Low-temperature lithium diffusion in simulated high-level boroaluminosilicate nuclear waste glasses
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In this paper, the first observations have been made of anomalously strong viscosity behavior and correspondingly strong bulk glass formation and resistance to crystallization in a melt quenched (MQ) prepared series of invert, modifier content greater than the glass former content, mixed oxy-sulfide Na 4 P 2 S 7-x O x , 0 ≤ x ≤ 5, (NaPSO) glasses. We find that these glasses even with 67 mole % modifier, Na 2 S, and only 33 mole% glass former P 2 S 5-x O x , exhibit a calorimetric fragility index, m cal , as small as 29 compared to typical values of ~ 60 to 80 for alkali silicate glasses with > 50 mole% SiO 2 and the theoretical minimum m cal of ~ 15. The m cal values were converted to kinetic viscosity fragility, m vis , values and used with the measured glass transition temperatures, T g s, to produce viscosity curves for the glasses using the Mauro-Yue-Ellison-Gupta-Allan (MYEGA) model. The viscosity of the glass with a minimum m cal value of x = 2.5 was then shown to exhibit a viscosity that was as strong as, and for some compositions stronger than, the viscosity of alkali aluminosilicate glasses which have three dimensional network structures compared to the one dimensional chain structures observed in these MOS invert glasses. Consistent with these small values of fragility indices and therefore predicted higher viscosity above the glass transition temperature, T g , in the supercooled liquid regime, these glasses are also particularly resistant to crystallization. For example, the x = 2.5 glass composition exhibits a crystallization temperature, T C , more than 150K above its T g . We find that the calorimetric fragility of these glasses varies systematically with the extent of network forming bridging oxygens (BOs) in the glasses. The structural change caused by incrementally replacing sulfur with oxygen has been found to have consistent, large effects on the thermal properties.
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In this work, a combined analytical method of NEXAFS measurement and DFT-calculation was employed for the evaluation of Cs states in clay minerals. The measured Cs M 4,5 NEXAFS spectra of Cs halides were analyzed using the DFT-calculations in order to establish the analytical methods. The NEXAFS spectra of the Cs halides were well reproduced by incorporating the core-hole strength. The Cs M 4,5 NEXAFS spectrum of the clay minerals was well reproduced by the DFT-calculations including the major transitions and tail structures with the established method. Further evaluation of this spectrum by charge density analysis suggested that these major transitions and the tail structures likely reflect the bonding state and the local environment around the Cs atoms. Comparison of electronic states of Cs in the clay mineral with those in the Cs halides by DFT-calculations has shown that the interaction between Cs and the nearest-neighbor atom is largest in the clay mineral, which differs from those of Cs halides. This happened due to the energy level of Cs-5s and 5p, which was closer to that of O-2s and 2p than the s and p orbitals of other alkali metal and alkali earth metal elements.
Cation dependent resistance of a commercial cation exchange membrane, Nafion™ 212, as well as the solubility of select active materials are investigated, demonstrating practical consequences of cation choice on redox flow battery (RFB) performance. The conductivity of alkali and methyl- or -alcohol substituted ammonium cations through pretreated Nafion™ 212 reveal that cation size is the dominant factor affecting ionic transport. Among the alkali series the resistance increases with larger ionic radii and similarly, with increasing steric bulk through substitution on ammonia. The solubility of ferrocyanide, a commonly used redox flow battery posolyte (or catholyte), as well as iron, cobalt, and chromium metal-organic compounds are determined for the same series of cations. Full cells are assembled using various cation mixtures and membrane pre-treatments to demonstrate practical effects of each variable. Here, we highlight the need to carefully select the correct cations for efficient electrolyte design, since certain cations may lead to high conductivity but low solubility, or vice versa, and provide design principles for RFBs using Nafion™ 212.
