Rotational Spectra of CH3CCH–NH3, NCCCH–NH3, and NCCCH–OH2

Microwave spectra of NCCCH–NH₃, CH₃CCH–NH₃, and NCCCH–OH₂have been recorded using a pulsed-nozzle Fourier-transform microwave spectrometer. The complexes NCCCH–NH₃and CH₃CCH–NH₃are found to have symmetric-top structures with the acetylenic proton hydrogen bonded to the nitrogen of the NH₃. The data for CH₃CCH–NH₃are further consistent with free or nearly free internal rotation of the methyl top against the ammonia top. For NCCCH–OH₂, the acetylenic proton is hydrogen bonded to the oxygen of the water. The complex has a dynamicalC_2vstructure, as evidenced by the presence of two nuclear-spin modifications of the complex. The hydrogen bond lengths and hydrogen-bond stretching force constants are 2.212 Å and 10.8 N/m, 2.322 Å and 6.0 N/m, and 2.125 Å and 9.6 N/m for NCCCH–NH₃, CH₃CCH–NH₃, and NCCCH–OH₂, respectively. For the cyanoacetylene complexes, these bond lengths and force constants lie between the values for the related hydrogen cyanide and acetylene complexes of NH₃and H₂O. The NH₃bending and weak-bond stretching force constants for CH₃CCH–NH₃are less than those found in NCCCH–NH₃, NCH–NH₃, and HCCH–NH₃, suggesting that the hydrogen bonding interaction is particularly weak in CH₃CCH–NH₃. The weakness of this hydrogen bond is partially a consequence of the orientation of the monomer electric dipole moments in the complex. In CH₃CCH–NH₃the antialigned monomer dipole moments lead to a repulsive dipole–dipole interaction energy, while in NCH–NH₃and NCCCH–NH₃the aligned dipoles give an attraction interaction.     

Broadband 2.84 μm luminescence properties and Judd–Ofelt analysis in Dy3+ doped ZrF4–BaF2–LaF3–AlF3–YF3 glass

2.84 μm luminescence with a bandwidth of 213 nm is obtained in Dy³⁺ doped (ZrF₄–BaF₂–LaF₃–AlF₃–YF₃) ZBLAY glass. Three intensity parameters and radiative properties have been determined from the absorption spectrum based on the Judd–Ofelt theory. The 2.84 μm emission characteristics and energy transfer mechanism upon excitation of a conventional 808 nm laser diode are investigated. The prepared Dy³⁺ doped ZBLAY glass possessing high predicted spontaneous transition probability (45.92 s^?1) along with large calculated emission cross section (1.17×10^?20 cm²) has potential applications in 2.8 μm laser.     

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.     

The NaNO3–KNO3 phase diagram

Many papers have been published in relation to the NaNO₃–KNO₃ phase diagram determination in the last 160 years. These papers fall in two categories: (1) the solid–liquid equilibrium is assumed to be of the eutectic type, and (2) the solid–liquid equilibrium is considered as a loop with a minimum. The discordance between the two views is related to the slow transition kinetics that complicate the assessment of thermal ‘fluctuations’, and also to the appearance of a metastable form of potassium nitrate. The main result of this paper is the experimental phase diagram constructed with new experimental data so that we can assure that the second option is correct. This phase diagram is defined by a eutectoid invariant, an asymmetric immiscibility gap and a continuous solid solution with a minimum of melting point. Additionally, the ABθ model simulates correctly the experimental piece of evidence.     

Thermal analysis of precipitation reactions in a Ti–25Nb–3Mo–3Zr–2Sn alloy

A study was undertaken on a Ti–25Nb–3Mo–3Zr–2Sn alloy using differential scanning calorimetry (DSC) in order to improve understanding of the precipitation reactions occurring during aging heat treatments. The investigation showed that isothermal ω phase can be formed in the cast and solution treated alloy at low aging temperatures. An exothermic peak in the temperature range of 300 to 400°C was detected for precipitation of the ω phase, with approximate activation energy of 176 kJ/mol. The ω phase begins to dissolve at temperatures around 400°C and precipitation of the α phase is favoured at higher temperatures between 400°C and 600°C. An exothermic peak with activation energy of 197 kJ/mol was measured for precipitation of the α phase. Deformation resulting in the formation of the stress induced α″ phase altered the DSC heating profile for the solution treated alloy. The exothermic peak associated with precipitation of the ω phase was not detected during heating of the deformed material and increased endothermic heating associated with recovery and recrystallisation was observed.     

Spectroscopic Properties of Er3+/Yb3+-codoped PbO–Bi2O3–Ga2O3–GeO2 Glasses

We investigate the spectroscopic properties of the 1.5-μm emission from the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions in PbO–Bi₂O₃–Ga₂O₃–GeO₂ glasses for applications in broadband fiber amplifiers. The measured emission peak locates at 1,532 nm with a full width at half-maximum of ∼45 nm. The glasses exhibit a large stimulated emission cross-section of 0.89 × 10⁻²⁰ cm² and a large product of 40.0. Infrared-to-green upconversion occurs simultaneously upon excitation of the 1.5-μm emission with a commercially available 980 nm laser diode. The green-upconversion intensity has a quadratic dependence on incident pump laser power, indicating a two-photon process. Energy transfer processes and nonradiative phonon-assisted decays could account for the population of the ²H_11/2 of Er³⁺. The results indicate the possibility towards the development of lead–bismuth–gallate–germanate based glasses as photonics devices.     

