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At least 37 records · Page 2

Applicability of iron phosphate glass medium for loading NaCl originated from seawater used for cooling the stricken power reactors

As the part of investigation for immobilization of the sludge as one of the radioactive wastes arising from the treatment of contaminated water at Fukushima Dai-ichi nuclear power plant, applicability of vitrification method has been evaluated as a candidate technique. The aim of this study is to evaluate the influence of NaCl as one of the main constituents of sludge, on glass formation and glass properties. Two kinds of iron phosphate glass (IPG) media in the xFe{sub 2}O{sub 3}-(100-x)P{sub 2}O{sub 5}, with x=30 and 35 (mol%) were chosen and the glass formation, structure and properties including density, coefficient of thermal expansion, glass transition temperature, onset crystallization temperature and chemical durability of NaCl-loaded IPG were studied. The results are summarized as follows. Sodium chloride, NaCl could be loaded into IPG medium as Na{sub 2}O and Cl contents and their loading ratio could be up to 19 and 15 mol%, respectively. Majority of Cl content of raw material NaCl was thought to be volatilized during glass melting. Loading NaCl into IPG induces to de-polymerize glass network of phosphate chains, leads to decrease both glass transition and onset crystallization temperatures, and to increase coefficient of thermal expansion. NaCl-loaded IPG indicated good chemical durability in case of using 35Fe{sub 2}O{sub 3}- 65P{sub 2}O{sub 5} medium. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Influence of temperature and frequency on ionic conductivity of Li{sub 3}PO{sub 4}–Pb{sub 3}(PO{sub 4}){sub 2}–BiPO{sub 4} phosphate glasses

Highlights: • Results of ionic conductivities of Li{sub 3}PO{sub 4}–Pb{sub 3}(PO{sub 4}){sub 2}–BiPO{sub 4} phosphate glasses. • Determination of glass transition temperature using DSC method. • Study of temperature and frequency on ionic conductivity of Li{sub 3}PO{sub 4}–Pb{sub 3}(PO{sub 4}){sub 2}–BiPO{sub 4} phosphate glasses. - Abstract: Lithium–Lead–Bismuth phosphates glasses having, a composition 30Li{sub 3}PO{sub 4}–(70 − x)Pb{sub 3}(PO{sub 4}){sub 2}–xBiPO{sub 4} (45 ≤ x ≤ 60 mol%) were prepared by using the melt quenching method 1000 °C. The thermal stability of theses glasses increases with the substitution of Bi{sub 2}O{sub 3} with PbO. The ionic conductivity of all compositions have been measured over a wide temperature (200–500 °C) and frequency range (1–106 Hz). The ionic conductivity data below and above T{sub g} follows Arrhenius and Vogel–Tamman–Fulcher (VTF) relationship, respectively. The activation energies are estimated and discussed. The dependence in frequency of AC conductivity is found to obey Jonscher’s relation.

36 MATERIALS SCIENCE↗

A Review of Iron Phosphate Glasses and Recommendations for Vitrifying Hanford Waste

This report contains a comprehensive review of the research conducted, world-wide, on iron phosphate glass over the past ~30 years. Special attention is devoted to those iron phosphate glass compositions which have been formulated for the purpose of vitrifying numerous types of nuclear waste, with special emphasis on the wastes stored in the underground tanks at Hanford WA. Data for the structural, chemical, and physical properties of iron phosphate waste forms are reviewed for the purpose of understanding their (a) outstanding chemical durability which meets all current DOE requirements, (b) high waste loadings which can exceed 40 wt% (up to 75 wt%) for several Hanford wastes, (c) low melting temperatures, can be as low as 900°C for certain wastes, and (d) high tolerance for “problem” waste components such as sulfates, halides, and heavy metals (chromium, actinides, noble metals, etc.). Several recommendations are given for actions that are necessary to smoothly integrate iron phosphate glass technology into the present waste treatment plans and vitrification facilities at Hanford.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Influence of silver nanoparticles on the spectroscopic properties of Sm{sup 3+} doped boro-phosphate glasses

