Preparation and properties of transparent SnO–P2O5 glasses

Colorless, transparent SnO–P₂O₅ (SP) glasses with 60–70 mol% SnO compositions were prepared by melting at 880–1000 °C in Ar atmosphere using commercial SnO and P₂O₅ powders as raw materials and vitreous carbon crucibles. SP glasses are characterized by glass transition temperature, onset of crystallization, thermal expansion coefficient and weight loss after immersion test. The viscosity of 67SnO–33P₂O₅ glass was measured by a penetration method in the range of 10^7.9–10^10.5 Pa s at 267–290 °C. The results of optical properties show that the transparent SP glasses have high refractive indexes over 1.75 and high transmission over 80% in the visible and IR region of 380 and 2700 nm.     

High temperature protonic conduction in Sr-doped LaP3O9

Electrical conduction of Sr-doped LaP₃O₉ ([Sr]/{[La] + [Sr]} = 2–10 mol%) was investigated under 0.4–5 kPa of p(H₂O) and 0.01–100 kPa of p(O₂) or 0.3–3 kPa of p(H₂) at 573–973 K. Sr-doped LaP₃O₉ showed apparent H/D isotope effect on conductivity regardless of the Sr-doping level under both H₂O/O₂ oxidizing and H₂/H₂O reducing conditions at investigated temperatures. Conductivities of the material were almost independent of p(O₂) and p(H₂O). These results demonstrated that the Sr-doped LaP₃O₉ exhibited protonic conduction under wide ranges of p(O₂), p(H₂O) and temperature. The conductivity of the Sr-doped LaP₃O₉ increased with increasing Sr concentration up to its solubility limit, ca. 3 mol%, while the further Sr-doping slightly degraded the conductivity. These indicate that Sr²⁺ substitution for La³⁺ leads to proton dissolution into the material and induced protonic conduction. Conductivities of the 3 mol% Sr-doped sample were 2 × 10^- 6–5 × 10^− 4 S cm^− 1 at 573–973 K.     

Spectroscopic properties of Sm3+ ions in lead fluorophosphate glasses

The Sm³⁺-doped lead fluorophosphate glasses of composition 44P₂O₅–17K₂O–9Al₂O₃–(24?x)PbF₂–6Na₂O–xSm₂O₃, where x=0.01, 0.05, 0.1, 0.5, 1.0 and 2.0 mol%, have been prepared by conventional melt quenching technique and are characterized through differential thermal analysis, Raman, absorption and emission spectra and decay rate measurements. Free-ion Hamiltonian model for energy level analysis and Judd–Ofelt theory for spectral intensities have been used to analyze the spectroscopic properties of Sm³⁺ ions in lead fluorophosphate glasses. The decay rates for the ⁴G_5/2 level of Sm³⁺ ions have been measured and are found to be single exponential at lower concentration (≤0.1 mol% Sm₂O₃) and turn into non-exponential at higher concentrations (≥0.5 mol% Sm₂O₃) due to energy transfer through cross-relaxation. The experimental lifetimes for ⁴G_5/2 level of Sm³⁺ ions are found to decrease from 2.54 to 0.92 ms when the concentration increased from 0.01 to 2.0 mol% Sm₂O₃ due to energy transfer. In order to know the nature of the energy transfer mechanism, the non-exponential decay rates are well fitted to Inokuti–Hirayama model for S=6, which indicates that the energy transfer process is of dipole–dipole type.     

Effect of nanocrystallization on the electronic conductivity of vanadate–phosphate glasses

Electronically conducting glasses of the composition xV₂O₅·(100 − x)P₂O₅ for 60 < x < 90 were prepared. The glasses of the composition corresponding to x = 90 exhibited the highest electrical conductivity and they were studied in more detail. The effects of the annealing of the samples on their electrical conductivity, structure and other characteristics were studied by impedance spectroscopy, X-ray diffractometry, DSC and SEM microscopy. It was shown that, at temperatures close to the crystallization temperature T_c (determined from DSC), these glasses turned into nanomaterials consisting of crystalline grains of V₂O₅ (average size 25–35 nm) embedded in the glassy matrix. Their electrical conductivity was higher and the temperature stability was better than those of the starting glasses. It is postulated that the major role in this conductivity enhancement is played by the interfacial regions between crystalline and amorphous phases. The annealing at temperatures exceeding T_c led to massive crystallization and to a conductivity drop. The XRD and SEM observations have shown that the material under study undergoes structural changes: from amorphous at the beginning, to partly crystalline after the annealing at 340 °C and to polycrystalline after the annealing at 530 °C.The obtained results are in agreement with those of our earlier studies on mixed electronic–ionic conducting glasses of the ternary Li₂O–V₂O₅–P₂O₅ system.     