Colour emission tunability in Ho3+–Tm3+–Yb3+ co-doped Y2O3 upconverted phosphor

The frequency upconversion (UC) emission throughout the visible region from the Y₂O₃:Ho³⁺?CTm³⁺?CYb³⁺ co-doped phosphors synthesized by using low temperature combustion process upon excitation with a diode laser operating at 980?nm have been presented. The colour emission tunability in co-doped phosphor has been observed on increasing the pump power and seen by the naked eyes. The tunability in colour emission has also been visualized by CIE chromaticity diagram. The variation in UC emission intensity of the ¹G₄????³H₆ (Tm³⁺) and ⁵F₃????⁵I₈ (Ho³⁺) transitions lying in the blue region has been monitored with increase in the pump power and marked that their ratio can be used to determine the temperature. The developed phosphor has been used to record fingerprints. The observed most intense visible colour emission from the developed material may be used for photodynamic therapy and as an alternative of traditional fluorescent biolabels.     

The system Na2CO3–MgCO3 at 3 GPa

It was suggested that Na–Mg carbonates might play a substantial role in mantle metasomatic processes through lowering melting temperatures of mantle peridotites. Taking into account that natrite, Na₂CO₃, eitelite, Na₂Mg(CO₃)₂, and magnesite, MgCO₃, have been recently reported from xenoliths of shallow mantle (110–115?km) origin, we performed experiments on phase relations in the system Na₂CO₃–MgCO₃ at 3?GPa and 800–1250°C. We found that the subsolidus assemblages comprise the stability fields of Na-carbonate?+?eitelite and eitelite?+?magnesite with the transition boundary at 50?mol% Na₂CO₃. The Na-carbonate–eitelite eutectic was established at 900°C and 69?mol% Na₂CO₃. Eitelite melts incongruently to magnesite and a liquid containing about 55?mol% Na₂CO₃ at 925?±?25 °C. At 1050 °C, the liquid, coexisting with Na-carbonate, contains 86–88?mol% Na₂CO₃. Melting point of Na₂CO₃ was established at 1175?±?25 °C. The Na₂CO₃ content in the liquid coexisting with magnesite decreases to 31?mol% as temperature increases to 1250°C. According to our data, the Na- and Mg-rich carbonate melt, which is more alkaline than eitelite, can be stable at the P–T conditions of the shallow lithospheric mantle with thermal gradient of 45?mW/m² corresponding to temperature of 900 °C at 3?GPa.     

Ceramic synthesis of 0.08BiGaO_3–0.90BaTiO_3–0.02LiNbO_3 under high pressure and high temperature

In this paper, the preparation of 0.08BiGaO_3–0.90BaTiO_3–0.02LiNbO_3 is investigated at pressure 3.8 GPa and temperature 1100–1200?C. Experimental results indicate that not only is the sintered rate more effective, but also the sintered temperature is lower under high pressure and high temperature than those of under normal pressure. It is thought that the adscititious pressure plays the key role in this process, which is discussed in detail. The composition and the structure of the as-prepared samples are recorded by XRD patterns. The result shows that the phases of Ba TiO_3, BaBiO_(2.77), and Ba_2Bi_4Ti_5O_(18) with piezoelectric ceramic performance generate in the sintered samples. Furthermore, the surface morphology characteristics of the typical samples are also investigated using a scanning electron microscope. It indicates that the grain size and surface structure of the samples are closely related to the sintering temperature and sintering time. It is hoped that this study can provide a new train of thought for the preparation of lead-free piezoelectric ceramics with excellent performance.     

Electrical transport characteristics of ZnO–Bi2O3–B2O3 glasses

Optically clear glasses in the ZnO–Bi₂O₃–B₂O₃ (ZBBO) system were fabricated via the conventional melt-quenching technique. Dielectric constant and loss measurements carried out on ZBBO glasses unraveled nearly frequency (1 kHz–10 MHz)-independent dielectric characteristics associated with significantly low loss (D?=?0.004). However, weak temperature response was found with temperature coefficient of dielectric constant 18?±?4 ppm °C^?1 in the 35–250 °C temperature range. The conduction and relaxation phenomena were rationalized using universal AC conductivity power law and modulus formalism respectively. The activation energy for relaxation determined using imaginary parts of modulus peaks was 2.54 eV which was close to that of the DC conduction implying the involvement of similar energy barriers in both the processes. Stretched and power exponents were temperature dependent. The relaxation and conduction in these glasses were attributed to the hoping and migration of Bi³⁺ cations in their own and different local environment.     

Subsolidus phase relation in the Bi_2O_3–Fe_2O_3–La_2O_3 system

Bismuth-containing semiconductor material is a hot topic in photocatalysts because of its effective absorption under the visible light.In this paper,we expect to explore a new bismuth-based photocatalyst by studying the subsolidus phase relations of the Bi2O3–Fe2O3–La2O3system.The X-ray diffraction data shows that in this ternary system the ternary compound does not exist,while seven binary compounds(including one solid solution series Bi1 xLaxO1.5with 0.167≤x≤0.339)are obtained and eight compatibility triangles are determined.     

Specific Features of the Local Structure and Transport Properties of ZrO2–Sc2O3–Y2O3 and ZrO2–Sc2O3–Yb2O3 Crystals

Optics and Spectroscopy - The specific features of the local structure of ZrO2–Sc2O3–Y2O3 and ZrO2–Sc2O3–Yb2O3 crystals are revealed by optical spectroscopy using the Eu3+...     

Stability of Thin-Film Cu–As2S3 and Ag–As2S3 Structures

Technical Physics - Thin-film Cu–As2S3 and Ag–As2S3 structures obtained by successively evaporating Cu(Ag) and As2S3 in vacuum on glass substrates have been studied. Samples of these...     

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