The Sm{sup 3+} doped novel boro-phosphate glasses containing silver nanoparticles (NPs) (SmBPxA) have been prepared following the melt quenching technique and their structural and spectroscopic behavior were studied through HR-TEM, optical absorption and photoluminescence spectral measurements. The TEM analysis validates the existence of Ag NPs with an average diameter of ~8 nm. The Surface plasmon resonance (SPR) band of silver NPs was found at around 600 nm from the absorption spectrum of the Sm{sup 3+} ions free glass sample. The optical band gap energy (E{sub opt}) corresponding to the direct and indirect allowed transitions and the Urbach energy (ΔE) values were determined from the absorption spectral measurements. The luminescence intensity is found to get enhance when the Ag NPs were embedded along with the Sm{sup 3+} ions in the prepared glasses due to the local electric field effect around the rare earth (RE) ion site produced by the SPR of Ag NPs.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Luminescence performance of Eu{sup 3+} doped lead free zinc phosphate glasses for red emission

Luminescence performance of zinc phosphate glasses containing Eu{sup 3+} ion with the chemical compositions (60-x)NH{sub 4}H{sub 2}PO{sub 4}-20ZnO-10BaF{sub 2}-10NaF-x Eu{sub 2}O{sub 3} (where x = 0.2, 0.5, 1.0 and 1.5 mol%) has been studied. The Fourier Transform Infrared Spectroscopy (FT-IR) shows several vibrations bands. Luminescence spectra of these glasses exhibit characteristic emission of Eu{sup 3+} ion with an intense and most prominent red emission (614 nm) which is attributed to {sup 5}D{sub 0}→{sup 7}F{sub 2} transition. Judd-Ofelt (Ω{sub 2}, Ω{sub 4}) parameters have been evaluated from the luminescence intensity ratios of {sup 5}D{sub 0}→{sup 7}F{sub J} (where J = 2 and 4) to {sup 5}D{sub 0}→{sup 7}F{sub 1} transition as well as absorption spectra under different constraints. Using J-O parameters and excitation spectra, the radiative parameters are calculated for different Eu{sup 3+} doped glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Iron phosphate glass for immobilization of 99Tc

Technetium-99 (99Tc) can bring serious environmental threats because of its long half-life (t1/2 = ~2.1 x 105 years), high fission yield (~6%), and high solubility and mobility in the ground water. The high volatility makes it difficult to immobilize 99Tc in continuous melters vitrifying 99Tc-containing nuclear wastes in borosilicate glasses. This work explores a possibility of incorporating a high concentration of 99Tc, surrogated by the non-radioactive Re, in an iron phosphate glass by melting mixtures of iron phosphate glass frits with 1.5-6 mass% KReO4 at ~1000 C. The retention of Re achieved was ~1.1 mass%. The normalized Re release by the 7-day Product Consistency Test was <10*2 g/m2. Surprisingly, the Re escaped from the melt within a short time of heating, especially when the temperature was increased. Therefore, 99Tc volatilization would still be a challenging task for its immobilization in iron phosphate glasses.

Xu, Kai↗

Unexpected effects of inorganic phosphate glass on crystallization and thermo-rheological behavior of polyethylene terephthalate

The effects of ultra-low glass transition temperature (T g ) phosphate glass (Pglass) on the thermal, morphological, rheological, mechanical, and crystallization properties of hybrid Pglass/poly(eththylene terephthalate)(PET) were investigated. Nano- and micro-scale distribution of the Pglass in the PET polymer matrix was observed. The polydispersed Pglass in the PET matrix functioned as a nucleation agent, resulting in increasing crystallization temperature. The Pglass in the PET matrix decreased the T g , indicating a plasticizing effect of the Pglass in the hybrids that was confirmed by the significantly decreased complex viscosity of the PET matrix. In addition, with increasing temperature, a non-terminal behavior of the viscoelastic properties occurred due to the hybrid structural changes and improved miscibility of the hybrid components. In conclusion, the obtained solid-state variable temperature 31 P and 1 H NMR spectroscopy results showed strong Pglass concentration dependency of the interactions at the PET-Pglass interface.

36 MATERIALS SCIENCE↗

Concentration dependent spectroscopic properties of Dy{sup 3+} ions doped boro-phosphate glasses

Dy{sup 3+} ions doped boro-phosphate glasses have been synthesized by melt quenching method and characterized through FTIR, absorption and luminescence spectral measurements. The presence of various stretching and bending vibrations of different borate and phosphate groups were identified from the FTIR spectra. In order to examine the electronic band structure of the studied glasses, Optical energy gap (E{sub opt}) and Urbach energy (ΔE) values were estimated from the absorption spectra. The Judd-Ofelt (JO) intensity parameters were calculated to examine the symmetry of the ligand environment around the Dy{sup 3+} ions site. The emission spectra exhibit two intense emission bands at around 482 nm (blue) and 574 nm (yellow) corresponding to the {sup 4}F{sub 9/2}→{sup 6}H{sub 15/2} and {sup 4}F{sub 9/2}→{sup 6}H{sub 13/2} transitions respectively. The emission spectra were characterized through Commission International d’Eclairage (CIE) 1931 chromaticity diagram to explore its suitability for WLED applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

