Effect of cobalt-60 γ radiation on the physical and chemical properties of poly(ethylene terephthalate) polymer

The structural, optical, and morphological properties of Co⁶⁰ γ irradiation on poly(ethylene terephthalate) polymer samples were studied with X-ray diffraction (XRD), ultraviolet–visible spectroscopy, scanning electron microscopy (SEM), and Raman spectroscopy. The diffraction pattern of virgin sample showed that the polymer was semicrystalline in nature. However, because of irradiation, the crystallinity decreased up to a dose level of 110 kGy and increased up to 300 kGy. The crystallite size, strain, and dislocation were calculated from the XRD data, and the crystallite size decreased from 291.07 to 346.90 Å. The absorption edge shifted from 315 to 330 nm, and the band gap of the samples decreased from 3.79 to 3.66 eV. The SEM micrographs showed radial bulging along with inhomogeneous liner exfoliation, and also, a rocky shape pattern with different sizes was observed. A significant change was found in the Raman spectra of the γ-irradiated polymer at the highest dose. The results of the structural, optical, and morphological studies show recovery characteristics at the highest dose level of 300 kGy. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study of Eu3+–Gd3+ co-doped Ba–Bi–B glasses for red-laser applications: Physical,structural, photoluminescence and time-resolved spectral characteristics

A series of Eu³⁺ and Eu³⁺/Gd³⁺ co-doped barium-bismuth-borate (Ba–Bi–B) glasses were prepared by melt-quench technique. And deliberated the physical, structural, and spectroscopic properties of all glasses and explored the energy transfer process from Gd³⁺ to Eu³⁺ ions. The density of glasses increased with increasing of Gd³⁺ concentration in co-doped glasses. Characteristics of steady-state and time-resolved photoluminescence (PL) of Eu-doped and Eu³⁺-Gd³⁺ co-doped glasses under different excitation wavelengths suggested the prospects of the investigated glass system for display device applications. PL spectrum displays a strong red emission peak centered at 612 nm due to the Eu³⁺: ⁵D₀→ ⁷F₂ transition. Less intense emissions centered at 577 nm (⁷F₀), 590 nm (⁷F₁), 651 nm (⁷F₃) and 700 nm (⁷F₄) are also observed from the radiative transitions of the excited state ⁵D₀ of Eu³⁺ions. The values of radiative parameters such as transition probability, branching ratios, and stimulated emission cross-sections were obtained from Judd–Ofelt theory analysis and indicated the aptness of the Ba–Bi–B glasses for optical devices. A 5-fold enhancement in the PL intensity was observed in 1.0 mol% Eu³⁺ and 3.0 mol% Gd³⁺ co-doped glass under λ_Exci. = 394 nm excitation. The calculated commission Internationale de l'eclairage color coordinates and correlated color temperature values show that the Ba–Bi–B glasses are useful for red-laser and display device applications.     

Single-crystal elastic constants of natural ettringite

The single-crystal elastic constants of natural ettringite were determined by Brillouin spectroscopy at ambient conditions. The six non-zero elastic constants of this trigonal mineral are: C₁₁ = 35.1 ± 0.1 GPa, C₁₂ = 21.9 ±0.1 GPa, C₁₃ = 20.0 ± 0.5 GPa, C₁₄ = 0.6 ± 0.2 GPa, C₃₃ = 55 ± 1 GPa, C₄₄ = 11.0 ± 0.2 GPa. The Hill average of the aggregate bulk, shear modulus and the polycrystal Young's modulus and Poisson's ratio are 27.3 ± 0.9 GPa, 9.5 ± 0.8 GPa, 25 ± 2 GPa and 0.34 ± 0.02 respectively. The longitudinal and shear elastic anisotropy are C₃₃/C₁₁ = 0.64 ± 0.01 and C₆₆/C₄₄ =0.60 ± 0.01. The elastic anisotropy in ettringite is connected to its crystallographic structure. Stiff chains of [Al(OH)₆]³⁻ octahedra alternating with triplets of Ca²⁺ in eight-fold coordination run parallel to the c-axis leading to higher stiffness along this direction. The determination of the elastic stiffness tensor can help in the prediction of the early age properties of cement paste when ettringite crystals precipitate and in the modeling of both internal and external sulfate attack when secondary ettringite formation leads to expansion of concrete.     

