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Sample records for alkali aluminosilicate glasses

  1. Alkali aluminosilicate melts and glasses: structuring at the middle range order of amorphous matter

    NASA Astrophysics Data System (ADS)

    Le Losq, C.; neuville, D. R.

    2012-12-01

    Rheological properties of silicate melts govern both magma ascension from the mantle to the surface of the earth and volcanological eruptions styles and behaviours. It is well known that several parameters impact strongly these properties, such as for instance the temperature, pressure, chemical composition and volatiles concentration, finally influencing eruptive behaviour of volcanoes. In this work, we will focus on the Na2O-K2O-Al2O3-SiO2 system, which is of a prime importance because it deals with a non-negligible part of natural melts, like for instance the Vesuvius (Italy) or Erebus (Antartica) magmas. In an oncoming paper in Chemical Geology (Le Losq and Neuville, 2012), we have communicated results of the study of mixing Na-K in tectosilicate melts containing a high concentration of silica (≥75mol%). In the present communication, we will enlarge this first point of view to tectosilicate melts presenting a lower silica concentration. We will first present our viscosity data, and then the Adam and Gibbs theory that allows theoretically modelling Na-K mixing in aluminosilicate melts by using the so-called "mixed alkali effect". On the basis of the rheological results, the Na-K mixing cannot be explained with the ideal "mixed alkali effect", which involves random exchange of Na-K cationic pairs. To go further and as rheological properties are directly linked with structural properties, we will present our first results obtained by Raman and NMR spectroscopy. These last ones provide important structural pieces of information on the polymerization state of glasses and melts, and also on the environment of tetrahedrally coordinated cations. Rheological and structural results all highlight that Na and K are not randomly distributed in aluminosilicate glasses and melts networks. Na melts present a network with some channels and a non-random distribution of Al and Si. K networks are different. They also present a non-random distribution of Al and Si, but in two sub

  2. Structural Role of Alkali Cations in Calcium Aluminosilicate Glasses as Examined Using Oxygen-17 Solid-State Nuclear Magnetic Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sukenaga, Sohei; Kanehashi, Koji; Shibata, Hiroyuki; Saito, Noritaka; Nakashima, Kunihiko

    2016-05-01

    The structural roles of alkali and calcium cations are important for understanding the physical and chemical properties of aluminosilicate melts and glasses. Recently, oxygen-17 nuclear magnetic resonance (17O NMR) studies of calcium-sodium aluminosilicate glasses showed that these structural roles are not randomly given, but rather each cation has its own preferential role. However, the relationship between cation type and role preference in calcium aluminosilicate glass is not completely understood. In the present study, the structural roles of lithium, sodium, and potassium cations in selected calcium aluminosilicate glasses are investigated using 17O solid-state NMR experiments. Data from these experiments clearly show that potassium cations have a notably stronger tendency to act as charge compensators within the network structure, compared to sodium and lithium cations. The result of 17O NMR experiment also showed that sodium and lithium cations in part act as network modifier alongside with calcium cations.

  3. Structural Role of Alkali Cations in Calcium Aluminosilicate Glasses as Examined Using Oxygen-17 Solid-State Nuclear Magnetic Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sukenaga, Sohei; Kanehashi, Koji; Shibata, Hiroyuki; Saito, Noritaka; Nakashima, Kunihiko

    2016-08-01

    The structural roles of alkali and calcium cations are important for understanding the physical and chemical properties of aluminosilicate melts and glasses. Recently, oxygen-17 nuclear magnetic resonance (17O NMR) studies of calcium-sodium aluminosilicate glasses showed that these structural roles are not randomly given, but rather each cation has its own preferential role. However, the relationship between cation type and role preference in calcium aluminosilicate glass is not completely understood. In the present study, the structural roles of lithium, sodium, and potassium cations in selected calcium aluminosilicate glasses are investigated using 17O solid-state NMR experiments. Data from these experiments clearly show that potassium cations have a notably stronger tendency to act as charge compensators within the network structure, compared to sodium and lithium cations. The result of 17O NMR experiment also showed that sodium and lithium cations in part act as network modifier alongside with calcium cations.

  4. Ring distributions in alkali- and alkaline-earth aluminosilicate framework glasses- a raman spectroscopic study

    USGS Publications Warehouse

    Sharma, S.K.; Philpotts, J.A.; Matson, D.W.

    1985-01-01

    Raman spectra of crystalline polymorphs of a number of tectosilicate minerals having various sizes of smallest rings of TO4 tetrahedra (T = Si, Al) have been investigated to identify the bands that are sensitive indicators of the smallest rings in the network. The information obtained from the Raman spectra of tectosilicate minerals (e.g., SiO2 polymorphs, NaAlSi3O8 (Ab), NaAlSiO4 (Ne), KAlSi3O8 (Or), and KAlSi2O6 (Lc)) is used to interpret the Raman spectra of the isochemical glasses. It is shown that the frequency of the dominant ??s (TOT) band in the spectra of both crystals and glasses is related to the dominant size of TO4 rings in the structure. In agreement with previous X-ray RDF work, it is found that in the glasses of Ab and Jd (NaAlSi2O6) compositions, six-membered rings of TO4 tetrahedra predominate. The Raman spectrum of Or glass, however, indicates that clusters of intermixed four- and six-membered rings of TO4 tetrahedra, similar to those existing in crystalline leucite, are also present in the glass. Raman evidence indicates that four-membered rings of TO4 tetrahedra predominate in the glass of An composition. Similarly, the higher frequency of the ??s (TOT) band in the spectrum of Ne glass as compared with the frequency the ??s (TOT) band in the spectra of crystalline cargenieite and nephelite indicates either an admixture of the four- and six-membered rings or the puckering of six-membered rings in the glass structure. ?? 1985.

  5. Structure and rheological properties in alkali aluminosilicate melts

    NASA Astrophysics Data System (ADS)

    Le Losq, Charles; Neuville, Daniel

    2010-05-01

    Rheological properties of silicate melts govern both magma ascension from the mantle to the surface of the earth and volcanological eruptions styles and behaviors. In this mind, it is very important to understand which parameters influence these properties. Up to now, we know for example that viscosity of silicate melts is dependent of temperature, pressure and chemical composition. In this work, we will focus on the Na2O-K2O-Al2O3-SiO2 system, which is of a prime importance because it deals with a non-negligible part of natural melts like haplogranitic rhyolitic alkali magmas. We will first present our viscosity measurements and some modelisation concepts based on the Adam and Gibbs theory. From configurational entropy theory we obtain some macroscopic information's that we can link to the structure of glasses and melts. In this mind, we have investigated them with Raman and NMR spectroscopies. These spectroscopies provide information on speciation and polymerization of glasses and melts. We will present and discuss structural and rheological variations as a function of temperature and chemical change.

  6. Crystallization of a barium-aluminosilicate glass

    NASA Technical Reports Server (NTRS)

    Drummond, C. H., III; Lee, W. E.; Bansal, N. P.; Hyatt, M. J.

    1989-01-01

    The crystallization of a celsian glass composition was investigated as a possible high-temperature ceramic matrix material. Heat treatments invariably resulted in crystallization of the hexaclesian phase unless a flux, such as lithia, was added or a nucleating agent used (e.g., celsian seeds). TEM analysis revealed complex microstructures. Glasses with Mo additions contained hexacelsian, mullite, and an Mo-rich glass. Li2O additions stabilized celsian but mullite and Mo-rich glass were still present.

  7. Effects of Thermal and Pressure Histories on the Chemical Strengthening of Sodium Aluminosilicate Glass

    NASA Astrophysics Data System (ADS)

    Svenson, Mouritz; Thirion, Lynn; Youngman, Randall; Mauro, John; Bauchy, Mathieu; Rzoska, Sylwester; Bockowski, Michal; Smedskjaer, Morten

    2016-03-01

    Glasses can be chemically strengthened through the ion exchange process, wherein smaller ions in the glass (e.g., Na+) are replaced by larger ions from a salt bath (e.g., K+). This develops a compressive stress (CS) on the glass surface, which, in turn, improves the damage resistance of the glass. The magnitude and depth of the generated CS depends on the thermal and pressure histories of the glass prior to ion exchange. In this study, we investigate the ion exchange-related properties (mutual diffusivity, CS, and hardness) of a sodium aluminosilicate glass, which has been densified through annealing below the initial fictive temperature of the glass or through pressure-quenching from the glass transition temperature at 1 GPa prior to ion exchange. We show that the rate of alkali interdiffusivity depends only on the density of the glass, rather than on the applied densification method. However, we also demonstrate that for a given density, the increase in CS and increase in hardness induced by ion exchange strongly depends on the densification method. Specifically, at constant density, the CS and hardness values achieved through thermal annealing are larger than those achieved through pressure-quenching. These results are discussed in relation to the structural changes in the environment of the network-modifier and the overall network densification.

  8. Non-bridging Oxygens in Calcium Aluminosilicate Glass From Per-calcic to Peraluminous Compositions

    NASA Astrophysics Data System (ADS)

    Thompson, L.; Stebbins, J.

