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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Development of accident tolerant control rod for light water reactors

For an accident tolerant control rod (ATCR) designed to improve LWR (light water cooled reactor)core safety, the following inherent characteristics are required: sufficient neutron absorption, high-temperature stability and high miscibility with fuel materials to avoid uncontrollable recriticality. In the present work an ATCR is being developed to improve the safety of light water reactors under all conditions including severe accidents. Promising neutron-absorbing materials for the ATCR include rare-earth sesquioxides (RE{sub 2}O{sub 3}), hafnium dioxide (HfO{sub 2}) and mixtures of these materials. A reactivity worth analysis of these materials in representative light water reactors revealed that a conventional control rod can be replaced by an ATCR without significant impact on the reactor operation conditions. A high-temperature compatibility of the candidate ATCR materials and iron, which is a main component of control rod cladding, was examined experimentally, and no significant reaction occurred upon heating to 1600 Celsius degrees for 1 hour. That is, the ATCR is expected to have no significant damage prior to extensive fuel pin failure in severe accidents, thus avoiding uncontrollable recriticality after reactor shutdown even in case of injection of non-borated or insufficiently borated water for emergency cooling of the reactor.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2016

Micro arc oxidation of aluminum for nuclear applications

Dry cask storage and transport of used (spent) nuclear fuel rely upon the basket and shell of the cask to transfer the decay heat from the fuel assemblies. Cask licensees have considered the use of light metal (aluminum) oxidation to enhance the emissivity of aluminum alloy or aluminum based Metal Matrix Composites (MMC) used in the cask basket. However, traditional anodization techniques suffer from issues that make fabrication and regulatory acceptance problematic. The Micro Arc Oxidation (MAO) technology overcomes the problems associated with traditional anodization in the production of consistent, uniform and reliable high emissivity coatings of aluminum alloys. Samples of AA 2219 and an aluminum-based MMC were treated using a proprietary MAO process and subjected to a number of tests to confirm suitability of the coated material. The treated material was inspected using macro photography and Scanning Electron Microscopy (SEM). A consistent, uniform black, porous surface with a typical surface roughness of Ra = 7-8 μm was observed. Emissivity of treated surfaces with thicknesses ranging from 24 microns to 40 microns was measured using an integrating sphere. In all cases, the emissivity coefficient at room temperature in the ranges of 400 to 700 nanometers and 1000 to 1650 nanometers was above 0.8, reaching 0.94 depending on the thickness. The MAO process yield was tested by coating 400 spent fuel basket components to ensure a minimum specified thickness. 97% of the tested points met or exceeded the minimum thickness required. The defect density was very low and 100% of the components met the quality assurance criteria. In-service surface performance was tested by exposing the treated surface to a number of high temperature environments (air, vacuum, nitrogen) and thermal cycling in air. In all cases, the surface remained unchanged. Test samples were exposed to 90 Celsius degrees borated and demineralized water for 48 hours with no change to the sample treated surface. Finally, tests sample were exposed to 60 C. degrees borated water for 168 hours with no change to the sample treated surface. MAO technology appears to be a viable method to provide consistent, durable, and high emissivity coatings, that can be used in the fabrication and licensing of dry storage/transportation casks.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Comparison of Subdivided Versus Full-Length Fuel Pin Burnup in the ATF-2 Safety Analysis

