, because their concentration increases with increasing Tl₂O content. In the structure of boron oxide, impurity hydrogen enters predominantly into the composition of H⁺[O_2/2BO^?] structural-chemical units, for which the dissociation energy is higher than that for the H⁺[BO_4/2]^? structural-chemical units. The increase in the concentration of H⁺[BO_4/2]^? structural-chemical units is accompanied by the increase in the number of dissociated protons, which are charge carriers in glasses of the Tl₂O-B₂O₃ system.     

Crystallization of glasses in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The crystallization of strontium borate glasses containing 16.7–43.0 mol % SrO is investigated. New crystalline compounds of the hypothetical compositions 2SrO · 3B₂O₃ (metastable) and SrO · 5B₂O₃ (stable below 750°C), as well as the metastable diborate modification β-SrO · 2B₂O₃, are revealed, and their X-ray powder diffraction data are obtained. It is demonstrated that, with a deficit of strontium oxide, the 4SrO · 7B₂O₃ compound forms solid solutions. Strontium triborate SrO · 3B₂O₃, which was previously prepared only through the dehydration of crystal hydrates, is produced using crystallization of glasses. The thermal stability of this compound is studied. The influence of the dispersity on the stability of different crystalline phases is discussed. Variants of the phase diagram for the SrO · B₂O₃-B₂O₃ system in the case of monolithic and dispersed samples are proposed from analyzing the experimental results and the data available in the literature.