First-principles quantum-mechanical calculations (CRYSTAL09 code, B3LYP functional) were performed on alkali titanates A{sub 2}Ti{sub n}O{sub 2n+1} with layered structure (n=3,4,6). Monoclinic structural types with unshifted (P2{sub 1}/m) and with shifted (C2/m) layers were considered. Crystal energies and full structural details were obtained for all Li, Na, and K phases. Neutron diffraction data were collected on powder samples of P2{sub 1}/m-Li{sub 2}Ti{sub 3}O{sub 7} (a=9.3146(3), b=3.7522(1), c=7.5447(3) Å, β=97.611(4)°) and C2/m-K{sub 2}Ti{sub 4}O{sub 9} (a=18.2578(8), b=3.79160(9), c=12.0242(4) Å, β=106.459(4)°) and their structures were Rietveld-refined. Computed energies show the P2{sub 1}/m arrangement as favoured over the C2/m one for n=3, and the opposite holds for n=6. In the n=4 case the P2{sub 1}/m configuration is predicted to be more stable for Li and Na, and the C2/m one for K titanates. Analysis of Li–O and K–O crystal-chemical environments from experiment and theory shows that the alkali atom bonding is stabilized/destabilized in the different phases consistently with the energy trend. - Graphical abstract: Display Omitted - Highlights: • The P2{sub 1}/m structure-type is found to be more stable for A{sub 2}Ti{sub 3}O{sub 7} layer titanates. • The C2/m structure-type is found to be more stable for A{sub 2}Ti{sub 6}O{sub 13} layer titanates. • Tetratitanates are predicted to prefer the P2{sub 1}/m (Li and Na) or C2/m (K) structure. • Li–O and K–O bond distances follow a trend consistent with computed phase energies.
Alkali and alkali earth hydrides have been used as solid state reductants recently to yield many interesting new oxygen-deficient transition metal oxides. These reactions have tacitly been assumed to be a solid phase reaction between the reductant and parent oxide. We have conducted a number of experiments with physical separation between the reductant and oxides, and find that in some cases reduction proceeds even when the reagents are physically separated, implying reactions with in-situ generated H{sub 2} and, to a lesser extent, getter mechanisms. Our findings change our understanding of these topochemical reactions, and should enhance the synthesis of additional new oxides and nanostructures. - Graphical abstract: Topochemical reductions with hydrides: Solid state or gas phase reaction? Display Omitted - Highlights: • SrFeO{sub 2} and LaNiO{sub 2} were prepared by topochemical reduction of oxides. • Separating the reducing agent (CaH{sub 2}, Mg metal) from the oxide still results in reduction. • Such topochemical reactions can occur in the gas phase.
Nine new coordination compounds, namely, [Co(HDSPTP){sub 2}(H{sub 2}O){sub 4}]·4H{sub 2}O (H{sub 2}DSPTP=4’-(2,4-disulfophenyl)-3,2’:6’3”-terpyridine, 1 and 2), {[Ni(DSPTP)(H_2O)_4]·3H_2O}{sub n} (3), {[Cu(HDSPTP)_2(H_2O)_3]·8H_2O}{sub n} (4), {[Cu(HDSPTP)_2(H_2O)_3]·6H_2O}{sub n} (5), {[Cu(DSPTP)(H_2O)_2]·H_2O}{sub n} (6), {[Zn(DSPTP)(H_2O)_2]·2H_2O}{sub n} (7), {[Cd(DSPTP)(H_2O)_2]·2H_2O}{sub n} (8), and [Ag{sub 2}(DSPTP)(H{sub 2}O)]{sub n} (9), were constructed based on a new ligand containing both terpyridyl and sulfo groups. The reactions of H{sub 2}DSPTP with Co(NO{sub 3}){sub 2}.6H{sub 2}O resulted in two mononuclear complexes (compounds 1 and 2). They are polymorphisms that display different hydrogen bonding networks. They are selectively synthesized by altering the added alkalis. The reaction of H{sub 2}DSPTP with Ni(NO{sub 3}){sub 2}·6H{sub 2}O resulted in a 1D “S-shaped” coordination chain (compound 3). The reactions of Cu(II) with H{sub 2}DSPTP at different pH value resulted in the following three compounds: two kinds of 1D chains obtained at pH 3.0 and 4.0 for compounds 4 and 5, respectively, and a 3D framework based on binuclear ring units with 4-connected sra topology (Compound 6). The reactions of H{sub 2}DSPTP with ds-block ions resulted in the following three compounds: a Zn(II) (compound 7) and a Cd(II) (compound 8) 3D frameworks with structures similar to that in compound 6, and a 3D framework based on tetranuclear Ag(I) SBUs with binodal (4,8)-connected flu type 3D framework topology. The structural diversity is mainly attributed to the rich coordination modes (from monodentate to µ{sub 7}-mode) and conformations (cis–cis and cis–trans) of HDSPTP{sup −}/DSPTP{sup 2−} ligands and the metal center and can be controllable synthesized by altering the alkalis, and pH value. Thermal stability of all compounds was performed, and the thermal behaviors of compounds 6 and 8 were further explored by PXRD. Compound 6 exhibits low thermal stability and undergo a crystalline–crystalline-amorphous phase transition as temperature increases from 25 °C to 200 °C, and show amorphous–crystalline phase transition when rehydrated. However, compound 8 exhibits high thermal stability above 500 °C. Its crystalline phase can retain above 300 °C and undergo a crystalline–crystalline phase transition as temperature increased to 400 °C, and transit back to compound 8 when rehydrated. Moreover, luminescence properties of compounds 7–9 were also investigated. - Graphical abstract: Series of coordination compounds based on a new terpyridine-based ligand, 4’-(2,4-disulfophenyl)-3,2’:6’3’’-terpyridine, were constructed. The syntheses, structural diversity, thermal stability, phase transition, and luminescent properties of selected compounds were explored. - Highlights: • Nine coordination polymers based on a new terpyridine-based ligand were obtained. • Both metal ion and coordination modes of H2DSPTP affect the structural diversity. • The Co(II) compounds are polymorphisms. • The pH-dependent syntheses of Cu(II) compounds were observed. • Compounds 6 and 8 exhibit phase transmission as temperature increased.