    2008-12-01

    The role of non-bridging oxygen (NBO) and its effects on the thermodynamic and transport properties of aluminosilicate melts are not fully understood, although this species clearly must have a major influence on configurational entropy, viscosity, etc. Its existence along metaluminous joins in alkali- and alkaline-earth aluminosilicates was first postulated from viscosity measurements (Toplis et al., 1996, 2004) and then directly observed in several metaluminous calcium aluminosilicates by 17O nuclear magnetic resonance (NMR) spectroscopy. Much of the recent work has concentrated on glasses with an M+n/(M+nAl) ratio greater than or equal to 0.5 (metaluminous to peralkaline or per-alkaline earth); however, the observed viscosity maxima in several ternary systems occur when this ratio is less than 0.5 (peraluminous). Using NMR spectroscopy, this study investigates the effects of the Ca/Al ratio on the amount of NBO present in calcium aluminosilicate (CAS) glasses. 17O MAS NMR spectra of glasses with 60 mol% SiO2 show a decrease in NBO as the ratio R=Ca+2/(Ca+2Al) decreases, from 6.9% at R=0.56 to 1.0% at R=0.44. Measurable amounts of NBO thus persist well into the peraluminous region of the CAS system, but the species becomes undetectable (<0.5%) when R reaches 0.38 and 0.33. 27Al MAS NMR spectra of these glasses show an increase in the amount of five-coordinated aluminum as compositions become more peraluminous, as is well-known from previous studies (Neuville et al. 2006). Comparison with published viscosity measurements measured at both higher and lower mol % SiO2 (Toplis et al. 2004) suggests that the viscosity maximum does not correspond exactly with the disappearance of NBO from the glasses, but effects of temperature on speciation will need to be taken into account to accurately link glass structure with melt properties: recent work has shown, for example, that NBO content increases with temperature in CaAl2Si2O8 melt (Stebbins et al. 2008).

  9. Crystallization Kinetics of Calcium-magnesium Aluminosilicate (CMAS) Glass

    NASA Technical Reports Server (NTRS)

    Wiesner, Valerie L.; Bansal, Narottam P.

    2015-01-01

    The crystallization kinetics of a calcium-magnesium aluminosilicate (CMAS) glass with composition relevant for aerospace applications, like air-breathing engines, were evaluated using differential thermal analysis (DTA) in powder and bulk forms. Activation energy and frequency factor values for crystallization of the glass were evaluated. X-ray diffraction (XRD) was used to investigate the onset of crystallization and the phases that developed after heat treating bulk glass at temperatures ranging from 690 to 960 deg for various times. Samples annealed at temperatures below 900 deg remained amorphous, while specimens heat treated at and above 900 deg exhibited crystallinity originating at the surface. The crystalline phases were identified as wollastonite (CaSiO3) and aluminum diopside (Ca(Mg,Al) (Si,Al)2O6). Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were employed to examine the microstructure and chemical compositions of crystalline phases formed after heat treatment.

  10. Thermodynamic assessment of hydrothermal alkali feldspar-mica-aluminosilicate equilibria

    USGS Publications Warehouse

    Sverjensky, D.A.; Hemley, J.J.; d'Angelo, W. M.

    1991-01-01

    The thermodynamic properties of minerals retrieved from consideration of solid-solid and dehydration equilibria with calorimetric reference values, and those of aqueous species derived from studies of electrolytes, are not consistent with experimentally measured high-temperature solubilities in the systems K2O- and Na2O-Al2O3-SiO2-H2O-HCl (e.g., K-fs - Ms - Qtz - K+ - H+). This introduces major inaccuracies into the computation of ionic activity ratios and the acidities of diagenetic, metamorphic, and magmatic hydrothermal fluids buffered by alkali silicate-bearing assemblages. We report a thermodynamic analysis of revised solubility equilibria in these systems that integrates the thermodynamic properties of minerals obtained from phase equilibria studies (Berman, 1988) with the properties of aqueous species calculated from a calibrated equation of state (Shock and Helgeson, 1988). This was achieved in two separate steps. First, new values of the free energies and enthalpies of formation at 25??C and 1 bar for the alkali silicates muscovite and albite were retrieved from the experimental solubility equilibria at 300??C and Psat. Because the latter have stoichiometric reaction coefficients different from those for solid-solid and dehydration equilibria, our procedure preserves exactly the relative thermodynamic properties of the alkali-bearing silicates (Berman, 1988). Only simple arithmetic adjustments of -1,600 and -1,626 (??500) cal/mol to all the K- and Na-bearing silicates, respectively, in Berman (1988) are required. In all cases, the revised values are within ??0.2% of calorimetric values. Similar adjustments were derived for the properties of minerals from Helgeson et al. (1978). Second, new values of the dissociation constant of HCl were retrieved from the solubility equilibria at temperatures and pressures from 300-600??C and 0.5-2.0 kbars using a simple model for aqueous speciation. The results agree well with the conductance-derived dissociation

  11. Novel, inorganic composites using porous, alkali-activated, aluminosilicate binders

    NASA Astrophysics Data System (ADS)

    Musil, Sean

    Geopolymers are an inorganic polymeric material composed of alumina, silica, and alkali metal oxides. Geopolymers are chemical and fire resistant, can be used as refractory adhesives, and are processed at or near ambient temperature. These properties make geopolymer an attractive choice as a matrix material for elevated temperature composites. This body of research investigated numerous different reinforcement possibilities and variants of geopolymer matrix material and characterized their mechanical performance in tension, flexure and flexural creep. Reinforcements can then be chosen based on the resulting properties to tailor the geopolymer matrix composites to a specific application condition. Geopolymer matrix composites combine the ease of processing of polymer matrix composites with the high temperature capability of ceramic matrix composites. This study incorporated particulate, unidirectional fiber and woven fiber reinforcements. Sodium, potassium, and cesium based geopolymer matrices were evaluated with cesium based geopolymer showing great promise as a high temperature matrix material. It showed the best strength retention at elevated temperature, as well as a very low coefficient of thermal expansion when crystallized into pollucite. These qualities made cesium geopolymer the best choice for creep resistant applications. Cesium geopolymer binders were combined with unidirectional continuous polycrystalline mullite fibers (Nextel(TM) 720) and single crystal mullite fibers, then the matrix was crystallized to form cubic pollucite. Single crystal mullite fibers were obtained by the internal crystallization method and show excellent creep resistance up to 1400°C. High temperature flexural strength and flexural creep resistance of pollucite and polycrystalline/single-crystal fibers was evaluated at 1000-1400°C.

  12. DuraLith Alkali-Aluminosilicate Geopolymer Waste Form Testing for Hanford Secondary Waste

    SciTech Connect

    Gong, W. L.; Lutz, Werner; Pegg, Ian L.

    2011-07-21

    The primary objective of the work reported here was to develop additional information regarding the DuraLith alkali aluminosilicate geopolymer as a waste form for liquid secondary waste to support selection of a final waste form for the Hanford Tank Waste Treatment and Immobilization Plant secondary liquid wastes to be disposed in the Integrated Disposal Facility on the Hanford Site. Testing focused on optimizing waste loading, improving waste form performance, and evaluating the robustness of the waste form with respect to waste variability.

  13. Dominant toughening mechanisms in barium aluminosilicate (BAS) glass-ceramics

    NASA Astrophysics Data System (ADS)

    Griggs, Jason Alan

    The purpose of this study was to develop a barium aluminosilicate (BAS) glass-ceramic with improved strength and fracture toughness by controlling the morphology of the constituent phases through a series of thermal crystallization treatments. The specific objectives of this study were to (1) determine which toughening mechanisms are active in the BAS system, (2) provide quantitative estimates of the relative contributions of those mechanisms, and (3) identify the processing conditions that correspond to a glass-ceramic with optimal fracture toughness. The BAS system was chosen for this study because of its potential applications in CAD-CAM production of dental prostheses. It is concluded that load sharing and crack deflection are the only major sources of toughening in the BAS system. Theoretical predictions for toughening increases due to load sharing and crack deflection are insufficient to account for 100% of the increases observed. The excess increase in fracture toughness is produced by thermal mismatch between and crystal and glass phases. The strength and fracture toughness of BAS glass-ceramics are shown to increase with increasing crystal growth time over the entire range of treatments studied. The strength and fracture toughness increased from 63 ± 8 MPa and 0.89 ± 0.05 MPa*msp{1/2}, respectively for BAS glass to 141 ± 8 MPa and 1.87 ± 0.07 MPa*msp{1/2} respectively for a glass-ceramic treated for 256 h at 975sp°C. Fracture toughness was also shown to increase with increasing mean crystal size. A non-stoichiometric glass composition results in thermal compatibility between the glass and crystal phases, eliminating the weakening at large crystal sizes that can be associated with a spontaneous microcracking mechanism.

  14. Selective laser densification of lithium aluminosilicate glass ceramic tapes

    NASA Astrophysics Data System (ADS)

    Zocca, Andrea; Colombo, Paolo; Günster, Jens; Mühler, Thomas; Heinrich, Jürgen G.

    2013-01-01

    Tapes, cast by blade deposition of a lithium aluminosilicate glass slurry, were sintered using a YAG-fiber laser, with the aim of finding suitable parameters for an additive manufacturing process based on layer-wise slurry deposition and selective laser densification. The influence of the laser parameters (output power and scan velocity) on the sintering was evaluated, by scanning electron microscopy and by X-ray diffraction, on the basis of the quality of the processed layer. Well densified samples could be obtained only in a small window of values for the output power and the scan velocity. The measurement of the width of a set of single scanned lines allowed also to estimate the minimum resolution of the system along the layer plane.

