Silicon production from phosphate industry waste (Na2SiF6)

Production of salable goods from industrial waste can become an additional innovative component of liquid-metal technology of atomic engineering. In this paper, we used sodium silicofluoride (Na₂SiF₆), i.e., phosphate Ca(HPO₄)₂ production waste. Fundamentals of a worldwide unique ecologically clean low-temperature technology of Si reduction from Na₂SiF₆ and Si deposition on substrates in a liquid-metal loop in a single process was developed, as well as a gas-phase technology of Si reduction by sodium from gaseous SiF₄ released during thermal dissociation of Na₂SiF₆.     

Molecular dynamics study of particle emission by reactive cluster ion impact

Molecular dynamics (MD) simulations of sputtering process with fluorine cluster impact onto silicon targets were performed. By iterating collisional simulations on a same target, accumulation of incident atoms and evolution of surface morphology were examined as well as emission process of precursors. When (F₂)₃₀₀ clusters were sequentially irradiated on Si(1 0 0) target at 6 keV of total incident energy, column-like surface structure covered with F atoms was formed. As the number of incident clusters increased, sputtering yield of Si atoms also increased because the target surface was well fluoridised to provide SiF_x precursors. Size distribution of emitted particles showed that SiF₂ was the major sputtered particle, but various types of silicon-fluoride compounds such like Si₂F_x, Si₃F_x and very large molecules consists of 100 atoms were also observed. This size distribution and kinetic energy distribution of desorbed materials were studied, which showed that the sputtering mechanism with reactive cluster ions is similar to that under thermal equilibrium condition at high-temperature.     

Transport processes in heavy metal fluoride glasses

Na self-diffusion, Li self-diffusion, Na⁺–Li⁺ ion exchange, electrical conductivity, and mechanical relaxation have been studied below T_g on glasses of the system ZrF₄–BaF₂–LaF₃–AF (A=Na, Li), with A=10, 20, 30 mol%. Compared to the transport mechanism in alkali-containing silicate glasses, the mechanisms in these non-oxide glasses are anomalous. Thus the self-diffusion coefficient of Na decreases with increasing NaF content, whereas that of Li increases with increasing LiF content. Both the electrical conductivity and the Na⁺–Li⁺ ion exchange reach a minimum at ≈ 20 mol% LiF, and the mechanical relaxation shows one peak for the 20 and 30 mol% LiF-glasses and two peaks for the glass with 10 mol% LiF, evidencing both a contribution of F⁻ and Li⁺ ions to the transport. Moreover, the presence of the three partially interacting mobile species F⁻, Na⁺, Li⁺ obviously leads to an anionic–cationic mixed ion effect. Applying the Nernst–Einstein equation to the Li⁺ transport in LiF-containing glasses shows that its mechanism is dissimilar to that in oxide glasses. Calculated short jump distances possibly can be interpreted as an Li⁺ movement via energetically suitable sites near F⁻ ions. Likewise the Nernst–Planck model, successfully applied to the ionic transport in mixed alkali silicate glasses, obviously does also not hold for the present heavy metal fluoride glasses.     

Evaluation of Synthetic Magnesium Silicate as a New Polymer Filler

The paper reports on the performance of highly dispersed synthetic magnesium silicate as a filler of the styrene–butadiene rubber (SBR). The magnesium silicate has been precipitated and characterized by determination of particle size distribution, electrokinetic potential, nitrogen adsorption/desorption isotherms and SEM observation. At the subsequent stage of the study its surface has been modified by silane coupling agents. The unmodified and silane-grafted magnesium silicate samples have been used as fillers of SBR of standard testing composition. The vulcanizates obtained with the fillers have been tested as to their physical and mechanical performance. The vulcanizates filled with synthetic magnesium silicate have been found to show much better mechanical parameters than unfilled rubber. Modification of the synthetic magnesium silicates with silane coupling agents has further improved the mechanical characteristics of the vulcanizates.     