Effect of Li2O on the structure,electrical and dielectric properties of xLi2O·(20−x)CaO·30P2O5·30V2O5·20Fe2O3 glasses

Glasses of the general formula xLi₂O·(20?x)CaO·30P₂O₅·30V₂O₅·20Fe₂O₃ with x=0, 5, 10, 15 and 20 mol% were prepared; IR, density, electrical and dielectric properties have been investigated. Lithia-containing glasses revealed more (P₂O₇)^4?, FeO₆, V–O^? and PO^? groups and mostly have lower densities than those of lithia-free ones. The electrical properties showed random behavior by replacing Li₂O for CaO, which has been assigned to the change of the glass structure. The results of activation energy and frequency-dependent conductivity indicate that the conduction proceeds via electronic and ionic mechanisms, the former being dominant. The mechanism responsible for the electronic conduction is mostly thermally activated hopping of electrons from Fe(II) ions to neighboring Fe(III) sites and/or from V⁴⁺ to V⁵⁺. The dielectric constant (ε′) showed values that depend on the structure of glass according to its content of Li₂O. The (ε′) values are ranging between 3 and 41 at room temperature for 1 kHz, yet at high temperatures, glass with 20 mol Li₂O exhibits values of 110 and 3600 when measurement was carried out in the range 0.1–1 kHz, and at 5 MHz, respectively.     

Er–Pr doped tellurite glass nanocomposites for white light emitting diodes

In this paper, optical glass nanocomposites (nanoparticles sizes up to 100 nm) with composition TeO₂–WO₃–PbO–xEr₂O₃–yPr₆O₁₁ (x = 0.30 mol%, y = 0.70 mol%) embedded into polymer matrices was reported. The two types of polymers chosen for present study were: photopolymer oligoetheracryalte (OEA) and polymethylmethacrylate (PMMA), respectively. The incorporation of the titled nanoparticles into the polymer matrices is analyzed optically. The fluorescence spectra of the nanocomposites were compared with the fluorescence spectra of bulk glasses. Based on the comparison of Er^3 + and Pr^3 + ions' energy level schemes, possible energy transfer processes were identified. The prepared glasses are promising candidates for the white light emitting diodes applications.     

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.     

Formation and its mechanism of copper metal layers at surface by annealing in reduced atmosphere in CuO–Li2O–Nb2O5–SiO2 glass

A trace amount (0.5 mol%) of CuO-doped 40Li₂O–32Nb₂O₅–28SiO₂ glass (mol%) exhibits the formation of copper metal layers at the glass surface by annealing at temperatures (530 °C) below the glass transition temperature (544 °C) in the reduced atmosphere of 7% H₂–93%Ar. The coordination state of copper ions is examined from optical absorption and Fourier transform infrared (FT-IR) spectrum measurements, indicating the formation of Si–OH and Si–H bonds due to the diffusion of hydrogen into the inside of the glass and the reduction of Cu⁺ and Cu²⁺ ions. The mechanism of the formation of copper metals at the surface is proposed, in which the key points are the reduction of Cu²⁺ to Cu⁺ ions due to the hydrogen and the migration of Cu⁺ ions in the interior of the glass to the surface. The first finding on copper metal layers at the glass surface might have a potential for practical applications such as electrodes in glass.     

Infrared broadband emission of bismuth–thulium co-doped lanthanum–aluminum–silica glasses

The Bi–Tm co-doped SiO₂–Al₂O₃–La₂O₃ (SAL) glasses, which exhibited a broadband near-infrared (NIR) emission was investigated by the optical absorption and photoluminescence spectra. The super broadband near-infrared emission from 1000 to 2100 nm, which covered the whole O, E, S, C and L bands, was observed in the Bi–Tm co-doped samples, as a result of the overlap of the Bi-related emission band (centered at 1270 nm) and the emission from Tm^{3+ 3}H₄→³F₄ transition (1440 nm) as well as Tm^{3+ 3}F₄→³H₆ transition (1800 nm). Relative luminescence intensity at 1270, 1440 and 1800 nm wavelength varied depending on the mixing ratio of Bi and Tm and the full-width at half-maximum (FWHM) extending from 1000 to 1600 nm could be 400 nm. These results indicated that Bi–Tm co-doped SiO₂–Al₂O₃–La₂O₃ glasses could provide potential applications in tunable lasers as well as the broadband optical amplifiers in WDM system.     