  15. Cellular morphology of organic-inorganic hybrid foams based on alkali alumino-silicate matrix

    SciTech Connect

    Verdolotti, Letizia; Capasso, Ilaria; Lavorgna, Marino; Liguori, Barbara; Caputo, Domenico; Iannace, Salvatore

    2014-05-15

    Organic-inorganic hybrid foams based on an alkali alumino-silicate matrix were prepared by using different foaming methods. Initially, the synthesis of an inorganic matrix by using aluminosilicate particles, activated through a sodium silicate solution, was performed at room temperature. Subsequently the viscous paste was foamed by using three different methods. In the first method, gaseous hydrogen produced by the oxidization of Si powder in an alkaline media, was used as blowing agent to generate gas bubbles in the paste. In the second method, the porous structure was generated by mixing the paste with a “meringue” type of foam previously prepared by whipping, under vigorous stirring, a water solution containing vegetal proteins as surfactants. In the third method, a combination of these two methods was employed. The foamed systems were consolidated for 24 hours at 40°C and then characterized by FTIR, X-Ray diffraction, scanning electron microscopy (SEM) and compression tests. Low density foams (∼500 Kg/m{sup 3}) with good cellular structure and mechanical properties were obtained by combining the “meringue” approach with the use of the chemical blowing agent based on Si.

  16. Flux Decoupling and Chemical Diffusion in Redox Dynamics in Aluminosilicate Melts and Glasses (Invited)

    NASA Astrophysics Data System (ADS)

    Cooper, R. F.

    2010-12-01

    Measurements of redox dynamics in silicate melts and glasses suggest that, for many compositions and for many external environments, the reaction proceeds and is rate-limited by the diffusive flux of divalent-cation network modifiers. Application of ion-backscattering spectrometry either (i) on oxidized or reduced melts (subsequently quenched before analysis) or (ii) on similarly reacted glasses, both of basalt-composition polymerization, demonstrates that the network modifiers move relative to the (first-order-rigid) aluminosilicate network. Thus, the textures associated with such reactions are often surprising, and frequently include metastable or unstable phases and/or spatial compositional differences. This response is only possible if the motion of cations can be decoupled from that of anions. In many cases, decoupling is accomplished by the presence in the melt/glass of transition-metal cations, whose heterovalency creates distortions in the electronic band structure resulting in electronic defects: electron “holes” in the valence band or electrons in the conduction band. (The prevalence of holes or electrons being a function of bulk chemistry and oxygen activity.) These electronic species make the melt/glass a “defect semiconductor.” Because (a) the critical issue in reaction dynamics is the transport coefficient (the product of species mobility and species concentration) and (b) the electronic species are many orders of magnitude more mobile than are the ions, very low concentrations of transition-metal ions are required for flux decoupling. For example, 0.04 at% Fe keeps a magnesium aluminosilicate melt/glass a defect semiconductor down to 800°C [Cook & Cooper, 2000]. Depending on composition, high-temperature melts can see ion species having a high-enough transport coefficient to allow decoupling, e.g., alkali cations in a basaltic melt [e.g., Pommier et al., 2010]. In this presentation, these ideas will be illustrated by examining redox dynamics

  17. Intrinsic differences in atomic ordering of calcium (alumino)silicate hydrates in conventional and alkali-activated cements

    SciTech Connect

    White, Claire E.; Daemen, Luke L.; Hartl, Monika; Page, Katharine

    2015-01-15

    The atomic structures of calcium silicate hydrate (C–S–H) and calcium (–sodium) aluminosilicate hydrate (C–(N)–A–S–H) gels, and their presence in conventional and blended cement systems, have been the topic of significant debate over recent decades. Previous investigations have revealed that synthetic C–S–H gel is nanocrystalline and due to the chemical similarities between ordinary Portland cement (OPC)-based systems and low-CO{sub 2} alkali-activated slags, researchers have inferred that the atomic ordering in alkali-activated slag is the same as in OPC–slag cements. Here, X-ray total scattering is used to determine the local bonding environment and nanostructure of C(–A)–S–H gels present in hydrated tricalcium silicate (C{sub 3}S), blended C{sub 3}S–slag and alkali-activated slag, revealing the large intrinsic differences in the extent of nanoscale ordering between C–S–H derived from C{sub 3}S and alkali-activated slag systems, which may have a significant influence on thermodynamic stability, and material properties at higher length scales, including long term durability of alkali-activated cements.

  18. Fictive temperature-independent density and minimum indentation size effect in calcium aluminosilicate glass

    SciTech Connect

    Gross, T. M.; Tomozawa, M.

    2008-09-15

    Using the calcium aluminosilicate system a glass was developed that exhibits fictive temperature-independent density by creating an intermediate glass between normal and anomalous glasses. Normal glass, such as soda-lime silicate glass, exhibits decreasing density with increasing fictive temperature while anomalous glass, such as silica glass, exhibits increasing density with increasing fictive temperature. This intermediate glass composition was found to exhibit the minimum indentation size effect during indentation hardness testing. It appears that the indentation size effect is correlated with a deformation-induced fictive temperature increase, which is accompanied by a density change and hardness change in the vicinity of the indentation. It is suggested from these observations that indentation size effect originates from the energy required to create interfaces and defects such as shear bands, subsurface cracks, and point defects near the indenter-specimen boundary, which accompany the volume change.

  19. Chemical durability of soda-lime-aluminosilicate glass for radioactive waste vitrification

    SciTech Connect

    Eppler, F.H.; Yim, M.S.

    1998-09-01

    Vitrification has been identified as one of the most viable waste treatment alternatives for nuclear waste disposal. Currently, the most popular glass compositions being selected for vitrification are the borosilicate family of glasses. Another popular type that has been around in glass industry is the soda-lime-silicate variety, which has often been characterized as the least durable and a poor candidate for radioactive waste vitrification. By replacing the boron constituent with a cheaper substitute, such as silica, the cost of vitrification processing can be reduced. At the same time, addition of network intermediates such as Al{sub 2}O{sub 3} to the glass composition increases the environmental durability of the glass. The objective of this study is to examine the ability of the soda-lime-aluminosilicate glass as an alternative vitrification tool for the disposal of radioactive waste and to investigate the sensitivity of product chemical durability to variations in composition.

  20. Electric field-induced softening of alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    McLaren, C.; Heffner, W.; Tessarollo, R.; Raj, R.; Jain, H.

    2015-11-01

    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  1. Electric field-induced softening of alkali silicate glasses

    SciTech Connect

    McLaren, C.; Heffner, W.; Jain, H.; Tessarollo, R.; Raj, R.

    2015-11-02

    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  2. Optical absorption and luminescence study of cobalt-doped magnesium aluminosilicate glass ceramics

    NASA Astrophysics Data System (ADS)

    Malyarevich, A. M.; Denisov, I. A.; Yumashev, K. V.; Dymshits, O. S.; Zhilin, A. A.

    2002-08-01

    Linear and nonlinear optical properties of cobalt-doped magnesium aluminosilicate transparent glass ceramics that were prepared under different conditions have been studied. It has been shown that absorption and luminescence spectra and absorption bleaching of these glass ceramics are defined mainly by tetrahedrally coordinated Co 2+ ions located in magnesium aluminum spinel nanocrystals. The lifetimes of the 4 T 1 ( 4 F) and 4 T 2 ( 4 F) excited states of the tetrahedral Co 2+ ions were found to be in the ranges 2540 and 120450 ns, respectively, depending on the Co concentration. 2002 Optical Society of America

  3. Water solubility in calcium aluminosilicate glasses investigated by first principles techniques

    SciTech Connect

    Bouyer, Frederic; Geneste, Gregory; Ispas, Simona; Kob, Walter; Ganster, Patrick

    2010-12-15

    First-principles techniques have been employed to study the reactivity of water into a calcium aluminosilicate glass. In addition to the well known hydrolysis reactions Si-O-Si+H{sub 2}O{yields}Si-OH+Si-OH and Si-O-Al+H{sub 2}O{yields}Si-OH+Al-OH, a peculiar mechanism is found, leading to the formation of an AlO{sub 3}-H{sub 2}O entity and the breaking of Al-O-Si bond. In the glass bulk, most of the hydrolysis reactions are endothermic. Only a few regular sites are found reactive (i.e. in association with an exothermic reaction), and in that case, the hydrolysis reaction leads to a decrease of the local disorder in the amorphous vitreous network. Afterwards, we suggest that ionic charge compensators transform into network modifiers when hydrolysis occurs, according to a global process firstly suggested by Burnham in 1975. Our theoretical computations provide a more general model of the first hydrolysis steps that could help to understand experimental data and water speciation in glasses. -- Graphical Abstract: Reactivity within glass bulk: structures obtained after hydrolyses reactions (endothermic and exothermic processes) and mechanisms involving Si-OH, Al-OH, Si-OH-Al groups within aluminosilicates glasses (through ab initio molecular dynamics): formation of the Si-OH-Al entity coupled with an H exchange-Frederic Bouyer and Gregory Geneste. Display Omitted

  4. Structural implications of water dissolution in haplogranitic glasses from NMR spectroscopy: influence of total water content and mixed alkali effect

    NASA Astrophysics Data System (ADS)

    Schmidt, B. C.; Riemer, T.; Kohn, S. C.; Holtz, F.; Dupree, R.

