Synthesis of nano-sized titanium diboride in a melt of anhydrous sodium tetraborate

X-ray powder diffraction, scanning electron microscopy, infrared spectroscopy, and elemental analysis were used to study the interaction of titanium powder with finely powdered boron of particle size 10?C20 ??m in Na₂B₄O₇ ionic melt, in the temperature range 973?C1088 K, at the 5?C10 h contact duration. The TiB₂ formation was shown to occur at the temperatures 1018 K or above, that is, at the borax melting temperature. According to the scanning electron microscopy, theTiB₂ powder consists of the 70?C75 nm particles, and its coherent scattering region calculated from the XRD data amounts to 55 nm.     

Phase equilibria in M2O-MgO-B2O3 (M=Na, Rb) systems

The Na₂O-MgO-B₂O₃ system (500-550°C) and Rb₂O-MgO-B₂O₃ system (550-700°C) were studied by the methods of powder X-ray diffraction and visual polythermal analysis, and their isothermal sections were constructed at 550 and 650-700°C, respectively. New ternary compounds were found to form: Na₂₄Mg₃B₁₀O₃₀, Na₄Mg₃B₂O₈, and Rb₂Mg₃B₂O₇.     

Interaction between Co2P4O12 and alkali metal nitrate (chloride) melts

Reactions between Co₂P₄O₁₂ and alkali metal nitrate (chloride) melts was studied in the temperature range 350–400°C (800–850°C) at different phosphate/melt ratios. The effect of the nature of an alkali metal and the ratio between the components in the Co₂P₄O₁₂-M^INO₃ (M^ICl) system on composition of the reaction products was established. The resulting crystalline phases (NaCoPO₄, Na₄Co₃(PO₄)₂P₂O₇, Na₉Co₃(PO₄)₅ and KCoPO₄) were studied by X-ray powder diffraction, IR and electron spectroscopy, and scanning electron microscopy. The features of transformation of the Co₂P₄O₁₂ framework into KCoPO₄ under the effect of excessive alkali metal ions in the melt are discussed.     

Synthesis of nanosized group IV borides in ionic melts of anhydrous sodium tetraborate

The preparation of nanosized Group IV metal diborides by reacting powdery titanium, zirconium, and hafnium with fine-grained boron in Na₂B₄O₇ ionic melts in the temperature range 600–850°C has been studied. Nanosized titanium, zirconium, and hafnium diborides are formed at temperatures of at least 750°C.     

Synthesis of Zirconium Diboride Nanoparticles by the Reaction of ZrCl4 with NaBH4 in an Ionic Potassium Bromide Melt

Nanosized particles of zirconium diboride are synthesized by the reaction of ZrCl₄ with NaBH₄ in an ionic KBr melt.

     

Synthesis and Characterization of Indium-borate Glass-ceramics Containing Ho0.01Ce0.74Zr0.25O1.995 Nanorods via Incorporation Method

Glasses in the system 5In₂O₃·94Na₂B₄O₇ were fabricated via melt quenching technique. The amorphous nature of the quenched glasses was confirmed by X‐ray powder diffraction studies, and the infrared spectra of the glasses show no boroxol ring formation in the structure of these glasses. Differential thermal analysis is shown glass transition temperature 696°C and crystallization temperature 1151°C. A cerium‐zirconium mixed oxide Ce_0.75Zr_0.25O₂ and Ho‐doped cerium‐zirconium mixed oxide were obtained by solid‐state method. Then glass powder and Ho‐doped cerium‐zirconium mixed oxide were mixed. The mixture was heated in a crucible. The glass‐ceramic sample was obtained by pouring the melts on stainless steel. Obtained samples were annealed at 450°C for 1 h to remove thermal strain. Differential thermal analysis for glass‐ceramic sample is shown glass transition temperature 668°C and crystallization temperature 1159°C. The scanning electron microscopy study for glass‐ceramic indicates that the crystallized glass consists of rod‐like crystals with average diameter of about 38 nm dispersed in the glassy regions.     