Spectroscopic characterization of Tm3+:TeO2–K2O–Nb2O5 glasses for 2-μm lasing applications

We have performed detailed experiments to investigate the spectroscopic properties of a new type of tellurite based host doped with thulium: Tm₂O₃:(0.70)TeO₂–(0.15)K₂O–(0.15)Nb₂O₅ having Tm₂O₃ concentrations of 0.125, 0.25, 0.5, and 1.0 mol%. By performing a Judd–Ofelt analysis of the absorption bands, we obtained average radiative lifetimes of 2.57±0.20 and 0.35±0.01 ms for the ³H₄ and ³F₄ levels, respectively. Furthermore, we also observed that an increase in the Tm₂O₃ concentration from 0.125 to 1.0 mol% results in a decrease of the measured fluorescence lifetime from 814 to 439 μs and from 258 to 47 μs for the ³H₄ and ³F₄ levels, respectively, due to efficient non-radiative decay. The highest quantum efficiency of 32% was obtained for the sample doped with 0.125 mol% Tm₂O₃ for the ³H₄ level. Results show that cross relaxation becomes important as the ion concentration is increased, leading to the quenching of the 1460-nm band and enhancement of the 1860-nm emission. The highest emission cross section of 6.85×10^?21 cm² measured for the 1860-nm band reveals the potential of this host for the development of 2-μm lasers in bulk glass as well as fiber media.     

Detection of OH radical and O atom during triboluminescence of hydrated cerium/terbium sulfates

Triboluminescence of Се₂(SO₄)₃·8H₂O and Tb₂(SO₄)₃·8H₂O crystals has been studied. For the first time spectral evidence for a contribution of light-emitting products OH^? (283 and 290 nm maxima, 1–0 transition; 308.4 and 309.6 nm, 0–0 transition) and excited oxygen atom O^? (777 nm, 3P⁵P—3S⁵S) produced via mechano-chemical decomposition of H₂O and O₂ molecules in the destruction of crystal hydrates of the salts to the gas-phase component of triboluminescence has been obtained.     

Infrared spectra of acetylene–water complexes: C2D2–H2O,C2D2–HDO,and C2D2–D2O

Infrared spectra of C₂D₂–water complexes are studied in the 4.1 μm region of the C₂D₂ ν₃ fundamental band using a tunable diode laser source to probe a pulsed supersonic slit jet. Relatively large vibrational red shifts (?27.7 to ?28.0 cm^?1) are observed which are more easily interpretable than for the analogous C₂H₂ vibration thanks to the absence of Fermi resonance effects for C₂D₂. Noticeable homogeneous line broadening leads to estimates of upper state predissociation lifetimes of about 0.5, 0.9 and 1.1 ns for C₂D₂–H₂O, –HDO, and –D₂O, respectively. Transitions involving K_a = 0 and 1 levels are observed for C₂D₂–HDO, but there is a puzzling absence of K_a = 1 for C₂D₂–H₂O and C₂D₂–D₂O.     

Optical characteristics of Tb-doped InBO3 nanocrystals

InBO₃ nanocrystals doped with Tb³⁺ ions are prepared via the sol–gel method. The structure, morphology, and optical properties of the nanocrystals are characterized by X-ray diffraction, high-resolution transmission electron microscopy, field-emission scanning electron microscopy, and photoluminescence analysis. The results show that a hexagonal InBO₃ phase forms at above 650 °C. A second phase of In₂O₃ begins to appear with Tb doping of over 3 mol%. The ⁵D₄→⁷F₅ (553 nm) transitions of Tb³⁺ ions in the InBO₃ host are observed at 2 mol%. The decay time of Tb-doped InBO₃ nanocrystals is about 2.1 ms. For Tb-doped InBO₃ nanocrystals excited at 237 nm and 553 nm wavelengths, the 2 mol% doping level yields the highest saturation of green emission. The emission shifts from green to yellow when the doping concentration is increased from 1 to6 mol%, due to the ⁵D₄→⁷F₅ transition.     