Single crystals of La{sub 0.516(3)}Na{sub 0.484(3)}MoO{sub 4}, Ce{sub 0.512(2)}Na{sub 0.488(2)}MoO{sub 4}, Pr{sub 0.502(2)}Na{sub 0.498(2)}MoO{sub 4,} Nd{sub 0.501(2)}Na{sub 0.499(2)}MoO{sub 4}, Sm{sub 0.509(2)}Na{sub 0.491(2)}MoO{sub 4}, and Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} were grown for the first time out of an alkali metal halide eutectic flux. All compounds crystallize in the tetragonal space group I4{sub 1}/a. UV/Vis measurements show the presence of an absorption edge for all compounds except Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4}. The temperature dependence of the magnetic susceptibility was measured for all compounds and found to be paramagnetic across the entire 2–300 K temperature range measured. - Graphical abstract: Single crystals of La{sub 0.516(3)}Na{sub 0.484(3)}MoO{sub 4}, Ce{sub 0.512(2)}Na{sub 0.488(2)}MoO{sub 4}, Pr{sub 0.502(2)}Na{sub 0.498(2)}MoO{sub 4,} Nd{sub 0.501(2)}Na{sub 0.499(2)}MoO{sub 4}, Sm{sub 0.509(2)}Na{sub 0.491(2)}MoO{sub 4}, and Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} were grown for the first time out of an alkali metal halide eutectic flux. All compounds crystallize in the tetragonal space group I4{sub 1}/a. Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} was found to possess the highest Mo{sup 5+} content at 20.6%. UV/Vis, magnetic susceptibility, and a bond valence sum analysis were performed on all samples. Display Omitted - Highlights: • Six lanthanide sodium molybdates have been synthesized and characterized. • An in situ reduction was carried out using Mo as a metal reducing agent. • UV/Vis and magnetic susceptibility data were collected. • Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} was found to possess the highest Mo{sup 5+} content at 20.6%.
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Single crystals of six new alkali lanthanide silicates and germanates were synthesized via the flux growth method. A2CeSi3O9 (A = Rb, Cs) and Cs2CeGe3O9 crystallize in the Wadeite structure with space group P63/m and lattice parameters a = 7.1950(2) Å and c = 10.5109(3) Å for the Rb analogue. K2CeSi3O9 crystallizes in a previously unobserved monoclinic distortion of the Wadeite structure with space group P21/n and lattice parameters a = 7.0801(2) Å, b = 10.458(2) Å, c = 12.238(2) Å and β = 90.07(3)°. Finally, Cs8Dy2Ge16O39 and Cs8Dy2Ge16O38F2 crystallize in two new structure types that are related to each other and to the Wadeite structure. Cs8Dy2Ge16O39 crystallizes in the monoclinic space group P2/c with lattice parameters a = 12.4054(3) Å, b = 7.4310(2) Å, c = 24.5761(6) Å, and β = 90.8849(16)° and Cs8Dy2Ge16O38F2 crystallizes in the orthorhombic space group Pnn2 with lattice parameters a = 12.3489(4) Å, b = 12.4805(5) Å, and c = 7.3802(3) Å. The synthesis and structure of the six compounds are reported and the crystallochemical reasons for the formation of each structure are discussed.