Phase equilibria in the BaO-Bi2O3-B2O3 system

Phase equilibria in the BaO-Bi₂O₃-B₂O₃ system have been investigated by X-ray powder diffraction analysis and DTA. Quasi-binary sections have been determined, and an isothermal section of the system in the subsolidus region has been constructed. The BaO-Bi₂O₃-B₂O₃ ternary system has been divided into 22 triangles of coexisting phases. It has been found that four bismuth barium borates exist, namely, Ba₃BiB₃O₉, BaBi₂B₄O₁₀, BaBiB₁₁O₁₉, and BaBiBO₄. Ba₃BiB₃O₉ undergoes a phase transition at 850°C and exists up to 885°C, where it decomposes in the solid state. BaBiB₁₁O₁₉ and BaBi₂B₄O₁₀ melt congruently at 807 and 730°C, respectively. BaBiBO₄ melts incongruently at 780°C. X-ray powder diffraction data for the low-temperature polymorph of Ba₃BiB₃O₉ are presented.     

Crystallization of MgFe2O4 from a glass in the system K2O/B2O3/MgO/P2O5/Fe2O3

Spherical magnetic Mg-Fe-O nanoparticles were successfully prepared by the crystallization of glass in the system K₂O/B₂O₃/MgO/P₂O₅/Fe₂O₃. The magnetic glass ceramics were prepared by melting the raw materials using the conventional melt quenching technique followed by a thermal treatment at temperatures in the range 560–700 °C for a time ranging from 2 to 8 h. The studies of the X-ray diffraction, electron microscopy and FTIR spectra confirmed the precipitation of finely dispersed spherical (Mg, Fe) based spinel nanoparticles with a minor quantity of hematite (α-Fe₂O₃) in the glass matrix. The average size of the magnetic nano crystals increases slightly with temperature and time from 9 to 15 nm as determined by the line broadening from the XRD patterns. XRD studies show that annealing the glass samples for long periods of time at temperature ≥604 °C results in an increase of the precipitated hematite concentration, dissolution of the spinel phase and the formation of magnesium di-borate phase (Mg₂B₂O₅). For electron microscopy, the particles were extracted by two methods; (i) replica extraction technique and (ii) dissolution of the glass matrix by diluted acetic acid. An agglomeration of the nano crystals to larger particles (25–35 nm) was observed.     

Synthesis and Characterization of Nd~(3+)-Doped Indium-sodium Tetraborate Glasses

Glasses in the system xNd₂O₃·(10?x)In₂O₃·90Na₂B₄O₇ (with x=0, 1, 3, 5 mol%) were fabricated via a melt quenching technique. The amorphous nature of the quenched glasses was confirmed by X‐ray powder diffraction studies. The infrared spectra of the glasses show no boroxol ring formation in the structure of these glasses. Optical absorption of glasses shows that the transition ⁴I_9/2→⁴G_5/2+²G_7/2 is more intense than the other transitions, which shifts from 580 nm (for the free Nd³⁺ ion ) to 584 nm. The peak in fluorescence spectra for x=5 mol% Nd³⁺ in the region 800–900 nm under excitation wavelength 584 nm was attributed to ⁴F_3/2→⁴I_9/2 transition. Differential thermal analysis for (x=5 mol% Nd³⁺) shows glass transition (ca. 600°C) and crystallization temperatures (ca. 1155, 975°C). The scanning electron microscopy studies indicate the amorphous state of glass sample.     

Electrical properties of crystalline borates

Anisotropy of electrical and dielectric properties of α- and β-BaB₂O₄, Ba₂Na₃(B₃O₆)₂F, LiB₃O₅, and CsLi(B₃O₅)₂ single crystals is reported and discussed. In these crystals, alkali ions are dominant charge carriers; pre-heating to 300°C eliminates the humidity, preheating to 500 or 600°C, stabilizes the structure and electrical properties of crystals. Then, both ionic conductivity and dielectric response are determined by movement of alkali ions, and temperature dependences of the ionic conductivity and static permittivity are well reproducible.     

Synthesis of nanometric β-barium metaborate powder from different borate solutions by ultrasound-assisted precipitation

In this study, the synthesis of barium metaborate powder (BaB₂O₄) was carried out by ultrasound-assisted precipitation using different borate solutions. Different solutions such as borax (Na₂B₄O₇, BD), boric acid (H₃BO₃, BA), and sodium metaborate (NaBO₂, SMB) were used in the synthesis and an ultrasonic immersion horn probe was used as the major source of ultrasound. The effect of reaction temperature and time, pH, and crystallization time on the BaB₂O₄ yield (%) was investigated. The ultrasound-assisted synthesis up to 90 % yield could be achieved using a 0.2 M BD solution at 80 °C, reacting for 5 min at pH 13 followed by 2 h of crystallization. Following crystallization, the obtained powder was heated up to 140, 250, 650, and 750 °C for 2.5 h, and it was shown that β-BaB₂O₄ nanometric powders were obtained after the 750 °C heat treatment.     