The Accident Tolerant Fuels (ATF) campaign, under the Fuel Cycle Research and Development (FCRD) Advanced Fuels program, was developed after the Fukushima Daiichi Nuclear Power Plant disaster in 2011. Under ATF, fuel and cladding concepts are to be developed and tested that may more readily withstand an accident similar to the one that occurred at Fukushima Daiichi. ATF is a combination of industry, universities, and national laboratories in an effort to develop advanced accident tolerant cladding and fuel concepts. The end goal of the ATF program is to insert a lead test rod (LTR) or lead test assembly (LTA) into an operating commercial power light water reactor by 2022. In order to meet this 2022 insertion goal, ATF is split into three separate phases: ATF-1, ATF-2, and ATF-3. The first phase of the ATF program, ATF-1, is the concept feasibility study and early irradiation testing. Feasibility, fabrication, and out-of-pile testing are happening at universities and laboratories all over the United States. Irradiation testing of these concepts is happening at the Advanced Test Reactor (ATR) at the Idaho National Laboratory (INL). Early irradiation testing involves testing clad and/or fuel in drop-in capsules in the ATR. Currently, these capsules are in the relatively low-flux positions in the ATR, but some newer concepts and concepts that require higher burnup will be moved to the higher-flux positions later on during irradiation. Currently, Oak Ridge National Laboratory (ORNL), Westinghouse Electric Company, Areva, and General Electric (GE) have inserted capsules for ATF-1, although more concepts are planned. The second phase of ATF, ATF-2, is the focus of this paper. ATF-2 is the loop testing of fuel pins with new cladding and fuel concepts to simulate pressurized water reactor (PWR) and boiling water reactor (BWR) environments. ATF-2 will concurrently be happening at the ATR and at the Halden Reactor in Norway. The ATF-2 irradiation at the ATR will only simulate a PWR environment. ATF-2 will be inserted into the ATR pressurized water loop, Loop 2A, in the Center Flux Trap (CFT), where chemistry, temperature, and pressure can all be controlled separately from the primary coolant system and other loops in ATR. Loop 2A will be borated, pressurized to 2200 psi nominal, and have an average water temperature of 300 deg. C. A borated loop with fueled rodlets is extremely rare for Nuclear Energy experiments in the ATR, so ATF-2 will demonstrate new and unique capabilities for INL. ATF-3 is the testing of fresh and irradiated ATF concepts at the Transient Reactor Test (TREAT) Facility. The TREAT Reactor is planned for restart, re-establishing U.S. transient testing capabilities after nearly 20 years of non-operations. TREAT will test ATF concepts under transient conditions, such as a reactivity insertion accident. In addition to fresh fuel pins, TREAT will use from ATF2 and do transient testing on those irradiated pins. The information TREAT will provide to the vendors to support fuel licensing will be valuable, showing that these concepts do enhance the accident tolerance of the fuel in commercial reactors. (author)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

A low-cost, fluorine-free electrolyte for improved sodium batteries

Sodium batteries are an attractive alternative to lithium-ion technologies due to sodium’s lower cost and natural abundance—over 1,000 times greater than lithium, comprising approximately 2.4% of the Earth’s crust. However, most current electrolytes rely on fluorine-containing components, which raise economic and environmental concerns. This study explores fluorine-free, borate-based electrolytes that offer improved cycling stability and significant cost and sustainability benefits. We demonstrate stable sodium metal stripping and plating on aluminum foil, enabling anode-free cell configurations with over 50% capacity retention after 700 cycles. Spectroscopic and electrochemical analyses reveal the effects of solvents and salt composition on solvation, ionic conductivity, and oxidative stability. In full-cell configurations, the fluorine-free electrolyte maintains more than 98% capacity retention after 400 cycles. Furthermore, these findings represent a critical step toward the development of cost-effective, environmentally friendly, and high-performance sodium battery systems suitable for future electrification.

anode-free sodium batteries↗
DOE OSTI2018

The homometallic warwickite V{sub 2}OBO{sub 3}

Highlights: • New mixed valent vanadium borate. • Multiple phase transitions on cooling. • High resolution synchrotron powder X-ray diffraction data. - Abstract: The synthesis, structure and elementary magnetic characterization of the homometallic warwickite V{sub 2}OBO{sub 3} are reported. The material adopts the orthorhombic warwickite structure type at room temperature, space group Pnma (No. 62) with lattice parameters a = 9.2317(1) Å, b = 3.1172(1) Å, and c = 9.5313(1) Å. Temperature-dependent magnetic susceptibility, electrical resistivity, and specific heat measurements show anomalies near 35 K, between 135 K and 150 K, and near 260 K, with the transition at ~ 35 K likely to a ferrimagnetic state. High resolution synchrotron powder X-ray diffraction data at temperatures between 295 K and 90 K display significant peak splitting upon cooling, indicating that at least one crystallographic symmetry change occurs at low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

A novel electrolyte salt additive for lithium-ion batteries with voltages greater than 4.7 V

Here, lithium bis(2-methyl-2-fluoromalonato)borate (LiBMFMB), as an additive in conventional electrolyte for LiNi 0.5 Mn 1.5 O 4 , exhibits improved coulombic efficiencies and cycling stability. Cyclic voltammograms indicate the cells with additive form good SEIs during the first cycle whereas no additive cell needs more cycles to form a functional SEI. XPS reveals LiBMFMB could reduce the decomposition of LiPF 6 salt and solvents, resulting in thinner SEI.