Oxygen diffusion studies on (Y2O3)2(Sc2O3)9(ZrO2)89

The oxygen tracer diffusion coefficient (D?) has been measured for 9 mol% scandia 2 mol% yttria co-doped zirconia solid solution, (Y₂O₃)₂(Sc₂O₃)₉(ZrO₂)₈₉, using isotopic exchange and line scanning by Secondary Ion Mass Spectrometry, as a function of temperature. The values of the tracer diffusion coefficient are in the range of 10^? 8–10^? 7 cm² s^? 1 and the Arrhenius activation energy was calculated to be 0.9 eV; both valid in the temperature range of 600–900 °C. Electrical conductivity measurements were carried out using 2-probe and 4-probe AC impedance spectroscopy, and a 4-point DC method at various temperatures. There is a good agreement between the measured tracer diffusion coefficients (D?, Ea = 0.9 eV) and the diffusion coefficients calculated from the DC total conductivity data (D_σ, Ea = 1.0 eV), the latter calculated using the Nernst–Einstein relationship.     

Surface modification of Ni and Co metal nanowires through MeV high energy ion irradiation

Nickel (Ni) and cobalt (Co) metal nanowires were fabricated by using an electrochemical deposition method based on an anodic alumina oxide (Al₂O₃) nanoporous template. The electrolyte consisted of NiSO₄ · 6H₂O and H₃BO₃ in distilled water for the fabrication of Ni nanowires, and of CoSO₄ · 7H₂O with H₃BO₃ in distilled water for the fabrication of the Co ones. From SEM and TEM images, the diameter and length of both the Ni and Co nanowires were measured to be ∼ 200 nm and 5–10 μm, respectively. We observed the oxidation layers in nanometer scale on the surface of the Ni and Co nanowires through HR–TEM images. The 3 MeV Cl²⁺ ions were irradiated onto the Ni and Co nanowires with a dose of 1 × 10¹⁵ ions/cm². The surface morphologies of the pristine and the 3 MeV Cl²⁺ ion-irradiated Ni and Co nanowires were compared by means of SEM, AFM, and HR–TEM experiments. The atomic concentrations of the pristine and the 3 MeV Cl²⁺ ion-irradiated Ni and Co nanowires were investigated through XPS experiments. From the results of the HR–TEM and XPS experiments, we observed that the oxidation layers on the surface of the Ni and Co nanowires were reduced through 3 MeV Cl²⁺ ion irradiation.     

Comparative study of the spectroscopic properties of Yb3+/Er3+ codoped tellurite glasses modified with R2O (R=Li,Na and K)

Spectroscopic characterization of Yb³⁺/Er³⁺ codoped TeO₂–R₂O–ZnO–Ln₂O₃ glasses as a function of network modifiers (R=Li, Na and K) has been investigated. The Judd–Ofelt parameters (Ω_t), quantum efficiency in near infrared (1.55 μm) and visible up-conversion (546 and 660 nm) and quality factor spectroscopy (χ) were calculated. Three up-conversion emission bands centered at 525, 546 and 660 nm were observed as maxima for glasses containing potassium. The measured lifetime of ⁴I_13/2, ⁴F_9/2 and ⁴S_3/2 from Er³⁺ and ⁴F_5/2 from Yb³⁺ levels increased when potassium (K) replaced lithium (Li) and Na. The maximum emission cross-section (ECS) for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ was calculated to be 1.02×10^?20 cm² for TeO₂–Li₂O–ZnO–Ln₂O₃ glasses. The energy transfer efficiency (ET) from Yb³⁺ to Er³⁺, (⁴F_5/2)+(⁴I_15/2)→(⁴F_7/2)+(⁴I_13/2), was calculated using the measured lifetimes of Yb³⁺ with and without the presence of acceptor (Er³⁺). The maximum calculated ET was 58% for 0.25 mol% of Er³⁺ and 3 mol% of Yb³⁺ for TeO₂–K₂O–ZnO–Ln₂O₃ glass composition.     

High lithium ion conducting glass-ceramics in the system Li2S–P2S5

Highly ion-conductive Li₂S–P₂S₅ glass-ceramic electrolytes were prepared by controlling the compositions and heat treatment temperatures of the glasses. The 70Li₂S·30P₂S₅ (mol%) glass-ceramic heated at 360 °C showed the highest conductivity of 3.2 × 10^− 3 S cm^− 1 at room temperature and the lowest activation energy of 12 kJ mol^− 1 for conduction in the binary system Li₂S–P₂S₅. The outstanding property was attributed to both the precipitation of the new crystal as a metastable phase and the increase in crystallinity of the phase. With increasing heat treatment temperatures, the metastable phase changed into thermodynamically stable phases such as the Li₄P₂S₆ crystal by heat treatment up to 550 °C, resulting in low conductivities of the glass-ceramics. It was, thus, found that the formation of superionic metastable phases by heating the Li₂S–P₂S₅ glasses is responsible for the marked enhancement on the conducting properties of the glass-ceramics.     