Photoluminescence of Er silicates on microstructured Si substrate

Large amounts of Er silicates were fabricated on microstructure Si substrates by spin-coating of ErCl₃/ethanol solutions and post-thermal processing techniques. Preoxidation of the substrate enhances the formation of Er silicates (Er₂Si₂O₇, Er₂SiO₅), particularly the portion of Er₂Si₂O₇. The Er silicates fully cover the microstructured substrate, showing no granular morphologies. Very narrow XRD peaks also suggest large grain size of the Er silicate crystals. As-fabricated samples show strong photoluminescence (PL) at room temperature around 1530 nm. The PL intensity is shown to be largely dependent on the conditions of preoxidation, annealing temperature and time, while the decay time is defect-limited, and mainly dependent on the annealing conditions rather than the preoxidation. We suggest that Er silicates can thus be incorporated into ordered Si microstructures, such as photonic crystals, to develop more functional light emitting devices.     

Isotopically selective CVD of silicon by IRMPD of Si2F6

The IRMPD of Si₂F₆ by a CO₂ TEA laser was applied to isotopically selective CVD of silicon. A white film, probably consisting of polymers of SiF₂, was deposited on a metal foil during the irradiation of natural Si₂F₆ with the laser radiation at 951.19 cm^–1 and about 1.5 J cm^–2. Upon heating, the film became dark brown, evolving SiF₄. The³⁰Si content was found to be as high as about 20%.     

Effect of ultrasound on the synthesis of low-modulus zeolites from a metakaolin

It was studied the effect of ultrasonic processing (22 kHz) of the aqueous suspension of metakaolin, sodium hydroxide and alumina with a molar ratio 2Al₂Si₂O₇:12NaOH:2Al₂O₃ on the low-modulus zeolite synthesis processes. To investigate the XRD, SEM, IR, EDS had been used. It was shown that after ultrasonic processing, sodium aluminates are formed, what leads to a change in process of further synthesis. It was found that without ultrasonic processing on the stage of thermal treatment at 650 °C, SOD zeolite (|Na₆|[Al₆Si₆O₂₄]) and sodium aluminosilicate (Na₆Al₄Si₄O₁₇) are synthesized. In the sample after ultrasound during thermal treatment, only sodium aluminosilicates of cubic syngony (Na₆Al₄Si₄O₁₇ and Na₈Al₄Si₄O₁₈) are formed. It was demonstrated that sodium aluminosilicates are precursors for the formation of LTA zeolite (|Na₁₂|[Al₁₂Si₁₂O₄₈]). As a result zeolitization of sodium aluminosilicates after the hydrothermal crystallization in alkaline solution, the sonicated sample contained 97 wt% LTA. Without ultrasonic processing, the product of synthesis contained 50 wt% SOD and 40 wt% LTA.     

Novel clays: Solid-state synthesis,characterization and cation exchange selectivity

Several novel swelling mica-type clays have been synthesized by solid-state processes. Synthetic clays of ideal compositions such as Na₂Si₆Al₂Mg₆O₂₀F₄ · xH₂O (Na-2-mica), Na₃Si₅Al₃Mg₆O₂₀F₄ · xH₂O (Na-3-mica) and Na₄Si₄Al₄Mg₆O₂₀F₄ · xH₂O (Na-4-mica) have been prepared and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and ²⁷Al and ²⁹Si solid-state magic angle spinning nuclear magnetic resonance (MASNMR) spectroscopy. Powder XRD showed that all syntheses yielded water swollen micas with c-axis spacing of ∼1.2 nm except in the case of Na-2-mica which also showed a small peak of anhydrous mica phase with a c-axis spacing of 0.96 nm. Solid-state ²⁷Al MASNMR spectroscopy revealed that almost all the Al is present in the tetrahedral environment of the different micas. Solid-state ²⁹Si MASNMR spectroscopy revealed different Si (Al) nearest neighbor environments depending upon the composition of the various micas. Selective cation exchange studies were performed on the various micas using 0.5 N NaCl solution containing 12.9 ppm Sr²⁺ or 8.12 ppm of La³⁺. The results showed, for the first time, that Na-3-mica has a high selectivity for the trivalent cation tested. The previously reported high selectivity of these synthetic micas for the divalent cations has been confirmed. These selective cation exchange studies are of relevance in cation separations from drinking and waste waters.     