25 ENERGY STORAGE↗
DOE OSTI2024

A Fluorinated Lewis Acidic Organoboron Tunes Polysulfide Complex Structure for High–Performance Lithium–Sulfur Batteries

Many challenges in lithium-sulfur (Li–S) batteries are associated with the radical change in lithium polysulfide (LPS) solubility during cycling, but chemical approaches to address such inconsistency are still lacking. Here, the use of a strong Lewis acidic fluorinated organoboron, tri(2,2,2-trifluoroethyl) borate (TFEB), is reported as a multi-functional mediator to simultaneously overcome multiple technical barriers in practical Li–S batteries. TFEB acts as an anion acceptor and forms strong molecular complexes with Lewis basic LPS. The TFEB-LPS complexes have consistent solubility across the full polysulfide spectrum and deliver several times improved better redox kinetics, unlocking a true redox catalytic mechanism that covers the majority of redox events in thick sulfur cathodes. As a result, Li–S batteries evaluated under practical conditions exhibit significantly improved discharge capacity, rate capability, and cycling stability with the addition of the TFEB additive. More importantly, TFEB also contributes to the stabilization of lithium anode in the presence of polysulfides by generating strong interfacial film. These attributes significantly improve the cycling stability of practical Li–S pouch cells, which are assembled with a unit energy density of 219 Wh kg –1 . Finally, the results provide new molecular insights on the design of unlocking solvation networks of practical Li–S systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Effect of Gamma Radiation on Absorption of Light in Potassium-Aluminoborate Glasses with Additions of Iron Oxide

The effect of radiation on the absorption of light by potassium–alumina–borate glasses with various concentrations of iron additions and various thicknesses was investigated. It was shown that in contrast to samples of small thickness (1 mm) a bleaching effect was observed in the samples with a thickness of 8 mm. A possible mechanism involving the formation of nanostructured units is proposed for the observed effect.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2012

Reactive belite stabilization mechanisms by boron-bearing dopants

Belite-rich cements hold promise for reduced energy consumption and CO{sub 2} emissions, but their use is hindered by the slow hydration rates of ordinary belites. This drawback may be overcome by activation of belite by doping. Here, the doping mechanism of B and Na/B in belites is reported. For B-doping, three solid solutions have been tested: Ca{sub 2-x/2{open_square}x/2}(SiO{sub 4}){sub 1-x}(BO{sub 3}){sub x}, Ca{sub 2}(SiO{sub 4}){sub 1-x}(BO{sub 3}){sub x}O{sub x/2} and Ca{sub 2-x}B{sub x}(SiO{sub 4}){sub 1-x}(BO{sub 4}){sub x}. The experimental results support the substitution of silicate groups by tetrahedral borate groups with the concomitant substitution of calcium by boron for charge compensation, Ca{sub 2-x}B{sub x}(SiO{sub 4}){sub 1-x}(BO{sub 4}){sub x}. Otherwise, the coupled Na/B-doping of belite has also been investigated and Ca{sub 2-x}Na{sub x}(SiO{sub 4}){sub 1-x}(BO{sub 3}){sub x} series is confirmed to exist for a large range of x values. Along this series, {alpha}'{sub H}-C{sub 2}S is the main phase (for x {>=} 0.10) and is single phase for x = 0.25. Finally, a new structural description for borax doping in belite has been developed for {alpha}'{sub H}-Ca{sub 1.85}Na{sub 0.15}(SiO{sub 4}){sub 0.85}(BO{sub 3}){sub 0.15}, which fits better borax activated belite cements in Rietveld mineralogical analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Multi-scale boron penetration toward stabilizing nickel-rich cathode