Dimorphie von SrTa4O11 - ein Schritt von der tetragonalen Bronzestruktur zur Struktur von CaTa4O11

Dimorphism of SrTa₄O₁₁–a Step from the Tetragonal Structure of Bronzes to the Structure of CaTa₄O₁₁ Hexagonal SrTa₄O₁₁ is a new modification and isostructural with CaTa₄O₁₁. It was obtained by heating the already known SrTa₄O₁₁ in a chlorine atmosphere at 1000–1100°C. The Guinier powder pattern could be indexed with the following hexagonal unit cell: a = 6.25 Å; c = 12.33 Å. In air at 1180°C SrTa₄O₁₁(hex.) changes into the well-known TTB-modification (corresponding to the tetragonal tungsten bronzes). The transition of SrTa₄O₁₁(TTB) to SrTa₄O₁₁(hex.) was only observed in the presence of a transporting agent (Cl₂) or a mineralizer (melt of B₂O₃) at temperatures below 1100°C. This transition could not be achieved by means of a solid state reaction. In a (Ca, Sr) Ta₄O₁₁ solid solution with at least 78 At.-% Ca the hexagonal form could be stabilized even at temperatures where otherwise the TTB-modification occurred.     

Nano‐Fe3O4@SiO2‐SO3H: A magnetic,reusable solid‐acid catalyst for solvent‐free reduction of oximes to amines with the NaBH3CN/ZrCl4 system

In this study, the immobilization of sulfonic acid on silica‐layered magnetite was carried out by the reaction of ClSO₃H with silica‐layered magnetite. The prepared magnetic nanoparticles of Fe₃O₄@SiO₂‐SO₃H were then characterized using scanning electron microscopy, energy dispersive X‐ray spectroscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, vibrating sample magnetometry, and transmission electron microscopy. The sulfonated nanocomposite exhibited excellent catalytic activity and reusability in the reduction of various aldoximes and ketoximes with NaBH₃CN in the presence of ZrCl₄. All reactions were carried out under solvent‐free conditions (r.t. or 75–80°C) within 3–70 min to afford amines in high to excellent yields.     

High temperature reactions of titanium(IV) oxide with some alkali persulfates and their decomposition products

The solid state reactions between TiO₂ and Na₂S₂O₈ or K₂S₂O₈ have been investigated using TG, DTG, DTA, IR, and X-ray diffraction studies in the range of 20 to 1000°C.It has been shown that TiO₂ reacts stoichiometrically (1 : 1) with Na₂S₂O₈ in the range of 160 and 220°C forming the complex sodium monoperoxodisulfato—titanium(IV) as characterized by IR and X-ray analysis. The new complex then decomposes into the reactants above 190°C.An exothermic reaction has been observed between TiO₂ and molten K₂S₂O₇ at mole ratio 1:2 respectively and higher, in the range of 280 and 350°C. The IR and X-ray analyses have shown the formation of a complex namely, potassium tetrasulfato titanium(IV) for which the formula and structure have been proposed. This complex decomposes at higher temperatures into K₂SO₄ and a mixed sulfate of potassium and titanium. The mixed sulfate melts at 620°C and decomposes into K₂SO₄, TiO₂, and the gaseous SO₃.On the other hand, Na₂S₂O₈ decomposes in a special mode producing a polymeric product of Na₁₀S₉O₃₂. Decomposition of this species occurs after melting at 560°C into Na₂SO₄ and sulfur oxides. The decomposition reaction has been proved to be catalysed by TiO₂ itself.     

Process for the conversion of highly caustic spent sodium borohydride fuel

The presence of caustic soda in the spent sodium borohydride (NaBH₄) fuel in high concentrations creates environmental problems associated with the transportation and the disposal of the fuel, orits recycling into NaBH₄. It is clear that the high level of caustic soda in the spent fuel requires efficient and proper formulation of its industrial recycling applications. The present study regards the conversion process of the caustic soda present in high concentrations in spent NaBH₄ fuels. Properties of the caustic used in NaBH₄ fuel is characterized using a comprehensive technique. A specific application is presented here, which includes the treatment of the spent fuel solution with anhydrous borax (Na₂B₄O₇) at 90?°C for 3?h followed by calcination after the crystallization, resulting in the conversion of this highly caustic spent NaBH₄ fuel into sodium metaborate (NaBO₂), which is an environmentally friendlier and an economically valuable material.     