    2001-09-01

    To study the effects of total water content and alkali substitution on the structure of aluminosilicate glasses, two series of glasses belonging to the ternary system Quartz (Qz)-Albite (Ab)-Orthoclase (Or) were synthesized and investigated with nuclear magnetic resonance (NMR) spectroscopy. Series I consisted of seven glasses with normative composition Ab 39Or 32Qz 29 (AOQ) and water contents ranging from 0 to 6 wt%. Series II consisted of dry and hydrous glasses (˜2.0 wt% H 2O) with five compositions along the join Qz 37Ab 63-Qz 34Or 66 (AQ-OQ) varying the alkali content (Na/K) at constant Si/Al ratio. All glasses were investigated with 1H, 23Na, 27Al and 29Si magic angle spinning (MAS) NMR. 29Si MAS spectra of AOQ glasses showed no change upon hydration, suggesting little variation of the Si environments although the large linewidth of the 29Si signal may hide the presence of some Si Q 3-OH. The isotropic chemical shift (δ iso) of 27Al showed no change upon hydration, regardless of the amount of dissolved water. The 27Al mean quadrupolar coupling constant (C q) decreased with increasing water content, indicating a general increase of symmetry of the charge distribution around Al, which suggests the absence of significant amounts of Al Q 3-OH. Nonetheless, the evolution of C q upon hydration suggests a correlation with OH concentration in the quenched glass. The evolution of 23Na isotropic chemical shifts upon hydration appears to be correlated with total water content or with the concentration of dissolved H 2O molecules. In general, the NMR data are consistent with the water solubility model of Kohn et al. (1989), involving the exchange of charge balancing cations by protons. However, in addition to the presence of molecular water, 1H-NMR results showed at least two types of OH groups of which one may be related to Al-OH. Although the small intensity of this signal indicates that only a minor fraction of OH groups is present in this species, it demonstrates

  5. Effect of water on the heat capacity of polymerized aluminosilicate glasses and melts

    NASA Astrophysics Data System (ADS)

    Bouhifd, M. Ali; Whittington, Alan; Roux, Jacques; Richet, Pascal

    2006-02-01

    The effect of water on heat capacity has been determined for four series of hydrated synthetic aluminosilicate glasses and supercooled liquids close to albite, phonolite, trachyte, and leucogranite compositions. Heat capacities were measured at atmospheric pressure by differential scanning calorimetry for water contents between 0 and 4.9 wt % from 300 K to about 100 K above the glass transition temperature ( Tg). The partial molar heat capacity of water in polymerized aluminosilicate glasses, which can be considered as independent of composition, is =-122.319+341.631×10-3T+63.4426×105/T2 (J/mol K). In liquids containing at least 1 wt % H 2O, the partial molar heat capacity of water is about 85 J/mol K. From speciation data, the effects of water as hydroxyl groups and as molecular water have tentatively been estimated, with partial molar heat capacities of 153 ± 18 and 41 ± 14 J/mol K, respectively. In all cases, water strongly increases the configurational heat capacity at Tg and exerts a marked depressing effect on Tg, in close agreement with the results of viscosity experiments on the same series of glasses. Consistent with the Adam and Gibbs theory of relaxation processes, the departure of the viscosity of hydrous melts from Arrhenian variations correlates with the magnitude of configurational heat capacities.

  6. Temperature dependence of elastic properties in alkali borate binary glasses

    NASA Astrophysics Data System (ADS)

    Kawashima, Mitsuru; Matsuda, Yu; Kojima, Seiji

    2011-05-01

    The elastic properties of alkali borate glasses, xM 2O·(100 - x)B 2O 3 (M = Li, Na, K, Rb, Cs, x = 14, 28), have been investigated by Brillouin scattering spectroscopy from room temperature up to 1100 °C. Above the glass transition temperature, Tg, the longitudinal sound velocity, VL, decreases markedly on heating. Such significant changes of the elastic properties result from the breakdown of the glass network above Tg. Alkali borate family with the same x shows the similar behavior in the temperature variations of VL up to around Tg. The absorption coefficient, αL, increases gradually above Tg. With the increase of the size of an alkali ion, the slope of VL just above Tg decreases. Since the fragility is related to the slope, the present results suggest that the fragility of alkali borate glasses increases as the size of alkali ion decreases. Such an alkali dependence of the fragility is discussed on the basis of the fluctuation of the boron coordination number.

  7. Influence of aluminum speciation on the stability of aluminosilicate glasses against crystallization

    NASA Astrophysics Data System (ADS)

    Zheng, Qiuju; Smedskjaer, Morten M.; Youngman, Randall E.; Potuzak, Marcel; Mauro, John C.; Yue, Yuanzheng

    2012-07-01

    In this letter, we investigate the correlation between glass microstructure and glass stability (GS) in soda lime aluminosilicates. We find a loss of GS (i.e., an onset of crystallization) in the glasses above a critical concentration of Al2O3 when heating at the standard rate of 20 K/min. This loss in GS may be attributed to formation of five-fold coordinated Al species when [Al2O3]/[Na2O] > 1. The primary crystalline phase is identified as nepheline, in which Al exists in four-fold coordination. This implies that the five-fold coordinated Al is energetically less stable compared to Al in a tetrahedral environment.

  8. Evidence of two erbium sites in standard aluminosilicate glass for EDFA.

    PubMed

    Peretti, R; Jurdyc, A M; Jacquier, B; Burov, E; Pastouret, A

    2010-09-27

    Site distributions of Er(3+)-doped aluminosilicate preforms of standard EDFA were studied by the low temperature Resonant Fluorescence Line Narrowing (RFLN) spectroscopy. Two erbium concentration samples with the same glass base were investigated. At very low erbium concentration, two classes of sites were identified, related to the number of AlO(6) octahedral linked by two oxygen edge-sharing to Er(3+) in the coordination sphere. As erbium concentration is increased, the high AlO(6) coordinated class of sites is smeared out by the optical response of the one AlO(6) coordinated class of sites. PMID:20940961

  9. Structure and properties of sodium aluminosilicate glasses from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Xiang, Ye; Du, Jincheng; Smedskjaer, Morten M.; Mauro, John C.

    2013-07-01

    Addition of alumina to sodium silicate glasses considerably improves the mechanical properties and chemical durability and changes other properties such as ionic conductivity and melt viscosity. As a result, aluminosilicate glasses find wide industrial and technological applications including the recent Corning® Gorilla® Glass. In this paper, the structures of sodium aluminosilicate glasses with a wide range of Al/Na ratios (from 1.5 to 0.6) have been studied using classical molecular dynamics simulations in a system containing around 3000 atoms, with the aim to understand the structural role of aluminum as a function of chemical composition in these glasses. The short- and medium-range structures such as aluminum coordination, bond angle distribution around cations, Qn distribution (n bridging oxygen per network forming tetrahedron), and ring size distribution have been systematically studied. In addition, the mechanical properties including bulk, shear, and Young's moduli have been calculated and compared with experimental data. It is found that aluminum ions are mainly four-fold coordinated in peralkaline compositions (Al/Na < 1) and form an integral part of the rigid silicon-oxygen glass network. In peraluminous compositions (Al/Na > 1), small amounts of five-fold coordinated aluminum ions are present while the concentration of six-fold coordinated aluminum is negligible. Oxygen triclusters are also found to be present in peraluminous compositions, and their concentration increases with increasing Al/Na ratio. The calculated bulk, shear, and Young's moduli were found to increase with increasing Al/Na ratio, in good agreement with experimental data.

  10. Striking role of non-bridging oxygen on glass transition temperature of calcium aluminosilicate glass-formers

    SciTech Connect

    Bouhadja, M.; Jakse, N.; Pasturel, A.

    2014-06-21

    Molecular dynamics simulations are used to study the structural and dynamic properties of calcium aluminosilicate, (CaO-Al{sub 2}O{sub 3}){sub 1−x}(SiO{sub 2}){sub x}, glass formers along three joins, namely, R = 1, 1.57, and 3, in which the silica content x can vary from 0 to 1. For all compositions, we determined the glass-transition temperature, the abundances of the non-bridging oxygen, triclusters, and AlO{sub 5} structural units, as well as the fragility from the temperature evolution of the α-relaxation times. We clearly evidence the role played by the non-bridging oxygen linked either to Al atoms or Si atoms in the evolution of the glass-transition temperature as well as of the fragility as a function of silica content along the three joins.

  11. Alkali-lead-iron phosphate glass and associated method

    DOEpatents

    Boatner, L.A.; Sales, B.C.; Franco, S.C.S.

    1994-03-29

    A glass composition and method of preparation utilizes a mixture consisting of phosphorus oxide within the range of about 40 to 49 molar percent, lead oxide within the range of about 10 to 25 molar percent, iron oxide within the range of about 10 to 17 molar percent and an alkali oxide within the range of about 23 to 30 molar percent. The glass resulting from the melting and subsequent solidifying of the mixture possesses a high degree of durability and a coefficient of thermal expansion as high as that of any of a number of metals. Such features render this glass highly desirable in glass-to-metal seal applications. 6 figures.

  12. Alkali-lead-iron phosphate glass and associated method

    DOEpatents

    Boatner, Lynn A.; Sales, Brian C.; Franco, Sofia C. S.

    1994-01-01

    A glass composition and method of preparation utilizes a mixture consisting of phosphorus oxide within the range of about 40 to 49 molar percent, lead oxide within the range of about 10 to 25 molar percent, iron oxide within the range of about 10 to 17 molar percent and an alkali oxide within the range of about 23 to 30 molar percent. The glass resulting from the melting and subsequent solidifying of the mixture possesses a high degree of durability and a coefficient of thermal expansion as high as that of any of a number of metals. Such features render this glass highly desirable in glass-to-metal seal applications.