Nickel-rich layered oxides LiNi x Co y Mn 1-x-y O 2 (x≥0.8) have been recognized as the preferred cathode materials to develop lithium-ion batteries with high energy density (>300Wh kg -1 ). However, the poor cycling stability and rate capability stemming from intergranular cracks and sluggish kinetics hinder their commercialization. To address such issues, a multi-scale boron penetration strategy is designed and applied on the polycrystalline LiNi 0.83 Co 0.11 Mn 0.06 O 2 particles that are pre-treated with pore construction. The lithium-ion conductive lithium borate in grain gaps functions as the grain binder that can bear the strain/stress from anisotropic contraction/expansion, and provides more pathways for lithium-ion diffusion. As a result, the intergranular cracks are ameliorated and the lithium-ion diffusion kinetics is improved. Moreover, the coating layer separates the sensitive cathode surface and electrolyte, helping to suppress the parasitic reactions and related gas evolution. In addition, the enhanced structural stability is acquired by strong B-O bonds with trace boron doping. As a result, the boron-modified sample with an optimized boron content of 0.5% (B5-NCM) exhibits a higher initial discharge capacity of 205.5mAh g -1 at 0.1C (1C=200mA g -1 ) and improved capacity retention of 81.7% after 100 cycles at 1C. Furthermore, the rate performance is distinctly enhanced by high lithium-ion conductive LBO (175.6mAh g -1 for B5-NCM and 154.6mAh g -1 for B0-NCM at 5C).

25 ENERGY STORAGE↗
DOE OSTI2013

Boric acid flux synthesis, structure and magnetic property of MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn)

Three new borates MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn) have been synthesized by boric acid flux methods, which are isotypic to NiB₁₂O₁₄(OH)₁₀. Single-crystal XRD was performed to determine the crystal structures in detail. They all crystallize in the monoclinic space group P2₁/c. The size of MO{sub 6} (M=Mg, Mn, Fe, Co, Ni, Zn) octahedron shows a good agreement with the Shannon effective ionic radii of M²⁺. Magnetic measurements indicate MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering down to 2 K. The values of its magnetic superexchange constants were evaluated by DFT calculations, which explain the observed magnetic behavior. The UV–vis diffuse reflectance spectrum of ZnB₁₂O₁₄(OH)₁₀ suggests a band gap ~4.6 eV. DFT calculations indicate it has a direct band gap 4.9 eV. The optical band gap is contributed by charge transfers from the occupied O 2p to the unoccupied Zn 4s states. - Graphical abstract: Experimental and theoretical studies indicate MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering. DFT calculations show ZnB₁₂O₁₄(OH)₁₀ has a direct band gap of 4.9 eV. Highlights: • MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn) are synthesized by two-step boric acid flux method. • Single-crystal XRD was performed to determine the crystal structures in detail. • Size of MO₆ (M=Mg, Mn, Fe, Co, Ni, Zn) agrees with the effective ionic radii. • MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering down to 2 K. • DFT calculations indicate ZnB₁₂O₁₄(OH)₁₀ has a direct band gap 4.9 eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Syntheses and luminescence study for La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O (0≤x≤0.40) and the dehydrated products β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} (0≤x≤0.15)

La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O with the Eu{sup 3+}-doping upper limit of 40 atom% were synthesized hydrothermally. Thereafter, thermal treatments at 710 °C were applied to obtain β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9}. The solid solution range is even narrower, i.e. 0≤x≤0.15, due to the mismatch between La{sup 3+} and Eu{sup 3+}. The host borate system shows a typical concentration quenching effect at x=0.20 under CT excitation, and this is postponed to x=0.30 under the f−f excitation. β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} shows a very intense absorption of charge transfer, and gives strong red emissions at 615 nm with large R/O ratios (1.9–2.4). The saturation effect appears at x=0.11, which is probably due to the lattice distortion. Eu{sup 3+} luminescence was applied as the structural probe to study the local coordination environment change during the dehydration and re-crystallization processes of La{sub 0.93}Eu{sub 0.07}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O. - Highlights: • La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O (0≤x≤0.40) were prepared by hydrothermal method. • The Eu{sup 3+}-doping limit in β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} is 15 atom% proved by powder XRD. • La{sub 1−x}Eu{sub x}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O show relatively weaker red emissions. • β-La{sub 1−x}Eu{sub x}B{sub 5}O{sub 9} shows an intense CT absorption together with strong red emissions. • Eu{sup 3+} luminescence was studied when annealing La{sub 0.93}Eu{sub 0.07}[B{sub 5}O{sub 8}(OH){sub 2}]·1.5H{sub 2}O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Elucidating structural order and disorder phenomena in mullite-type Al{sub 4}B{sub 2}O{sub 9} by automated electron diffraction tomography