X-ray absorption studies of gamma irradiated Nd doped phosphate glass

This paper presents the X-ray absorption near edge structure (XANES) studies of Nd doped phosphate glasses before and after gamma irradiation. The intensity and location of L{sub III} edge white line peak of Nd changes depending on its concentration as well as on the ratio of O/Nd in the glass matrix. The decrease in the peak intensity of white line after gamma irradiation indicates towards reduction of Nd{sup 3+} to Nd{sup 2+} in the glass matrix, which increases with an increase in the doses of gamma irradiation. Similarity in the XANES spectra of Nd doped phosphate glasses and Nd{sub 2}O{sub 3} suggests that coordination geometry around Nd{sup 3+} in glass samples may be identical to that of Nd{sub 2}O{sub 3}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Investigations on optical properties of Sm{sup 3+} ion doped boro-phosphate glasses

The Sm{sup 3+} doped Boro-phosphate glasses with the chemical composition 60H{sub 3}BO{sub 3}+20Li{sub 2}CO{sub 3}+10ZnO+(10−x) H{sub 6}NO{sub 4}P+xSm{sub 2}O{sub 3} (where x= 0.1, 0.5, 1 and 2 in wt%) have been prepared by melt quenching technique. The prepared glasses were characterized through optical absorption and luminescence spectral measurements. The band gap energies corresponding to the direct and indirect allowed transitions and the Urbach’s energy values were estimated from the absorption spectra. Judd-Ofelt intensity parameters have been derived to predict the radiative properties of the various emission transitions. In order to identify the emission color of the prepared glasses, the emission intensities were analyzed using CIE 1931 color chromaticity diagram. The energy transfer process takes place between Sm{sup 3+}−Sm{sup 3+} ions through cross-relaxation mechanism have also been investigated and the results were discussed and reported.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Phosphate glass core/silica clad fibres with a high concentration of active rare-earth ions

We report a study of silica-clad composite optical fibres having a phosphate glass core doped with active rare-earth elements. The phosphate glass core allows a high concentration of active rare-earth ions to be obtained, and the silica cladding ensures high mechanical strength and facilitates fusion splicing of such fibres to silica fibres. Owing to the high concentration of active rare-earth ions, this type of fibre is potentially attractive for applications where a small cavity length and high lasing efficiency are needed. (paper)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Physical and absorption properties of titanium nanoparticles incorporated into zinc magnesium phosphate glass

We report the influences of Titania (TiO{sub 2}) nanoparticles (NPs) on the physical and optical properties of melt quench synthesized zinc magnesium phosphate glasses. Five glass samples with composition (42 − x)P{sub 2}O{sub 5}–50ZnO–8MgO–xTiO{sub 2}, where x = 0, 1, 2, 3, 4 mol% are prepared and characterized. XRD pattern verified the amorphous nature of all samples. TEM images manifested the growth of Ti NPs of average size ≈ 5.78 nm. TiO{sub 2} NP concentration dependent variation in the physical properties including glass density, molar volume, molar refractivity, electronic polarizability and ionic packing density are determined. The values of glass refractive indices, density and ionic packing density are increased with the increase of TiO{sub 2} NP contents. Conversely, the Urbach energy, direct and indirect optical band gap are found to decrease with the increase of TiO{sub 2} NP concentration. These glass compositions may be potential for various solid state devices including laser. - Highlights: • TiO{sub 2} NP embedded self-cleaning phosphate glass are synthesized for the first time. • Well dispersed and uniform sized TiO{sub 2} NPs are grown. • Absorption spectra revealed prominent peak in the UV region. • TiO{sub 2} NPs strongly influenced the physical and absorption features of synthesized glasses. • The effects of TiO{sub 2} NPs on the physical and optical properties of these glasses are determined.

36 MATERIALS SCIENCE↗

Ultraviolet optical absorptions of semiconducting copper phosphate glasses

Results are presented of a quantitative investigation of the change in UV optical absorption in semiconducting copper phosphate glasses with batch compositions of 40, 50, and 55 percent CuO, as a function of the Cu(2+)/Cu(total) ratio in the glasses for each glass composition. It was found that optical energy gap, E(opt), of copper phosphate glass is a function of both glass composition and Cu(2+)/Cu(total) ratio in the glass. E(opt) increases as the CuO content for fixed Cu(2+)/Cu(total) ratio and the Cu(2+)/Cu(total) ratio for fixed glass composition are reduced.