Phase equilibria in the Bi2O3-BaB2O4-B2O3 system in the subsolidus region

The phase equilibria in the concentration triangle Bi₂O₃-BaB₂O₄-B₂O₃ of the BaO-Bi₂O₃-B₂O₃ system have been investigated by X-ray powder diffraction and DTA. Barium bismuth borates of the composition BaBi₂B₄O₁₀ and BaBiB₁₁O₁₉ have been found to exist. These borates melt at 730 and 807°C, respectively. The quasi-binary sections have been determined. It has been shown that the isothermal section of the Bi₂O₃-BaB₂O₄-B₂O₃ in the subsolidus region at 600°C is characterized by 13 triangles of coexisting phases.     

Phase Relations in the Solidus Region of the SrO-Bi2O3-B2O3 System

Phase equilibria in the SrO-Bi₂O₃-B₂O₃ system have been investigated by X-ray powder diffraction analysis and DTA. Ternary compounds SrBiBO₄ and Sr₇Bi₈B₁₈O₄₆ congruently melting at 820 ± 5°C and 760 ± 5°C have been found. Quasi-binary sections are determined and the isothermal section of the system in the region Bi₂O₃-Sr₂Bi₂O₆-Sr₃B₂O₆-B₂O₃ at 600°C has been constructed.     

Study of tin dioxide–sodium stannate composite obtained by decomposition of peroxostannate as a potential anode material for lithium-ion batteries

A tin dioxide–sodium stannate composite has been obtained by the thermal treatment of sodium peroxostannate nanoparticles at 500°C in air. X-ray powder diffraction study has revealed that the composite includes crystalline phases of cassiterite SnO₂, sodium stannate Na₂Sn₂O₅, and sodium hexahydroxostannate Na₂Sn(OH)₆. Scanning electron microscopy has shown that material morphology does not change considerably as compared with the initial tin peroxo compound. Electrochemical characteristics have been compared for the anodes of lithium-ion batteries based on tin dioxide–sodium stannate composite and anodes based on a material manufactured by the thermal treatment of graphene oxide–tin dioxide–sodium stannate composite at 500°C in air.     

Synthesis and characterization of poly(aminoborane) as a new boron nitride precursor

During the solution reaction of NaBH₄/(NH₄)₂SO₄ in tetraglyme to form borazine, polymeric aminoborane (NH₂BH₂)_x has been isolated as a white powder. The powder was characterized by thermal gravimetric analysis/differential scanning calorimetry, infrared and mass spectroscopies, and powder X‐ray diffraction. Solid‐state ¹⁵N and ¹¹B nuclear magnetic resonance firmly proved that the chain‐like poly(aminoborane) evolved a partially condensed B₃N₃ ring structure by dehydrogenative condensation between chains at 200 °C. Pyrolysis of the polymer in a nitrogen stream up to 1400 °C led to a 75% yield of hexagonal boron nitride with an interlayer spacing of 3.37 Å. Copyright © 1999 John Wiley & Sons, Ltd.     

Breaking the Passivation: Sodium Borohydride Synthesis by Reacting Hydrated Borax with Aluminum

A significant obstacle in the large-scale applications of sodium borohydride (NaBH₄) for hydrogen storage is its high cost. Herein, we report a new method to synthesize NaBH₄ by ball milling hydrated sodium tetraborate (Na₂B₄O₇ ⋅ 10H₂O) with low-cost Al or Al₈₈Si₁₂, instead of Na, Mg or Ca. An effective strategy is developed to facilitate mass transfer during the reaction by introducing NaH to enable the formation of NaAlO₂ instead of dense Al₂O₃ on Al surface, and by using Si as a milling additive to prevent agglomeration and also break up passivation layers. Another advantage of this process is that hydrogen in Na₂B₄O₇ ⋅ 10H₂O serves as a hydrogen source for NaBH₄ generation. Considering the low cost of the starting materials and simplicity in operation, our studies demonstrate the potential of producing NaBH₄ in a more economical way than the commercial process.