Etching of SiC by energetic F2: Molecular dynamics simulation

Molecular dynamics (MD) simulations were performed to investigate F₂ continuously bombarding silicon carbide (SiC) surfaces with energies in the range of 50-200 eV at normal incidence and room temperature. The Tersoff-Brenner form potential was used. The simulation results show that the uptake of F atoms, the etch yields of C and Si from the initial substrate, and the surface structure profile are sensitive to the incident energy. Like occurrence in Si etching, steady-state etching is observed and an F-containing reaction layer is formed through which Si and C atoms are removed. A carbon-rich surface layer after bombarding by F₂ is observed which is in good agreement with experiments. In the reaction layer, SiF in SiF₂ species are dominant; with increasing incident energy, the total fraction of SiF and SiF₂ increases, while the amount of SiF₃ and SiF₄ decreases. Finally, etching mechanisms are discussed.     

Transport numbers in the molten system NaF–KF–AlF3–Al2O3

Transport numbers in the molten system NaF–KF–AlF₃ (Al₂O₃, CaF₂) were investigated by the Hittorf method. It was confirmed that in molten cryolite, Na₃AlF₆, 1,010 °C, the current is transported almost exclusively by the Na⁺ cations (t(Na⁺)?=?0.99). When AlF₃ was added to a Na₃AlF₆ melt, the transport number of sodium cations decreased to 0.74 at the composition corresponding to NaAlF₄. In molten K₃AlF₆, the transport number of K⁺ cations equals 0.836 at 1,005 °C. In melts containing both Na⁺ and K⁺, the cations contribute to the charge transport approximately in the ratio of the squares of their ionic radii. When 5 mass % of CaF₂ was added to the molten NaF–KF–AlF₃ system, it remarkably influenced the transport numbers of potassium and fluoride anions.     

Compositionally controlled semimetal to superconducting transition in NaF doped LaOFeAs: Enhancement in Tc due to Na-doping

We report the synthesis of LaOFeAs based oxypnictide superconductors (La_1?xNa_xO_1?xF_xFeAs) using sodium fluoride as a fluorinating agent. NaF doping leads to a systematic decrease in both the a and c lattice parameters. Resistivity measurements show the onset resistivity transition temperature at 30.9 (±0.05) K and corresponding Meissner transition at 28 (±0.05) K in La_0.85Na_0.15O_0.85F_0.15FeAs which is highest in LaOFeAs type superconductors synthesized at ambient pressure. Further increase of NaF content in LaOFeAs leads to suppression of T_c. The above superconductors show a negative value of the Seebeck coefficient which indicates that electrons are the dominant charge carriers.     

Availability of water glass/Bi2O3 composites in dielectric and gamma-ray screening applications

ABSTRACT

Sodium silicate (Na₂Si₃O₇) also known as water glass is a very low cost material which is used in many industrial applications such as a builder in detergents, as a binder and adhesive etc. But so far the electrical properties of sodium silicate and its ability to screen radiation have never been investigated. In the present study, the frequency dependent electrical properties and gamma-ray shielding performance of water glass based bismuth oxide composites have been studied for the first time. In accordance with this purpose, Na₂Si₃O₇/Bi₂O₃ glassy composites have been prepared for searching their possible applications in electronics and radiation screening. The surface morphology of the samples have been determined by Scanning Electron Microscope (SEM). The frequency dependent electrical properties such as complex impedance, complex dielectric function and conductivity have been analyzed at room temperature between 1 and 40?MHz. As a result of alternative current (ac) electrical analysis, it has been determined that the Na₂Si₃O₇/Bi₂O₃ composites can be utilized as a dielectric layer in capacitors. On the other hand, since bismuth oxide is an anti-radiative material, the gamma-ray screening parameters such as mass attenuation coefficient, half layer and tenth layer values along with mean free path of the composites have been defined experimentally by using NaI(Tl) scintillation detector for the Ba-133 radiation source at 81 and 356?keV. The values of these parameters have also been checked by Monte–Carlo simulation. Since a good agreement has been assigned between experimental and Monte–Carlo simulation results, the related gamma ray shielding parameters have been determined by Monte–Carlo simulation for other gamma photon energies (140?keV, 208?keV, 468?keV, and 661?keV) which are generated from Tc-99, Lu-177, Ir-132, and Cs-137 sources. Ultimately, Na₂Si₃O₇/Bi₂O₃(35%) composite has been suggested as an eco-friendly, lead-free glassy structured material for the gamma radiation shielding in medical applications.     