Sonochemical water splitting in the presence of powdered metal oxides

Kinetics of hydrogen formation was explored as a new chemical dosimeter allowing probing the sonochemical activity of argon-saturated water in the presence of micro- and nano-sized metal oxide particles exhibiting catalytic properties (ThO₂, ZrO₂, and TiO₂). It was shown that the conventional sonochemical dosimeter based on H₂O₂ formation is hardly applicable in such systems due to catalytic degradation of H₂O₂ at oxide surface. The study of H₂ generation revealed that at low-frequency ultrasound (20 kHz) the sonochemical water splitting is greatly improved for all studied metal oxides. The highest efficiency is observed for relatively large micrometric particles of ThO₂ which is assigned to ultrasonically-driven particle fragmentation accompanied by mechanochemical water molecule splitting. The nanosized metal oxides do not exhibit particle size reduction under ultrasonic treatment but nevertheless yield higher quantities of H₂. The enhancement of sonochemical water splitting in this case is most probably resulting from better bubble nucleation in heterogeneous systems. At high-frequency ultrasound (362 kHz), the effect of metal oxide particles results in a combination of nucleation and ultrasound attenuation. In contrast to 20 kHz, micrometric particles slowdown the sonolysis of water at 362 kHz due to stronger attenuation of ultrasonic waves while smaller particles show a relatively weak and various directional effects.     

Electronic core levels of hydroxyls at the surface of chromia related to their XPS O 1s signature: A DFT + U study

The Cr 2p and O 1s binding energy (BE) levels have been calculated by first principles methods for different models of hydroxylated (0001)-Cr₂O₃ surfaces. Several surface terminations have been considered. The calculations allow us to reproduce the O 1s shifts between O in oxide and OH groups. It is found that two main effects account for the OH binding energy shifts. On the one hand, the increased covalency of the O–H bond with respect to the Cr–O bond, lowers the electronic O (1s and 2p) energy, and in consequence the BE of the core levels (O 1s) are higher. On the other hand, the lower the OH coordination number, the higher the valence and core levels energy, and the lower the BE. Consequently, mono-coordinated hydroxyls have a binding energy near that of O^2? in the oxide (ΔBE_OH–O = ? 0.2–0.0 eV). Two-fold coordinated hydroxyls have a slightly higher BE (ΔBE_OH–O = + 0.3 eV). Three-fold coordinated OH groups have a higher binding energy (ΔBE_OH–O = + 0.6?0.7 eV), corresponding to that experimentally measured for OH groups. Finally, water adsorbed above OH groups exhibits a still higher BE (ΔBE_HOH–O = + 0.9–1.0 eV). The ΔBE are slightly under-estimated under the initial state approximation, and overestimated under the final state (Z + 1) approximation.     

The structure and extinction of nonpremixed methane/nitrous oxide and ethane/nitrous oxide flames

Knowledge of combustion of hydrocarbon fuels with nitrogen-containing oxidizers is a first step in understanding key aspects of combustion of hypergolic and gun propellants. Here an experimental and kinetic-modeling study is carried out to elucidate aspects of nonpremixed combustion of methane (CH₄) and nitrous oxide (N₂O), and ethane (C₂H₆) and N₂O. Experiments are conducted, at a pressure of 1 atm, on flames stabilized between two opposing streams. One stream is a mixture of oxygen (O₂), nitrogen (N₂), and N₂O, and the other a mixture of CH₄ and N₂ or C₂H₆ and N₂. Critical conditions for extinction are measured. Kinetic-modeling studies are performed with the San Diego Mechanism. Experimental data and results of kinetic-modeling show that N₂O inhibits the flame by promoting extinction. Analysis of the flame structure shows that H radicals are produced in the overall chain-branching step 3H₂ + O₂ ? 2H₂O + 2H, in which molecular hydrogen is consumed. Hydrogen is also consumed in the overall step N₂O + H₂ ? N₂ + H₂O where stable products are formed. Inhibition of the flames by N₂O is attributed to competition between these two overall steps.