Spectroscopic and electrochemical investigations of lead–lead dioxide glasses and vitroceramics with applications for rechargeable lead–acid batteries

A new class of glass and vitroceramic electrodes with applications for rechargeable batteries was obtained by a melt quenching method. The structural characterization of the samples having the xPb·(100−x)PbO₂ composition, where x=0, 10, 20, 30, 40 and 50 mol% Pb, was performed by UV–vis and FTIR spectroscopies investigations.UV–vis and FTIR data reveal that the excess of lead content in the host matrix generates the transformation and/or disintegration of [PbO₆] octahedral structural units into [PbO₄] structural units or Pb²⁺ ions and non-bonding oxygen ions centers.The electrochemical performances of the glass and vitroceramics electrodes were investigated by cyclic voltammetry. The shapes of the cyclic voltammograms and redox peaks depend on the electrolyte solution concentration and the lead content in host matrix. Differences between these waves are determined by the type of electrochemically active species existing in the glass or glass ceramics. The improved performance of the vitroceramic electrodes is attributed to the presence of the lead metallic phase that seems to offer an easier route for the charge process of the electrodes. Thus, the presence of these phases generates more electrochemically active species, inhibits the secondary reactions implying PbO, takes up the ionic conduction of the larger electrolyte solution and increases the charge/discharge rate of the electrochemical processes.     

Tunable Visible Emission of Ag-Doped CdZnS Alloy Quantum Dots

Highly luminescent Ag-ion-doped Cd_1−xZn_xS (0 ≤ x ≤ 1) alloy nanocrystals were successfully synthesized by a novel wet chemical precipitation method. Influence of dopant concentration and the Zn/Cd stoichiometric variations in doped alloy nanocrystals have been investigated. The samples were characterized by X-ray diffraction (XRD) and high resolution transmission electron microscope (HRTEM) to investigate the size and structure of the as prepared nanocrystals. A shift in LO phonon modes from micro-Raman investigations and the elemental analysis from the energy dispersive X-ray analysis (EDAX) confirms the stoichiometry of the final product. The average crystallite size was found increasing from 1.0 to 1.4 nm with gradual increase in Ag doping. It was observed that photoluminescence (PL) intensity corresponding to Ag impurity (570 nm), relative to the other two bands 480 and 520 nm that originates due to native defects, enhanced and showed slight red shift with increasing silver doping. In addition, decrease in the band gap energy of the doped nanocrystals indicates that the introduction of dopant ion in the host material influence the particle size of the nanocrystals. The composition dependent bandgap engineering in CdZnS:Ag was achieved to attain the deliberate color tunability and demonstrated successfully, which are potentially important for white light generation.     

Design and characterization of novel manganite perovskites Ba1-xBixTi1-xMnxO3 (0≤x≤0.2)