The Microstructure of Soda-Lime Silicate Glasses Detected by Electron Microscopy

Transmission electron microscopy and selected area electron diffraction performances were used to characterise the microstructure of a multicomponent soda-lime silicate glass, the composition of which corresponds to the miscibility gap in the SiO₂—Na₂O system. It has been stated that phase separation already exists in as prepared specimens, and the Na₂O-rich phase occurs in the form of nearly spherical droplets. The microstructure of these glasses was modified by high-temperature annealing in air and hydrogen, by irradiation with soft X- and gamma-irradiation and by mechanical stretching. In this way the quantity, size, shape and distribution of these particles was changed. A variety of induced changes affects the structure-sensitive properties of commercial soda lime silicate glasses, which can be potentially useful for new applications.     

Synthesis and luminescence properties of Na2Ba2Si2O7:Eu2+ phosphor

Green-emitting phosphor Na₂Ba₂Si₂O₇:Eu²⁺ has been synthesized by a conventional high-temperature solid-state reaction. The phase structure and luminescence properties are characterized by the X-ray powder diffraction, diffuse reflectance spectra, photoluminescence excitation and emission spectra, temperature-dependent emission spectra, respectively. It can be efficiently excited in the wavelength range of 325–400 nm and consists of a strong broad green band centered at about 501 nm, which is ascribed to 4f⁶6s⁰5d¹ → 4f⁷6s²5d⁰ transition of Eu²⁺. The critical quenching concentration of Eu²⁺ in the Na₂Ba₂Si₂O₇ host is about 0.8 mol % and corresponding quenching behavior is ascribed to be electric dipole–dipole interaction. Furthermore, the phosphor has good thermal stability property, and the activation energy for thermal quenching is calculated as 0.34 eV.     

10BaF2:NaF, Na3AlF6/TiO2 composite as a novel visible-light-driven photocatalyst based on upconversion emission

A rare-earth free upconversion luminescent material, 10BaF2：NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light （550 nm-610 nm） into ultraviolet light （290 nm 350 nm）, and two emission peaks at 304 nm and 324 nm are observed under the excitation of 583 nm at room temperature. Subsequently, 10BaF2：NaF, Na3AIF6/TiO2 composite photocatalyst is prepared and its catalytic activity is evaluated by the photocatalytic reduction of CO2 under visible light irradiation （λ〉 515 nm）. The results show that 10BaF2：NaF, Na3AIF6/TiO2 is a more effective photocatalyst for CO2 reduction than pure TiO2, their corresponding methanol yields are 179 and 0 μmol/g-cat under the same conditions. Additionally, the mechanism of photocatalytic reduction of CO2 on 10BaF2：NaF, Na3AIF6/TiO2 is proposed.     

Effect of processing parameters on the deposition rate of Si3N4/Si2N2O by chemical vapor infiltration and the in situ thermal decomposition of Na2SiF6