The crystal structure and disorder phenomena of Al{sub 4}B{sub 2}O{sub 9}, an aluminum borate from the mullite-type family, were studied using automated diffraction tomography (ADT), a recently established method for collection and analysis of electron diffraction data. Al{sub 4}B{sub 2}O{sub 9}, prepared by sol-gel approach, crystallizes in the monoclinic space group C2/m. The ab initio structure determination based on three-dimensional electron diffraction data from single ordered crystals reveals that edge-connected AlO{sub 6} octahedra expanding along the b axis constitute the backbone. The ordered structure (A) was confirmed by TEM and HAADF-STEM images. Furthermore, disordered crystals with diffuse scattering along the b axis are observed. Analysis of the modulation pattern implies a mean superstructure (AAB) with a threefold b axis, where B corresponds to an A layer shifted by ½a and ½c. Diffraction patterns simulated for the AAB sequence including additional stacking disorder are in good agreement with experimental electron diffraction patterns. - Graphical abstract: Crystal structure and disorder phenomena of B-rich Al{sub 4}B{sub 2}O{sub 9} studied by automated electron diffraction tomography (ADT) and described by diffraction simulation using DISCUS. - Highlights: • Ab-initio structure solution by electron diffraction from single nanocrystals. • Detected modulation corresponding mainly to three-fold superstructure. • Diffuse diffraction streaks caused by stacking faults in disordered crystals. • Observed streaks explained by simulated electron diffraction patterns.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

ESR, optical absorption, IR and Raman studies of xTeO{sub 2} + (70 - x)B{sub 2}O{sub 3} + 5TiO{sub 2} + 24R{sub 2}O:1CuO (x = 10, 35 and 60 mol%; R = Li, Na and K) quaternary glass system

Highlights: Black-Right-Pointing-Pointer Peak of Cu{sup 2+} is found to be maximum at around 794 nm for lithium boro tellurite glasses. Black-Right-Pointing-Pointer Variation in g{sub ||} and A{sub ||} values is due to change in environment of Cu{sup 2+} ion due to the structural change in the glass. Black-Right-Pointing-Pointer BO{sub 3}-BO{sub 4}{sup -} ring structure is interconnected by TeO{sub 3}{sup -} and TeO{sub 4}{sup -} groups, where the BO{sub 4}{sup -} groups are neighbors of TeO{sub 3}{sup -}groups. Black-Right-Pointing-Pointer The structure comprising, isolate a BO{sub 3}{sup -}, B{sub 2}O{sub 5}, BO{sub 4}{sup -}, and metaborates, which enables glass forming for Borate rich glasses. Black-Right-Pointing-Pointer Distorted TeO{sub 4/2} network with BO{sub 3}{sup -}-BO{sub 4}{sup -} ring structure and TeO{sub 3}{sup -} group is enables glass forming for tellurite rich glasses. -- Abstract: xTeO{sub 2} + (70 - x)B{sub 2}O{sub 3} + 5TiO{sub 2} + 24R{sub 2}O:1CuO (x = 10, 35 and 60; R = Li, Na and K) glass system were studied by spectroscopic techniques such as ESR, optical absorption, Raman and IR. From ESR spectra, the spin Hamiltonian parameter values indicate that the ground state of Cu{sup 2+} is d{sub x{sup 2}-y{sup 2}} and the site symmetry around the Cu{sup 2+} ion is tetragonally distorted octahedral coordination. Bonding parameters calculated from optical absorption and ESR data are found to change with alkali oxide and TeO{sub 2} content. Bonding parameters indicate a slight covalency for the in-plane {sigma} bonding as compared to in-plane and out-of-plane {pi} bonds. Both Raman and IR results show that glass network consists of TeO{sub 3}, TeO{sub 4}, BO{sub 3}, BO{sub 4} and RiO{sub 4} group as basic structural groups. BO{sub 3}-BO{sub 4}{sup -} ring structure interconnected by TeO{sub 3}{sup -} and TeO{sub 4}{sup -} groups, where the BO{sub 4}{sup -} groups are neighbors of the TeO{sub 3}{sup -} groups. BO{sub 3} {yields} BO{sub 4} transition is also observed, which correlates with the transition of TeO{sub 4} {yields} TeO{sub 3} via TeO{sub 3+1}.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Transition-metal substitution in PbAlBO{sub 4}: Synthesis, structural and spectroscopic studies of manganese containing phases