  13. Optical Properties of Tm(3+) Ions in Alkali Germanate Glass

    NASA Technical Reports Server (NTRS)

    Walsh, Brian M.; Barnes, Norman P.; Reichle, Donald J.; Jiang, Shibin

    2006-01-01

    Tm-doped alkali germanate glass is investigated for use as a laser material. Spectroscopic investigations of bulk Tm-doped germanate glass are reported for the absorption, emission and luminescence decay. Tm:germanate shows promise as a fiber laser when pumped with 0.792 m diodes because of low phonon energies. Spectroscopic analysis indicates low nonradiative quenching and pulsed laser performance studies confirm this prediction by showing a quantum efficiency of 1.69.

  14. Interpretation of the IR spectra of alkali borate glasses

    SciTech Connect

    Chekhovskii, V.G.

    1985-11-01

    This paper describes methods of interpretation of the IR spectra of alkali borate glasses. In view of the difficulties which are encountered in a strict interpretation of the IR spectra of crystalline oxygen-containing compounds with complex anions, semiempirical methods of interpretation are commonly used. The existence of glasses of groups with an atomic (ionic) arrangement close to that in the crystalline compounds makes it possible to a certain extent to use the spectra of crystalline compounds in the interpretation of the IR spectra of glasses. The alkali borate glass systems were chosen for this study because the information on their structure is the most detailed by comparison with other borate glasses. IR spectrospcopy showed that the spectral regions in which fundamental asymmetrical stretching vibrations in BO/sub 3/ and BO/sub 4/ polyhedra occur, in most cases, are fairly clearly defined independently of the combined or separate presence of these polyhedra. It is proposed that the bands in the IR spectra of sodium and lithium borate glasses be assigned to vibrations mostly localized on specific fragments of polyborate groups present in the glasses. The data from IR spectroscopy confirms that tetraborate groups are present in lithium borate glasses.

  15. Vibrational spectra and the structure of alkali borate glasses

    SciTech Connect

    Kolesova, V.A.

    1986-11-01

    This paper presents systematic data on the IR-absorption spectra of lithium borate glasses. Lithium borate glasses were synthesized from Li/sub 2/CO/sub 3/ and H/sub 3/BO/sub 3/ in Pt crucibles at temperatures from 800 to 1050 C. It was possible in the lithium borate system to obtain glasses continuing significantly more M/sub 2/O than the glasses in the sodium or potassium borate system. An analysis of the data on Raman spectra of alkali borate glasses suggests that the addition of M/sub 2/O to a B/sub 2/O/sub 3/ glass produces network disorder, the replacement of the boroxyl rings by rings of another configuration and the formation of BO/sub 4/ tetrahedra.

  16. Synthesis and studies on microhardness of alkali zinc borate glasses

    NASA Astrophysics Data System (ADS)

    Subhashini, Bhattacharya, Soumalya; Shashikala, H. D.; Udayashankar, N. K.

    2014-04-01

    The mixed alkali effect on zinc borate glasses have been reported. The glass systems of nominal composition 10Zn+xLi2O+yNa2O+80B2O3 (x = y = 0, 5, 10, 15 mol%) were prepared using standard melt quenching method. The structural, physical and mechanical properties of the samples have been studied using X-ray diffraction(XRD), density measurement and Vickers hardness measurement, respectively. A consistent increase in the density was observed, which explains the role of the modifiers (Li2O and Na2O) in the network modification of borate structure. The molar volume is decreasing linearly with the alkali concentration, which is attributed to the conversion of tetrahedral boron (BO4/2)- into (BO3/2)-. The microhardness studies reveals the anisotropy nature of the material. It further confirms that the samples belong to hard glass category.

  17. Contributions to the mixed-alkali effect in molecular dynamics simulations of alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    Lammert, Heiko; Heuer, Andreas

    2005-12-01

    The mixed-alkali effect in the cation dynamics in silicate glasses is analyzed via molecular dynamics simulations. Observations suggest a description of the dynamics in terms of stable sites mostly specific to one ionic species. As main contributions to the mixed-alkali slow down longer residence times and an increased probability of correlated backjumps are identified. The slow down is related to the limited accessibility of foreign sites. The mismatch experienced in a foreign site is stronger and more retarding for the larger ions, the smaller ions can be temporarily accommodated. Also correlations between unlike as well as like cations are demonstrated that support cooperative behavior.

  18. Synthesis and Properties of a Barium Aluminosilicate Solid Oxide Fuel Cell Glass-Ceramic Sealant

    SciTech Connect

    Meinhardt, Kerry D.; Kim, Dong-Sang; Chou, Y. S.; Weil, K. Scott

    2008-07-15

    A series of barium aluminosilicate glasses modified with CaO and B2O3, were prepared and evaluated with respect to their suitability in sealing planar solid oxide fuel cells (SOFCs). At a target operating temperature of 750ºC, the long-term CTE of one particular composition (35 mol% BaO, 15 mol% CaO, 10 mol% B2O3, 5 mol% Al2O3, bal. SiO2) was found to be particularly stable, due to devitrification to a mixture of glass and ceramic phases. This sealant composition exhibits minimal chemical interaction with the yttria-stabilized zirconia electrolyte, yet forms a strong bond with this material. Interactions with metal components were found to be more extensive and depended on the composition of the metal oxide scale that formed during sealing. Generally alumina-scale formers exhibited a more compact reaction zone with the glass than chromia-scale forming alloys. Mechanical measurements conducted on the bulk glass-ceramic and on seals formed using these materials indicate that the sealant is anticipated to display adequate long-term strength for most conventional stationary SOFC applications.

  19. Synthesis and properties of a barium aluminosilicate solid oxide fuel cell glass-ceramic sealant

    NASA Astrophysics Data System (ADS)

    Meinhardt, K. D.; Kim, D.-S.; Chou, Y.-S.; Weil, K. S.

    A series of barium aluminosilicate glasses modified with CaO and B 2O 3 were prepared and evaluated with respect to their suitability in sealing planar solid oxide fuel cells (SOFCs). At a target operating temperature of 750 °C, the long-term coefficient of thermal expansion (CTE) of one particular composition (35 mol% BaO, 15 mol% CaO, 10 mol% B 2O 3, 5 mol% Al 2O 3, and bal. SiO 2) was found to be particularly stable, due to devitrification to a mixture of glass and ceramic phases. This sealant composition exhibits minimal chemical interaction with the yttria-stabilized zirconia electrolyte, yet forms a strong bond with this material. Interactions with metal components were found to be more extensive and depended on the composition of the metal oxide scale that formed during sealing. Generally alumina-scale formers exhibited a more compact reaction zone with the glass than chromia-scale forming alloys. Mechanical measurements conducted on the bulk glass-ceramic and on seals formed using these materials indicate that the sealant is anticipated to display adequate long-term strength for most conventional stationary SOFC applications.

  20. The role of Al3+ on rheology and structural changes in sodium silicate and aluminosilicate glasses and melts

    NASA Astrophysics Data System (ADS)

    Le Losq, Charles; Neuville, Daniel R.; Florian, Pierre; Henderson, Grant S.; Massiot, Dominique

    2014-02-01

    Because of their importance in both the geosciences and the glass-making industry, alkali aluminosilicate melts have been the focal point of many past studies, but despite progress many problems remain unresolved, such as the complex behaviour of the thermodynamic properties of aluminium-rich alkali silicate melts. This paper presents a study of Na2O-Al2O3-SiO2 glasses and melts, containing 75 mol% SiO2 and different Al/(Al + Na) ratios. Their structure has been investigated by using Raman spectroscopy, as well as, 23Na, 27Al and 29Si 1D MAS NMR spectroscopy. Results confirm the role change of Na+ cations from network modifier to charge compensator in the presence of Al3+ ions. In addition, polymerization increases with increase of the Al/(Al + Na) ratio. These structural changes explain the observed variations in the viscosity of these melts. The viscosity data in turn allow us to calculate the configurational entropy of melts at the glass transition temperature [the Sconf(Tg)]. The variations of the Sconf(Tg) are strongly nonlinear, with sharp increases and decreases depending on the Al/(Al + Na) ratio. More importantly, a strong increase of the Sconf(Tg) is observed when a few Al2O3 is added to sodium silicate melt. A strong decrease is observed after crossing the tectosilicate join, when Al/(Al + Na) > 0.5 and when Al3+ ions are present in fivefold coordination, Al[5], in the glass. Furthermore, in situ27Al NMR spectra of the peraluminous melt show a clear increase of the Al[5] concentration with increasing temperature. When considered in combination with melt fragility and heat capacity, our data demonstrate that Al[5] is clearly a transient unit at high temperature in highly polymerized tectosilicate and peraluminous melts. However, when present in glasses, Al[5] increases the stability of the aluminosilicate network, hence the Tg of glasses. This could be explained by the ability of Al[5] to carry threefold coordinated oxygen atoms in its first coordination

  1. Network cation coordination in aluminoborosilicate and Mg- aluminosilicate glasses: pressure effects in recovered structural changes and densification

    NASA Astrophysics Data System (ADS)

    Bista, S.; Stebbins, J. F.; Sisson, T. W.; Hankins, W. B.