Silicon nitride (Si₃N₄) and oxynitride (Si₂N₂O) were deposited by chemical vapor infiltration (CVI) through a novel route involving the in-situ thermal decomposition of Na₂SiF₆ in commercial nitrogen precursors containing impurity oxygen. In addition, the quantitative effect of processing time (30, 60, 90, 120 min), temperature (1000, 1100, 1200 and 1300 °C), nitrogen precursor (N₂ or N₂-5%NH₃) and gas flow rate (46.5, 93, 120 and 240 cm³/min) on phase percentage and deposition rate of Si₃N₄ and Si₂N₂O was investigated. Analysis of variance shows that the parameter that most significantly impacts the total amount of deposited phase is the processing temperature, followed by processing time and nitrogen precursor. Regardless of the nitrogen precursor, at 1300 °C, Si₃N₄ and Si₂N₂O depositions follow an S-like and parabolic behavior, respectively. The incubation period shown by Si₃N₄ in N₂-5%NH₃ is associated to a decrease in the O₂ partial pressure during Si₂N₂O formation while the rapid increase at long processing times is attributed to the enhanced effect of hydrogen. PACS 81.15.Gh; 81.05.Je; 81.15.-z; 81.05.Rm; 47.85.L-     

Luminescence of La3F3[Si3O9]:Ce

The luminescence properties of Ce³⁺ in La₃F₃[Si₃O₉] are reported. Excitation and emission bands corresponding to 4f¹→5d¹ transitions of Ce³⁺ were identified. The center of gravity of the 5d states lies at remarkable high energy (43.2×10³ cm⁻¹) for Ce³⁺ in a silicate compound. This high value is attributed to the combined oxygen/fluoride coordination of the Ce³⁺ ion. Emission from the lowest 4f5d level to the ²F_5/2 and ²F_7/2 levels was found at 32.4×10³ and 30.4×10³ cm⁻¹. These results are compared with literature data on silicates and fluorides. From the values found for Ce³⁺, predictions are made for the positions of the 4f5d bands of Pr³⁺ and Er³⁺ in La₃F₃[Si₃O₉]. For both ions, it is concluded that in this host lattice emission is expected from high lying 4fⁿ energy levels.     

Investigation on Tm3+-doped silicate glass for 1.8 μm emission

A Tm³⁺-doped silicate glass (SiO₂–CaO–Na₂O–K₂O) with good thermal stability is prepared by the melt-quenching method. Intense 1.8 μm emission is obtained when pumped by an 808 nm laser diode. Based on the measured absorption spectra, radiative properties are predicted using Judd–Ofelt theory and Judd–Ofelt parameters Ω_λ (λ=2, 4, 6), as well as absorption and emission cross-sections are calculated and analyzed. The difference between the measured Tm³⁺:³F₄ lifetime and the calculated lifetime is also discussed. The emission property together with good thermal property indicates that Tm³⁺-doped silicate glass is a potential kind of laser glass for efficient 2 μm laser.     

Practical separation of silicon isotopes by IRMPD of Si2F6

Large-scale silicon isotope separation based on the IRMPD of natural Si₂F₆ has been carried out using a commercially available high power CO₂ TEA laser and a flow reaction system. The decomposition product SiF₄ containing 19–33% of ³⁰Si was obtained at a production rate of 1.5×10^–2–2.6×10^–2 mol·h^–1, depending on experimental parameters such as laser wavelength, laser fluence, pressure, and flow rate. SiF₄ containing 12% of ²⁹Si was obtained under slightly different conditions, i.e., at a shorter wavelength than that for ³⁰Si. When 39% of Si₂F₆ was decomposed at a slow flow rate, residual Si₂F₆ was found to have 99.7% of ²⁸Si. The production rate was 4.2×10^–2 mol·h^–1.     

Structure and Thermal Stability of Polystyrene/Layered Silicate Nanocomposites

Polystyrene/layered silicates nanocomposites were prepared by intercalation in solution method, using CHCl₃ and CCl₄ as solvents. The clay used was organically modified by hexadecyltrimethyl–ammonium bromide (CTAB) at various surfactant loadings. It was found that intercalated nanocomposite structure was obtained using CHCl₃ as solvent while exfoliated or partially exfoliated was the predominant form in the case of CCl₄. X-ray diffraction and thermogravimetric analysis were used to characterize the nanocomposite morphology and thermal stability, respectively. Enhancement in thermal stability was observed for PS-nanocomposites compared to that of pristine polymer as indicated by TGA measurements. This increment was more prevalent for exfoliated nanocomposites prepared with carbon tetrachloride as solvent.