Highlights: • Carbon-coated pyrophosphate materials AMoP2O7 (A = Li and Na) were prepared via freeze- drying method. • BVEL analysis revealed the remarkable difference in the alkali diffusion behaviors of two AMoP{sub 2}O{sub 7} polymorphs. • LiMoP{sub 2}O{sub 7} shows the superior electrochemical activity towards de/intercalation of Li{sup +} and Na{sup +} ions compared with NaMoP{sub 2}O{sub 7} - Abstract: The carbon-coated single-phase samples of the pyrophosphates AMoP{sub 2}O{sub 7} (A = Li and Na) were synthesized using freeze-drying followed by annealing in a sealed silica tube with the Fe/FeO getter. The Rietveld refinement of the X-Ray powder diffraction data proved both structures are built up as a network of corner-linked MoO{sub 6} octahedra and P{sub 2}O{sub 7} groups with A-cations located in the open tunnels running along the [100] (LiMoP{sub 2}O{sub 7}) and [101] (NaMoP{sub 2}O{sub 7}) directions. The bond valence energy landscapes (BVEL) analysis revealed three-dimensional pathways of alkali-ion migration with significantly different activation energies (0.8 eV for LiMoP{sub 2}O{sub 7} and 4.5 eV for NaMoP{sub 2}O{sub 7}) anticipating LiMoP{sub 2}O{sub 7} to exhibit faster Li{sup +} diffusion and better electrochemical characteristics. Both materials displayed electrochemical activity in Li- and Na-cells with reversible capacities of ∼20 mA h g{sup −1} for NaMoP{sub 2}O{sub 7} and more than 70 mA h g{sup −1} for LiMoP{sub 2}O{sub 7}, being in a good agreement with the BVEL results.
Zeolites are nanoporous aluminosilicates widely used as commercial adsorbents, heterogeneous catalysts, and ion-exchange materials due to their unique porosity, acidity, and thermal stability. The vast majority of synthetically-realized zeolite structures are prepared under hydrothermal conditions in alkaline media, and often in the presence of an organic structure-directing agent that facilitates the crystallization of diverse porous networks. Due to economic and environmental disadvantages of organic-based syntheses, it is often desirable to produce zeolites in organic-free media using alkali metal ions as the most commonly employed inorganic structure-directing agents (ISDAs). Here, in this study, we were inspired by the elemental compositions of natural zeolite minerals to examine the use of an alkaline earth metal ion as the ISDA to prepare zeolites with the PHI framework type. Two natural minerals exhibiting this crystal structure are phillipsite and harmotome. Both structures contain sodium and potassium as extra-framework cations, but only harmotome contains barium cations. Here we examined how the combination of alkali and alkaline earth ISDAs promote the formation of PHI-type zeolites. Our findings reveal that each isostructure is prepared under different synthesis conditions where simply adding barium to a growth mixture does not always lead to harmotome formation. Harmotome is formed in more dilute and alkaline growth media; however, time-resolved analyses of zeolite crystallization reveal that harmotome can be synthesized at low temperatures (ca. 65 °C) with rates that are 5-times faster than syntheses of phillipsite. This seemingly indicates that barium reduces the energetic barrier for PHI-type zeolite nucleation in ways that are not fully understood. Moreover, harmotome crystals exhibit an average particle size of ca. 60 nm, which is nearly 40-fold smaller than phillipsite crystals prepared under similar conditions. Collectively, these findings identify routes to control crystallization of PHI-type zeolites and may provide a broader strategy for using the composition of natural zeolite minerals to optimize the preparation of synthetic analogues.
Monovalent alkali halides such as NaI, CsI, and LiI are widely used as inorganic scintillators for radiation detection due to their light yield, the capability for the growth of large single crystals, relatively low cost, and other favorable characteristics. These materials are frequently activated through the addition of small amounts (e.g., a few hundred ppm) of elements such as thallium - or sodium in the case of CsI. The monovalent alkali halide scintillators can also be activated with low concentrations of Eu 2+ , however Eu activation has previously not been widely employed due to the non-uniform segregation of the divalent Eu dopant that leads to the formation of unwanted phases during Bridgman or other solidification crystal-growth methods. Specifically, for Eu concentrations near and above ~0.5%, Suzuki Phase precipitates form in the course of the melt-growth process, and these Suzuki Phase particles scatter the scintillation light. This adversely affects the scintillator performance via reduction in the optical transmission of the material, and depending on the crystal thickness and precipitated-particle concentration, this reduction can occur up to the point of opacity. Here we describe a post-growth process for the removal of Suzuki Phase precipitates from single crystals of the neutron scintillator LiI activated with Eu 2+ at concentrations up to and in excess of 3 wt.%, and we correlate the resulting neutron-detection performance with the thermal processing methods used to remove the Suzuki Phase particles. Furthermore, the resulting improved scintillator properties using increased Eu activator levels are applicable to neutron imaging and active interrogation systems, and pulse-height gamma-ray spectroscopy rather than pulse-shape discrimination can be used to discriminate between gamma ray and neutron interaction events.