    2015-12-01

    In this study, we compare the aluminum and boron coordination of glass samples recovered from piston-cylinder experiments carried out at 1 to 3 GPa and near to their ambient glass transition temperature (Tg), which we have found gives a more accurate picture of high pressure structural changes than experiments involving quenching from above the liquidus, as large pressure drops can occur in the latter. Aluminoborosilicate glasses with excess modifier (Ca, La and Y- aluminoborosilicate) quenched from melts at 1-3 GPa were studied with B-11 and Al-27 MAS NMR to assess relative effects on two different network cations. Structural changes in the Y-aluminoborosilicate are dramatic, going from mostly AlO4 at low pressure to mostly AlO5 and AlO6 at 3 GPa. Large increases in BO4 (vs. BO3) are also seen. Mg-aluminosilicate glasses, both tectosilicate (Mg2Al4Si6O20) and with excess modifier composition (Mg3Al2Si6O18) quenched from melts at 1-3 GPa pressure were studied with Al-27 MAS NMR. In contrast to our previous study (Bista et al., Am. Min., in press) of jadeite glass, where only 0.5% of fivefold aluminum was seen in glass recovered from 3 GPa, five and six fold aluminum species increase significantly with increasing pressure in both Mg aluminosilicate glass compositions studied here. We observe that the tectosilicate Mg aluminosilicate glass has more higher coordinated aluminum than the excess modifier containing composition in the pressure range in our study. In the previous study (Bista et al., in press) of jadeite and calcium aluminosilicate (Ca3Al2Si6O18) glasses, 6-8% densification was observed in glasses recovered from 3 GPa. In this study of Mg aluminosilicate glasses, we observe 12% densification in glasses recovered from 3 GPa. Both types of observation confirm that structural and density changes with pressure are enhanced by higher field strength modifier cations, and will be especially important in Mg- and Fe-rich mantle melts.

  2. Steam Reforming Technology Demonstration for Conversion of DOE Sodium-Bearing Tank Wastes at Idaho National Laboratory into a Leach-Resistant Alkali Aluminosilicate Waste Form

    SciTech Connect

    Ryan, K.; Bradley Mason, J.; Evans, B.; Vora, V.; Olson, A.

    2008-07-01

    The patented THOR{sup R} fluidized-bed steam reforming (FBSR) technology was selected by the U.S. Department of Energy (DOE) for treatment of sodium-bearing waste (SBW) in the Integrated Waste Treatment Unit (IWTU), currently under construction at the Idaho National Laboratory (INL) Site.1 SBW is an acidic waste created primarily from cleanup of the fuel reprocessing equipment at the Idaho Nuclear Technology and Engineering Center (INTEC) at the INL. The SBW contains high concentrations of nitric acid, and alkali and aluminum nitrates, along with many other inorganic compounds, including substantial levels of radionuclides. As part of the implementation of the THOR{sup R} process at INTEC, an engineering-scale technology demonstration (ESTD) was conducted using a specially designed pilot plant located at Hazen Research, Inc. in Golden Colorado. This ESTD confirmed the efficacy of the THOR{sup R} FBSR process to convert the SBW into a granular carbonate-based waste form suitable for disposal at the Waste Isolation Pilot Plant (WIPP). DOE authorized, as a risk reduction measure, the performance of an additional ESTD to demonstrate the production of an insoluble mineralized product, in the event that an alternate disposition path is required. The additional ESTD was conducted at the Hazen Research facility using the THOR{sup R} process and the same SBW simulant employed previously. An alkali aluminosilicate mineral product was produced that exhibited excellent leach resistance and chemical durability. The demonstration established general system operating parameters for a full-scale facility; provided process off-gas data that confirmed operation within regulatory limits; determined that the mineralized product exhibits superior leach resistance and durability, compared to Environmental Assessment (EA) and Low-activity Reference Material (LRM) glasses, as indicated by the Product Consistency Test (PCT); ascertained that Cs and Re (a surrogate for Tc) were non

  3. In situ structural analysis of calcium aluminosilicate glasses under high pressure.

    PubMed

    Muniz, R F; de Ligny, D; Martinet, C; Sandrini, M; Medina, A N; Rohling, J H; Baesso, M L; Lima, S M; Andrade, L H C; Guyot, Y

    2016-08-10

    In situ micro-Raman spectroscopy was used to investigate the structural evolution of OH(-)-free calcium aluminosilicate glasses, under high pressure and at room temperature. Evaluation was made of the role of the SiO2 concentration in percalcic join systems, for Al/(Al  +  Si) in the approximate range from 0.9 to 0.2. Under high pressure, the intensity of the main band related to the bending mode of bridging oxygen ([Formula: see text][T-O-T], where T  =  Si or Al) decreased gradually, suggesting that the bonds were severely altered or even destroyed. In Si-rich glasses, compression induced a transformation of Q (n) species to Q (n-1). In the case of Al-rich glass, the Al in the smallest Q (n) units evolved from tetrahedral to higher-coordinated Al (([5])Al and ([6])Al). Permanent structural changes were observed in samples recovered from the highest pressure of around 15 GPa and, particularly for Si-rich samples, the recovered structure showed an increase of three-membered rings in the Si/Al tetrahedral network. PMID:27300313

  4. In situ structural analysis of calcium aluminosilicate glasses under high pressure

    NASA Astrophysics Data System (ADS)

    Muniz, R. F.; de Ligny, D.; Martinet, C.; Sandrini, M.; Medina, A. N.; Rohling, J. H.; Baesso, M. L.; Lima, S. M.; Andrade, L. H. C.; Guyot, Y.

    2016-08-01

    In situ micro-Raman spectroscopy was used to investigate the structural evolution of OH‑-free calcium aluminosilicate glasses, under high pressure and at room temperature. Evaluation was made of the role of the SiO2 concentration in percalcic join systems, for Al/(Al  +  Si) in the approximate range from 0.9 to 0.2. Under high pressure, the intensity of the main band related to the bending mode of bridging oxygen ({ν\\text{B}} [T-O-T], where T  =  Si or Al) decreased gradually, suggesting that the bonds were severely altered or even destroyed. In Si-rich glasses, compression induced a transformation of Q n species to Q n‑1. In the case of Al-rich glass, the Al in the smallest Q n units evolved from tetrahedral to higher-coordinated Al ([5]Al and [6]Al). Permanent structural changes were observed in samples recovered from the highest pressure of around 15 GPa and, particularly for Si-rich samples, the recovered structure showed an increase of three-membered rings in the Si/Al tetrahedral network.

  5. Mixed alkali effect in glasses containing MnO2

    NASA Astrophysics Data System (ADS)

    Reddy, M. Sudhakara; Rajiv, Asha; Veeranna Gowda, V. C.; Chakradhar, R. P. S.; Reddy, C. Narayana

    2013-02-01

    Glass systems of the composition xLi2O-(25-x)K2O-70(0.4ZnO+0.6P2O5)+5MnO2 (x = 4,8,12,16 and 20 mol %) have been prepared by melt quenching technique. The thermal and mechanical properties of the glasses have been evaluated as a function of mixed alkali content. Glass transition temperature and Vickers's hardness of the glasses show a pronounced deviation from linearity at 12 mol% Li2O. Theoretically estimated elastic moduli of the glasses show small positive deviations from linearity. MAE in these properties has been attributed to the localized changes in the glass network. The absorption spectra of Mn2+ ions in these glasses showed strong broad absorption band at 514 nm corresponding to the transition 6A1g(S)→4T1g(G), characteristic of manganese ions in octahedral symmetry. The fundamental absorption edge in UV region is used to study the optical transitions and electronic band structure. From UV absorption edge, optical band gap energies have been evaluated. Band gap energies of the glasses have exhibited MAE and shows minimum value for 12 mol% Li2O glass.

  6. Optical response of alkali metal atoms confined in nanoporous glass

    SciTech Connect

    Burchianti, A; Marinelli, C; Mariotti, E; Bogi, A; Marmugi, L; Giomi, S; Maccari, M; Veronesi, S; Moi, L

    2014-03-28

    We study the influence of optical radiation on adsorption and desorption processes of alkali metal atoms confined in nanoporous glass matrices. Exposure of the sample to near-IR or visible light changes the atomic distribution inside the glass nanopores, forcing the entire system to evolve towards a different state. This effect, due to both atomic photodesorption and confinement, causes the growth and evaporation of metastable nanoparticles. It is shown that, by a proper choice of light characteristics and pore size, these processes can be controlled and tailored, thus opening new perspectives for fabrication of nanostructured surfaces. (nanoobjects)

  7. Aluminosilicate melts and glasses at 1 to 3 GPa: temperature and pressure effects on recovered structural and density changes

    NASA Astrophysics Data System (ADS)

    Bista, S.; Stebbins, J. F.; Hankins, B.; Sisson, T. W.