Highlights: ► Synthesis of mullite-type PbAl{sub 1−x}Mn{sub x}BO{sub 4} by solid state and glycerin methods. ► Fundamental parameter approach describes the X-ray powder diffraction profiles. ► Cell parameters anisotropically change with increasing Mn in the structure. ► Bond valence sums of Pb{sup 2+} linearly correlates eccentricity parameter. ► FTIR spectra confirm the trigonal planar BO{sub 3}. -- Abstract: Mullite-type metal borates PbAlBO{sub 4} with planar BO{sub 3} groups are potential candidates for nonlinear optical properties. We successively substituted aluminum with manganese in the composition PbAl{sub 1−x}Mn{sub x}BO{sub 4}, which would help tuning the crystal chemistry and related physical properties. The end member PbAlBO{sub 4} was synthesized by conventional solid state reaction; the other members of the PbAl{sub 1−x}Mn{sub x}BO{sub 4} series were prepared by glycerin method. The fundamental parameter approach was applied in the Rietveld refinements to describe the X-ray powder diffraction profiles. The cell parameters and interatomic bond distances were studied with respect to the chemical composition x. The MO{sub 6} octahedral distortion linearly increased with the averaged M-O bond distance, which is correlated with the increasing amount of manganese atoms in the structure. The change of the average crystal size and microstrain were explained in terms of Al/Mn ratio in the solid solution. While the empirical bond-valence sums (BVS) of one oxygen atom, bridging the edge-sharing MO{sub 6} octahedron, were found to be under-bonded, the other one was over-bonded. The stereoactivity of the 6s{sup 2} lone electron pair of the Pb{sup 2+} cation was characterized in terms of the absolute value of eccentricity parameter (|Φ{sub i}|). Both bond valence parameter (r{sub 0i}) and BVS of Pb showed a linear correlation with |Φ{sub i}|. Deconvolution of the absorption feature of the infrared powder spectra between 1000 cm{sup −1} and 1400 cm{sup −1} required four fitted bands, which were assigned to B-O stretching vibrations of the trigonal planar BO{sub 3} groups. With increasing Al{sup 3+} dilution in PbAl{sub 1−x}Mn{sub x}BO{sub 4} almost all observed modes shifted toward lower wavenumbers confirming the solid solution. The absorptions caused by the vibrations of the heavy atom Pb were observed in the far-IR region.

36 MATERIALS SCIENCE↗
DOE OSTI2013

The effects of re-firing process under oxidizing atmosphere and temperatures on the properties of strontium aluminate phosphors

Graphical abstract: The comparative emission spectra of standard and re-fired Phosphor A under oxidizing atmosphere at various temperatures. The colour of Phosphor A re-fired at higher temperatures above 900 °C shifted from yellowish-green to bluish-green in the dark. But, the bluish-green emission could only be seen when it was exposed to UV and disappeared as soon as the light source was removed. Moreover, the emission intensities decreased as the re-firing temperatures increased. This could be attributed to the oxidation of Eu{sup 2+} during the re-firing process. It is well known fact from the literature that the reduction of Eu{sup 3+} to Eu{sup 2+} in appropriate host materials needs an annealing process in a reducing atmosphere such as H{sub 2}, H{sub 2}/N{sub 2} mixture or CO. Up to now, the reduction phenomena of Eu{sup 3+} → Eu{sup 2+} in air have been found in phosphates (Ba{sub 3}(PO{sub 4}){sub 2}:Eu), sulphates (BaSO{sub 4}:Eu), borates (SrB{sub 4}O{sub 7}:Eu, SrB{sub 6}O{sub 10}:Eu and BaB{sub 8}O{sub 13}:Eu) and aluminates (Sr{sub 4}Al{sub 14}O{sub 25}:Eu). Interestingly, an apparent blue shift in the phosphorescence spectrum was observed in the samples re-fired at 1000 °C and above, indicating a minimal effect on the oxidation state or the electronic energy levels of the co-doped Dy{sup 3+} ions, which were thought to act as long-lived hole traps resulting in long afterglow. - Highlights: • This study examines the effects re-firing at oxidizing atmosphere of photoluminescence of three different commercial SrAl{sub 2}O{sub 4}:Eu{sup 2+},Dy{sup 3+}-phosphors. • All the commercial SrAl{sub 2}O{sub 4}:Eu{sup 2+},Dy{sup 3+}-phosphors completely lost their phosphorescence after being re-fired at 1300 °C. • Oxidizing environment and re-firing temperature naturally affecting the valance of Eu{sup 2+} may cause the basic lattice structure to be modified and also limit their applications at higher temperatures, such as third firing vetrosa décor or glaze applications in ceramic industry. • It was thought that this kind of study may be promising to provide many outcome studies, may act to encourage additional efforts along these lines. - Abstract: Inorganic phosphorescent pigments have a very wide application, consisting of ceramic decoration and glazes. Therefore, in the present study 3 different commercially available strontium aluminate phosphors (coded Phosphor A, B and C) emitting yellowish-green light were investigated to determine their behaviour when re-fired under oxidizing atmosphere. The phosphors were re-fired at 10 different temperatures and consequent effects were studied. All the samples were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), laser particle size, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and fluorescence spectrometer analysis. It was found that firing them under oxidizing atmosphere strongly affected their phosphorescence abilities especially over 800–900 °C, because doped europium ions (Eu{sup 2+}) in their structures are oxidized to Eu{sup 3+}. It was also concluded that the phosphor powders clumped as the temperature rose, leading to their particle size distributions to change.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Fe{sub 2}O{sub 3}-Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} glasses as lithium-free nonsilicate pH responsive glasses – Compatibility between pH responsivity and hydrophobicity