Intrinsic dosimetry is the method of measuring total absorbed dose received by the walls of a container holding radioactive material. By considering this dose in tandem with the physical characteristics of the radioactive material housed within the container, this method can provide enhanced pathway information for interdicted radioactive samples. Thermoluminescence (TL) dosimetry was used to measure ionizing radiation dose effects on stock borosilicate glass. Differences in TL glow curve shape and intensity were observed for glasses from different geographical origins. The different TL signatures strongly correlated with the concentration of alkaline earth metals and the ratio of sodium to the total amount of alkali metal present in the borosilicate glass.
Concentrated Solar Power (CSP) is considered as a viable large-scale renewable energy source to produce electricity. However, current costs to produce electricity from CSP are not cost competitive as compared to the traditional energy generation technologies based on fossil fuels and nuclear. It is envisioned that development of high efficiency and high heat capacity thermal storage fluids will increase system efficiency, reduce structural storage volume, and hence, contribute to reducing costs. Particularly, with respect to CSP, current high temperature energy storage fluids, such as molten salts, are relatively limited in terms of their thermal energy storage capacity and thermal conductivity. The current work explores possibility of boosting the thermal storage capacity of molten salts through latent heat of added phase change materials. We studied the advantage Of adding coated Zn micron-sized particles to alkali chloride salt eutectic for enhanced thermal energy storage. Zinc particles (0.6 mu m and 5 mu m) obtained from commercial source were coated with an organo-phosphorus shell to improve chemical stability and to prevent individual particles from coalescing with one another during melt/freeze cycles. Thermal cycling tests (200 melt/freeze cycles) showed that coated Zn particles have good thermal stability and are chemically inert to alkali chloride salt eutectic in both N-2 and in air atmospheres. Elemental mapping of the cross-sectional view of coated Zn particles from the composite after thermal cycles showed no signs of oxidation, agglomeration or other type of particle degradation. The measured enhancement in volumetric thermal storage capacity of the composite with just similar to 10 vol% of coated Zn particles over the base chloride salt eutectic varies from 15% to 34% depending on cycling temperature range (Delta T = 50 degrees C -100 degrees C. (C) 2015 Elsevier Ltd. All rights reserved.
In this work we test field-relevant potential-induced degradation (PID) behavior by encapsulating laboratory Cu(In,Ga)Se 2 (CIGS) solar cells and applying +1000 V uniformly on the face of the front glass. In this configuration, we find that K-rich borosilicate glass reduces the extent of PID relative to Na-rich soda-lime glass. We also find that the standard testing protocol of stressing cells at short-circuit leads to faster PID than stressing cells at open-circuit. We characterize two types of CIGS PID: The first, front shunting PID, is driven by front-glass stress and occurs when alkali metal cations accumulate in the i-ZnO buffer, where they increase shunt conductance to reduce fill factor. The second, p-n junction PID, results from back-glass stress as alkali metal cations pile up near the CIGS surface/CdS buffer, where they reduce charge carrier concentration, open-circuit voltage, and fill factor to degrade efficiency ~160 times faster than front shunting PID.
Highlights: •MSW, RDF and waste wood fuel blends were torrefied at 220 °C. •Chlorine is separated from metals catalytically active in PCDD/F formation. •Torrefaction of MSW and RDF reduces the risk for alkali-chloride corrosion in WtE. •Torrefaction of MSW generates less PCDD/F than RDF when combined with DC. -- Abstract: Torrefaction of municipal solid waste (MSW), refuse-derived fuel (RDF), and demolition and construction wood (DC) was performed at 220 °C and a residence time of 90 min in a bench-scale reactor. The levels of toxic polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) contained in emission from the torrefaction process were evaluated. In addition, main ash-forming elements and trace metals in the raw feedstock and char were determined. The use of MSW in fuel blends with DC resulted in lower PCDD and PCDF emissions after torrefaction, compared with the RDF blends. The migration of chlorine from the feedstock to the gas phase reduces the chlorine content of the char which may reduce the risk of alkali chloride-corrosion in char combustion. However, trace metals catalytically active in the formation of PCDD and PCDF remain in the char, thereby may promote PCDD and PCDF formation during subsequent char combustion for energy recovery; this formation is less extensive than when the feedstock is used.