    2013-12-01

    The effects of pressure on aluminosilicate melt and glass structure have been studied by both in-situ methods and by quenching and recovering glasses from high pressure and temperature. Significant increases in the coordination number of Al are now well known from the pressure range of 6-10 GPa. New results show that even at shallower mantle pressures of 1-3 GPa, typical aluminosilicate melts have significant concentrations of aluminum cations with coordination numbers greater than 4, with up to 10's of percents of AlO5 and AlO6. Here, we compare the densities and Al coordinations of glass samples recovered from piston-cylinder experiments carried out at 1 to 3 GPa and different temperatures. Samples of two different compositions (Ca3Al2Si6O18 and Na2Si3O7 with 0.5% Al2O3) were compressed and held at temperatures ranging from near to their ambient glass transitions (Tg) up to temperatures above the liquidus. Our 2 GPa sodium aluminosilicate and calcium aluminosilicate glasses quenched from near to Tg show about 5 and 6 percent recovered densification, respectively. In both compositions, samples that were quenched from above the melting point showed substantially lower recovered density and lower Al coordination number compared to the samples that were held near to Tg. For example, sodium aluminosilicate glass quenched from 510°C (near to Tg) had 70% more AlO5 than samples from 1200°C. Based on the measurement of actual cooling rates, fictive temperature differences for the glasses from these two extreme temperatures are not large enough to account for this apparent loss in density and Al-coordination during quench. The most likely cause for these differences is therefore probably the pressure drop during cooling from temperatures above liquidus, as the pressure medium does not respond quickly enough to the thermal contraction of the liquid and furnace parts to remain isobaric. Results from previous high T and P quenching studies thus give only minimum estimates

  8. The role of Al3+ on rheology and structural changes in sodium silicate and aluminosilicate glasses and melts

    NASA Astrophysics Data System (ADS)

    Le Losq, Charles; Neuville, Daniel R.; Florian, Pierre; Henderson, Grant S.; Massiot, Dominique

    2014-02-01

    Because of their importance in both the geosciences and the glass-making industry, alkali aluminosilicate melts have been the focal point of many past studies, but despite progress many problems remain unresolved, such as the complex behaviour of the thermodynamic properties of aluminium-rich alkali silicate melts. This paper presents a study of Na2O-Al2O3-SiO2 glasses and melts, containing 75 mol% SiO2 and different Al/(Al + Na) ratios. Their structure has been investigated by using Raman spectroscopy, as well as, 23Na, 27Al and 29Si 1D MAS NMR spectroscopy. Results confirm the role change of Na+ cations from network modifier to charge compensator in the presence of Al3+ ions. In addition, polymerization increases with increase of the Al/(Al + Na) ratio. These structural changes explain the observed variations in the viscosity of these melts. The viscosity data in turn allow us to calculate the configurational entropy of melts at the glass transition temperature [the Sconf(Tg)]. The variations of the Sconf(Tg) are strongly nonlinear, with sharp increases and decreases depending on the Al/(Al + Na) ratio. More importantly, a strong increase of the Sconf(Tg) is observed when a few Al2O3 is added to sodium silicate melt. A strong decrease is observed after crossing the tectosilicate join, when Al/(Al + Na) > 0.5 and when Al3+ ions are present in fivefold coordination, Al[5], in the glass. Furthermore, in situ27Al NMR spectra of the peraluminous melt show a clear increase of the Al[5] concentration with increasing temperature. When considered in combination with melt fragility and heat capacity, our data demonstrate that Al[5] is clearly a transient unit at high temperature in highly polymerized tectosilicate and peraluminous melts. However, when present in glasses, Al[5] increases the stability of the aluminosilicate network, hence the Tg of glasses. This could be explained by the ability of Al[5] to carry threefold coordinated oxygen atoms in its first coordination

  9. Synthesis and studies on microhardness of alkali zinc borate glasses

    SciTech Connect

    Subhashini, Bhattacharya, Soumalya Shashikala, H. D. Udayashankar, N. K.

    2014-04-24

    The mixed alkali effect on zinc borate glasses have been reported. The glass systems of nominal composition 10Zn+xLi{sub 2}O+yNa{sub 2}O+80B{sub 2}O{sub 3} (x = y = 0, 5, 10, 15 mol%) were prepared using standard melt quenching method. The structural, physical and mechanical properties of the samples have been studied using X-ray diffraction(XRD), density measurement and Vickers hardness measurement, respectively. A consistent increase in the density was observed, which explains the role of the modifiers (Li{sub 2}O and Na{sub 2}O) in the network modification of borate structure. The molar volume is decreasing linearly with the alkali concentration, which is attributed to the conversion of tetrahedral boron (BO{sub 4/2}){sup −} into (BO{sub 3/2}){sup −}. The microhardness studies reveals the anisotropy nature of the material. It further confirms that the samples belong to hard glass category.

  10. Intrinsic Impurities in Glass Alkali-Vapor Cells

    NASA Astrophysics Data System (ADS)

    Patton, B.; Ishikawa, K.; Jau, Y.-Y.; Happer, W.

    2007-07-01

    We report NMR measurements of metallic Cs133 in glass cells. The solid-liquid phase transition was studied by observing the NMR peaks arising from these two phases; surprisingly, many cells yielded two additional NMR peaks below the melting point. We attribute these signals to two distinct impurities which can dissolve in the liquid alkali metal and affect its chemical shift. Intentional contamination of cesium cells with O2 confirms this hypothesis for one peak. The other contaminant remains unknown but can appear in evacuated cells. Similar effects have been seen in Rb87 cells.

  11. Modeling the Structure of Complex Aluminosilicate Glasses: The Effect of Zinc Addition.

    PubMed

    Bernasconi, Andrea; Dapiaggi, Monica; Pavese, Alessandro; Agostini, Giovanni; Bernasconi, Maurizio; Bowron, Daniel T

    2016-03-10

    An empirical potential structure refinement of neutron and X-ray diffraction data combined with extended absorption fine structure evidence has been applied to the investigation of two distinct sets of complex aluminosilicate glasses containing different quantities of zinc. Data come from (i) neutron and X-ray total scattering experiments, which have been performed at the ISIS neutron spallation source (SANDALS beamline) and at the European Synchrotron Radiation Facility (ID11 beamline), and (ii) EXAFS experiments which have been performed at the European Synchrotron Radiation Facility (BM23 beamline). By careful examination of the modeled ensemble of atoms, a wide range of structural information has been extracted: coordination numbers, bond distances, cluster sizes, type of oxygen sharing, and the preference of large cations to adopt a charge-compensating role. The first series of glasses, which is characterized by a fixed network modifier element content (i.e., Na), shows how the introduction of Zn at the expense of Si and Al network forming elements does not significantly alter the polymerization degree, as a result of its dominant 4-fold coordination. In the case of the second series, which is characterized by fixed network forming element content (i.e., Si and Al), it is shown how the replacement of a network modifier element (i.e., Ca) with the introduction of Zn does not change the propensity of Zn to be mainly 4-fold coordinated by promoting the network. Where appropriate the experimental results have been compared with classical theoretical approaches such as stoichiometric models based on Zachariasen's rules and computational routines. PMID:26848740

  12. Mixed alkali effect on the spectroscopic properties of alkali-alkaline earth oxide borate glasses

    NASA Astrophysics Data System (ADS)

    Srinivas, G.; Ramesh, B.; Shareefuddin, Md.; Chary, M. N.; Sayanna, R.

    2016-05-01

    The mixed alkali and alkaline earth oxide borate glass with the composition xK2O - (25-x) Li2O-12.5BaO-12.5MgO-50B2O3 (x = 0, 5, 10, 15, 20 and 25mol %) and doped with 1mol% CuO were prepared by the melt quenching technique. From the optical absorption spectra the optical band gap, electronic polarizability(α02-), interaction parameter (A), theoretical and experimental optical basicity (Λ) values were evaluated. From the Electron Paramagnetic Resonance (EPR) spectral data the number of spins (N) and susceptibility (χ) were evaluated. The values of (α02-), and (Λ) increases with increasing of K2O content and electronic polarizability and interaction parameter show opposite behaviuor which may be due to the creation of non-bridging oxygens and expansion of borate network. The reciprocal of susceptibility (1/χ) and spin concentration (N) as a function of K2O content, varied nonlinearly which may be due to creation of non-bridging oxygens in the present glass system. This may be attributed to mixed alkali effect (MAE).

  13. Bonding Preferences of Non-Bridging Oxygens in Calcium Aluminosilicate Glass: Evidence from O-17 MAS and 3QMAS NMR on Calcium Aluminate Glass

    NASA Astrophysics Data System (ADS)

    Allwardt, J. R.; Lee, S.; Stebbins, J.

    2001-12-01

    Non-bridging oxygens (NBO's) play a significant role in the thermodynamic and transport properties in glasses and silicate melts. Previous oxygen-17 (O-17) triple quantum magic angle spinning (3QMAS NMR) data have shown the presence of NBO's in several calcium aluminosilicate (CAS) glasses on the CaAl2O4-SiO2 join (Stebbins and Xu 1997). The observed chemical shifts of these glasses are similar to those for the NBO in calcium silicate glasses (Stebbins et al. 1997 and Stebbins et al 1999); however, a recent O-17 MAS NMR study of crystalline CaAl2O4 showed that the NBO peak in an associated impurity phase is shifted to a higher frequency by 30 to 40 ppm from that of CAS and Ca-silicate glasses (Stebbins et al. in press). This finding suggests that Si is the preferred network cation for NBO's in aluminosilicate glasses and melts at the glass transition temperature. The preference for Si over that of Al as the network cation host for NBO's has also been suggested by Raman and other spectroscopic techniques (Mysen 1988). To investigate this apparent preference for Si-NBO, O-17 3QMAS and MAS experiments were conducted to examine the location of the NBO peak in the spectra of a calcium aluminate glass. Since the CaAl2O4 glass is difficult to make by conventional cooling methods, the binary eutectic composition (63CaO-37Al2O3) was chosen. The resulting O-17 MAS spectrum shows an intense, relatively narrow peak centered at 72 ppm, which nearly coincides with the peak location and width of the Al-O-Al peak in the crystalline Ca-aluminates (Stebbins et al. in press.) (70 ppm). There is a broader, less intense peak centered at 155 ppm that is assigned to the Al-NBO peak. This peak is in approximately the same location as that for a Ca-aluminate phase reported by Stebbins et al. (in press) (137 ppm). In addition, our 3QMAS data show that the peak maximum of the NBO in the Ca-aluminate (-85 and 150 ppm in isotropic and MAS dimensions, respectively) differs significantly from

  14. Barium oxide, calcium oxide, magnesia, and alkali oxide free glass

    DOEpatents

    Lu, Peizhen Kathy; Mahapatra, Manoj Kumar

    2013-09-24

    A glass composition consisting essentially of about 10-45 mole percent of SrO; about 35-75 mole percent SiO.sub.2; one or more compounds from the group of compounds consisting of La.sub.2O.sub.3, Al.sub.2O.sub.3, B.sub.2O.sub.3, and Ni; the La.sub.2O.sub.3 less than about 20 mole percent; the Al.sub.2O.sub.3 less than about 25 mole percent; the B.sub.2O.sub.3 less than about 15 mole percent; and the Ni less than about 5 mole percent. Preferably, the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide. Preferably, the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack. The SOFC stack comprises a plurality of SOFCs connected by one or more interconnect and manifold materials and sealed by the glass. Preferably, each SOFC comprises an anode, a cathode, and a solid electrolyte.