Bae, Byeong-Soo↗

Comment on “A model for phosphate glass topology considering the modifying ion sub-network” [J. Chem. Phys. 140, 154501 (2014)]

In a recent paper, Hermansen, Mauro, and Yue [J. Chem. Phys. 140, 154501 (2014)] applied the temperature-dependent constraint theory to model both the glass transition temperature, T{sub g}, and fragility, m, of a series of binary alkali phosphate glasses of the form (R{sub 2}O){sub x}(P{sub 2}O{sub 5}){sub 1−x}, where R represents an alkali species. Key to their success seems to be the retention of linear constraints between the alkali ion (R{sup +}) and the non-bridging oxygens near T{sub g}, which allows the model to mimic a supposed minimum for both T{sub g}(x) and m(x) located near x = 0.2. However, the authors have overlooked several recent studies that clearly show there is no minimum in m(x). We argue that the retention of the alkali ion constraints at these temperatures is unjustified and question whether the model calculations can be revised to meet the actual experimental data. We also discuss alternative interpretations for the fragility based on two-state thermodynamics that can accurately account for its compositional dependence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermodynamic Development of Corrosion Rate Modeling in Iron Phosphate Glasses

A two-year research program investigated links between the thermodynamic properties of phosphate glasses and their corrosion rates in different solutions. Glasses in the Na 2 O-CaO-P 2 O 5 and Na 2 O-Fe 2 O 3 -PO 5 systems were prepared and characterized. These glasses were then exposed in bulk and powder form to acid (0.1M HCl), basic (0.1M KOH) and neutral (deionized water) solutions at varying exposure times and temperatures. Analysis of the solution and the glass after exposure determined the rate and type of corrosion that occurred. Simultaneously, efforts were made to determine the thermodynamic properties of solid iron phosphate compounds. This included measurement of low temperature (5-300 K) heat capacities, measured at Brigham Young University; the attempted use of a Parr calorimeter to measure ambient temperature enthalpies of formation; and attempted measurement of temperature heat capacities. Only the first of the three tasks was successfully accomplished. In lieu of experimental measurement of enthalpies of formation, first-principles calculation of enthalpies of formation was performed at Missouri S&T; these results will be used in subsequent modeling efforts.

36 MATERIALS SCIENCE↗

Effect of nanosecond UV laser irradiation on luminescence and absorption in silver- and copper-containing phosphate glasses

Experimental evidence is presented that nanosecond UV laser irradiation of silver- and copper-containing barium phosphate glasses leads to luminescence quenching in the visible range. Subsequent heat treatment induces an absorption in the range 350 – 500 nm. These effects are due to the ionisation and fragmentation of subnanometre molecular clusters by laser radiation and subsequent (heat treatment-induced) formation of nanoparticles possessing plasmon resonance. Our numerical modelling results demonstrate the feasibility of producing stable Ag{sub n}Cu{sub m} hybrid molecular clusters in glass. Local modification of the optical properties of glass by laser light can be used for optical information recording. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Spectroscopy of PbS and PbSe Quantum Dots in Fluorine Phosphate Glasses

Transmission spectra of the narrow-bandgap semiconductor quantum dots PbS and PbSe in the fluorine phosphate glass are experimentally studied at different temperatures. Energies of 1s exciton transitions observed in the absorption spectra are used to determine characteristic sizes of the quantum dots under study. A nontrivial temperature behavior of the ground and excited quantum confined states in the quantum dots of different sizes are observed.

36 MATERIALS SCIENCE↗

IRON-PHOSPHATE GLASS FOR IMMOBILIZATION OF RADIOACTIVE TECHNETIUM

Technetium-99 (Tc-99) can bring a serious environmental threat because of its high fission yield, long half-life, and high solubility and mobility in the ground water. The present work investigated the immobilization of Tc-99 (surrogated by Re) by heat-treating mixtures of an iron-phosphate glass with 1.5 to 6 wt.% KReO{sub 4} at {approx}1000 C. The Re retention in the glass was as high as {approx}1.2 wt. % while the loss of Re by evaporation during melting was {approx}50%. Re was uniformly distributed within the glass. The normalized Re release by the 7-day Product Consistency Test was {approx}0.39 g/m{sup 2}, comparable with that in phosphate-bonded ceramics and borosilicate glasses. These results suggest that iron-phosphate glass can provide a good matrix for immobilizing Tc-99.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