Highlights: • Fe{sub 2}O{sub 3}-rich FeBiB glasses show high pH sensitivity and short pH response time. • Bi{sub 2}O{sub 3}-rich FeBiB glasses show relatively high contact angle for water. • FeBiB glasses are lithium-free nonsilicate pH responsive ones. • pH responsivity and hydrophobicity are obtained for optimum glass compositions. - Abstract: Lithium silicate-based glasses have widely been used as commercially available pH glass electrodes. It was revealed that Ti{sup 3+}-containing titanophosphate (TiO{sub 2}-P{sub 2}O{sub 5}, TP) glasses are pH responsive as lithium-free nonsilicate glasses for the first time. TP glasses with the compatibility between pH responsivity and self-cleaning property were obtained by the sequential post-annealing (oxidation and reduction) of as-prepared glasses. Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3} (BiB) glasses are relatively hydrophobic and are expected to show anti-fouling effect. They are unsuitable for pH responsive glasses, because they have high electrical resistivity. In the present study, xFe{sub 2}O{sub 3}·yBi{sub 2}O{sub 3}·(100 − x − y)B{sub 2}O{sub 3} glasses (xFeyBiB, x = 0–20 mol%, y = 20–80 mol%) glasses were selected as new pH responsive glasses with hydrophobicity, because Fe{sub 2}O{sub 3} is a representative component for causing hopping conduction to the glasses. BiB glass did not show pH responsivity, whereas xFeyBiB glasses showed good pH responsivity. xFeyBiB glasses are lithium-free nonsilicate pH responsive ones as well as TP glasses. The electrical resistivity and pH response time decreased with increasing Fe{sub 2}O{sub 3} content. The pH repeatability for standard solutions increased with increasing Bi{sub 2}O{sub 3} content. Silicate glass (20Fe70BiSi) showed better pH responsivity but lower contact angle than those of borate glass (20Fe70BiB). pH sensitivity increased in order of TP glasses (about 80%), xFeyBiB glasses (about 90%) and commercial pH responsive glass (about 100%). xFeyBiB glasses showed short pH response time compared to commercial pH responsive glass. The contact angle for water of xFeyBiB glasses was relatively high (about 90°) as well as BiB glasses, and increased slightly with increasing Bi{sub 2}O{sub 3} content regardless Fe{sub 2}O{sub 3} content. The high contact angle was related to low OH content determined by FT-IR measurement. Thus, 20Fe{sub 2}O{sub 3}·70Bi{sub 2}O{sub 3}·10B{sub 2}O{sub 3} glass was the most suitable one as pH responsive glasses with hydrophobicity. TP glasses are pH responsive ones with self-cleaning property, whereas xFeyBiB glasses are expected as pH responsive ones with anti-fouling property based on hydrophobicity.

36 MATERIALS SCIENCE↗