Polycrystalline manganite powders of Ba_1-xBi_xTi_1-xMn_xO₃ (x = 0, x = 0.1 and x = 0.2) were synthesized by the conventional solid-state reaction process. Their crystal structure, morphological, optical, dielectric and electrical properties were investigated. X-ray diffraction of the prepared samples was made at room temperature and confirmed the formation of a perovskite phase. Structural refinement, using the Rietveld method, revealed a tetragonal P4mm phase of pure BTO and a tetragonal P4/mmm phase with the presence of vacancies for both doped samples (x = 0.1 and x = 0.2). Scanning electron microscopy indicated that the perovskite samples had a grain size smaller than 1 μm. From UV–vis–NIR spectra, we found that the band gap reduces from 3.29 eV to 1.48 eV with the increase of Bi and Mn amounts, resulting in a shift of the absorption wavelength region toward the visible range. Dielectric analysis was conducted in a wide range of temperatures at different frequencies. Phase transitions were identified from thermal dielectric results, showing that the samples exhibited a non-relaxor behavior. The structural transformation from tetragonal to cubic structure corresponding to the transition from ferroelectric phase to paraelectric phase was observed in the dielectric properties investigation. The complex impedance spectroscopy indicated the presence of grain and grain boundary effects in the conduction mechanism. Electrical analysis showed that doping with Bi and Mn enhanced the DC conductivity. Furthermore, the DC conductivity temperature dependence confirmed that the studied samples present a semiconductor behavior. The activation energies of grain and grain boundaries depended on the amount of incorporated Bi and Mn. The activation energy of grain varied between 0.54 and 0.87 eV suggesting that the DC electrical conductivity is governed by ionized oxygen vacancies. The activation energy of grain boundaries varied between 0.85 and 0.58 eV.     

Homoepitaxial CVD diamond: Raman and time-resolved PL characterization

In this work, we report on the structural characterization of homoepitaxial Microwave Plasma Enhanced CVD diamond grown onto Ib diamond substrates by varying systematically the methane to hydrogen ratio in the gas mixture (1–7% CH₄). X-ray diffraction, Raman spectroscopy and photoluminescence (PL) have been used to characterize the diamond samples. Raman measurements pointed out the excellent crystalline quality and phase purity of the specimens. PL measurements in the 1.7–2.7 eV energy range have shown completely flat spectra, excluding the presence of nitrogen-related optical centers. Such results show that the homoepitaxial CVD diamond can be grown, at moderate microwave power (720 W), and at growth rates not too low ( 1 μm/h) preserving a good quality. Moreover, the homoepitaxial crystals exhibited a strong free-exciton recombination radiation at room temperature even at the highest methane concentration used (7%). Preliminary measurements of the lifetime of the free exciton at room temperature have been also performed. The excitation was produced by a 5 ns pulsed laser irradiation at energies above the diamond band gap. The results have been compared with the structural properties of the samples and correlated with the growth conditions.     

Structure and magnetic properties of BeO-Fe2O3-Al2O3-TeO2 glass-ceramic composites

In this work, glass-ceramics in the xBeO–20Fe₂O₃–(80-x)TeO₂ system with x = 0–25 mol% were synthesized by the traditional melt quenching route and studied by inductively coupled plasma optical emission spectroscopy, X-ray diffraction, confocal microscopy, infrared and Raman spectroscopy. BeO addition was found to support the crystallization process of Fe₂O₃ during melting, and an increased BeO content was associated with an increased fraction of the crystalline Fe₂O₃ phase and an increased size of these crystallites. Furthermore, samples doped with BeO exhibit an increasing polymerization of the residual tellurite glass network compared to the undoped sample. The magnetic properties and specific heat of all synthesized materials were measured, and the results show that all studied samples behave as spin-glasses. Also, the Morin transition of hematite was observed at 260 K with intensity depending on the material content in Fe₂O₃ crystalline phase, the formation of which correlates with the amount of added BeO.     

Model for Vickers microhardness prediction applied to SnO2 and TiO2 in the normal and high pressure phases

The Vickers microhardness of TiO₂ is calculated using elastic properties obtained by first principles calculations combined with Discrete Elements Method (DEM). The calculation is carried out in rutile and cotunnite phases. It was found that rutile phase, has a microhardness of 8.6 GPa and 12.8 GPa for the failure and fracture modes in agreement with experimental results range. In cotunnite phase the hardness for failure and fracture mode are 24.1 and 24.4 GPa, close to 26 GPa, applying Simunek model. To give insight to this methodology, the calculation is extended to SnO₂ in the normal phase. The microhardness value obtained in the failure mode is 2.67 GPa. The method developed here, to obtain the Vickers microhardness, could be applied to a systematic study of tailoring materials. Since hardness is related to elastic shear properties, our results can be used as an assessment of the material properties as solid lubricating at first order.