  15. Molecular dynamics simulation of alkali borate glass using coordination dependent potential

    SciTech Connect

    Park, B.; Cormack, A.N.

    1997-12-31

    The structure of sodium borate glass was investigated by molecular dynamics simulation using coordination dependent potential model. The simulated alkali borate glass consists of basic units, BO{sub 3} triangle, BO{sub 4} tetrahedra and structural groups such as boroxol ring and triborate units. The coordination of boron is converted from 3 to 4 by adding alkali oxide.

  16. Reconciling data on the iron oxidation state of anhydrous and hydrous aluminosilicate glasses and melts: a polymeric approach.

    NASA Astrophysics Data System (ADS)

    Moretti, R.

    2003-04-01

    The oxidation state of iron has been the object of attentive investigations during the last four decades. A first class of investigation involves glasses synthesized under nominally anhydrous conditions at atmospheric pressure: interpretation of iron oxidation state Vs. composition has given rise to some contradictions in literature about the structural role played by this element in silicate melts. Controversies are particularly relevant in the case of divalent iron, as testified by many spectroscopic determinations. The second class of investigation concerns hydrous aluminosilicate glasses synthesized under different T-P conditions. Again, no unique redox pattern has been found so far in literature, the ferric to ferrous iron ratio depending in a complex fashion on composition, temperature, pressure and oxygen fugacity of synthesis. The present study aims at showing that it is possible to reconcile such data by accounting for the acid-base properties of studied melts/glasses in the framework of a polymeric approach based on the concept of optical basicity and considering water speciation. Useful insights may thus be given about the dissociation equilibria of water in aluminosilicate melts/glasses. It is concluded that the developed model may be usefully employed for studying the evolution of the oxidation state of degassing and erupting silicate melts, showing that redox variations may be more reasonably ascribed to the melt compositional control rather than to changes in oxygen fugacity during magma migration from depth to surface.

  17. Heat capacity, glass transition temperature, size of cooperatively rearranging regions, and network connectivity of sodium silicate and alkali borate glasses

    SciTech Connect

    Borisova, N.V.; Ushakov, V.M.; Shultz, M.M.

    1994-07-01

    The radius of cooperatively rearranging domains at the glass transition in sodium silicate glasses and the number of bridging oxygen atoms in these domains are assessed within the framework of the kinetic theory of thermal fluctuations. The tendencies of the heat capacity, T{sub g}, and the cooperative rearrangement scale with the alkali oxide concentration in sodium silicate and alkali borate glasses are compared. The points of similarity and distinctions between them are revealed.

  18. Spectroscopic properties of Er3+- and Yb3+-doped soda-lime silicate and aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    Hehlen, Markus P.; Cockroft, Nigel J.; Gosnell, T. R.; Bruce, Allan J.

    1997-10-01

    A spectroscopic investigation of an extensive series of Er3+-doped and Er3+,Yb3+-codoped soda-lime-silicate (SL) and aluminosilicate (AS) glasses is presented. Compared to SL glasses, 4f transitions in AS glasses show higher oscillator strengths, larger inhomogeneous broadening, and smaller crystal-field splittings of the respective excited-state multiplets. The Er3+ excited-state relaxation dynamics is adequately described by a combination of the Judd-Ofelt model and the energy-gap law. With the exception of 4I13/2, multiphonon relaxation is dominant for all excited states, making it possible to efficiently pump the 1.55 μm 4I13/2-->4I15/2 emission by excitation of 4I11/2 at around 980 nm. The absolute 4I13/2 luminescence quantum yield, for low 980-nm excitation density (~5 W/cm2), η, is ~0.9 at 0.4 mol % Er2O3 and drops to about 0.65 upon increasing Er2O3 to 1.2 mol %, indicating the onset of energy-transfer processes. Samples with high OH- impurity concentration suffer from significantly higher quenching of 4I13/2 luminescence at higher Er3+ concentrations. Energy migration to the minority of Er3+ ions coordinated to OH-, followed by efficient multiphonon relaxation accounts for this effect. At low excitation densities, the strong near-infrared absorption of Yb3+ in combination with efficient Yb-->Er energy transfer increases the 4I13/2 population density in Yb3+,Er3+-codoped samples by up to 2 orders of magnitude compared to equivalent samples without Yb3+. The dependence of η on Yb3+ codotation of 0.4 mol % Er2O3-doped samples predicts that a minimum of ~0.8 mol % Yb2O3 is required to achieve efficient sensitization of Er3+ by Yb3+. The relative intensities of upconversion luminescence from 4S3/2 and 2H11/2 are used to analyze internal sample heating in detail. Due to the high absorption cross section of Yb3+, increasing the Yb3+ concentration in Yb3+,Er3+-codoped samples of given length increases the absorbed power and subsequently the total density of

  19. Spectroscopic investigations of Nd(3+)-doped alkali chloroborophosphate glasses.

    PubMed

    Moorthy, L R; Rao, T S; Jayasimhadri, M; Radhapathy, A; Murthy, D V R

    2004-09-01

    Optical absorption spectra were studied in wavelength region 400-900 nm for the Nd(3+)-doped alkali (R = Li, Na and K) chloroborophosphate glasses at room temperature. The energy level scheme of the 4f(3) electron configuration was deduced from the observed energy level data using a parametrized Hamiltonian (H(F1)) model which includes 20 free-ion interaction parameters. Reasonable correlation was obtained between the experimental and calculated energy levels. The Judd-Ofelt model for the intensity analysis of induced electric dipole transitions has been applied to the measured oscillator strengths of the absorption bands to determine the three phenomenological intensity parameters Omega(2), Omega(4) and Omega(6) for each glass. Using these parameters, the total radiative transition rates (A(T)), non-radiative relaxation rates (W(NR)), branching ratios (beta(R)), integrated cross-sections for the stimulated emission (Sigma), excited state emission intensities (f(ESE)) and excited state absorption intensities (f(ESA)) have been theoretically calculated for certain excited Nd(3+) fluorescent levels. From the results obtained, the conclusion is made about the possibility of using these glasses as laser media. PMID:15294227

  20. Structural, vibrational, and elastic properties of a calcium aluminosilicate glass from molecular dynamics simulations: The role of the potential

    SciTech Connect

    Bauchy, M.

    2014-07-14

    We study a calcium aluminosilicate glass of composition (SiO{sub 2}){sub 0.60}(Al{sub 2}O{sub 3}){sub 0.10}(CaO){sub 0.30} by means of molecular dynamics. To this end, we conduct parallel simulations, following a consistent methodology, but using three different potentials. Structural and elastic properties are analyzed and compared to available experimental data. This allows assessing the respective abilities of the potentials to produce a realistic glass. We report that, although all these potentials offer a reasonable glass structure, featuring tricluster oxygen atoms, their respective vibrational and elastic predictions differ. This allows us to draw some general conclusions about the crucial role, or otherwise, of the interaction potential in silicate systems.

  1. Alkali-aggregate reactivity of typical siliceious glass and carbonate rocks in alkali-activated fly ash based geopolymers

    NASA Astrophysics Data System (ADS)

    Lu, Duyou; Liu, Yongdao; Zheng, Yanzeng; Xu, Zhongzi; Shen, Xiaodong

    2013-08-01

    For exploring the behaviour of alkali-aggregate reactivity (AAR) in alkali-activated geopolymeric materials and assessing the procedures for testing AAR in geopolymers, the expansion behaviour of fly ash based geopolymer mortars with pure silica glass and typical carbonate rocks were studied respectively by curing at various conditions, i.e. 23°C and 38°C with relative humidity over 95%, immersed in 1M NaOH solution at 80°C. Results show that, at various curing conditions, neither harmful ASR nor harmful ACR was observed in geopolymers with the criteria specified for OPC system. However, with the change of curing conditions, the geopolymer binder and reactive aggregates may experience different reaction processes leading to quite different dimensional changes, especially with additional alkalis and elevated temperatures. It suggests that high temperature with additional alkali for accelerating AAR in traditional OPC system may not appropriate for assessing the alkali-aggregate reactivity behaviour in geopolymers designed for normal conditions. On the other hand, it is hopeful to control the dimensional change of geopolymer mortar or concrete by selecting the type of aggregates and the appropriate curing conditions, thus changing the harmful AAR in OPC into beneficial AAR in geopolymers and other alkali-activated cementitious systems.

  2. Sodium sulfate corrosion of silicon carbide fiber-reinforced calcium aluminosilicate glass-ceramic matrix composites. Master's thesis

    SciTech Connect

    Newton, P.J.

    1994-03-01

    Hot corrosion effects of Sodium Sulfate (NaSO4) coated Calcium Aluminosilicate (CAS)/Silicon Carbide (SiC) reinforced glass-ceramic matrix composite were investigated using Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX) and X-ray Diffraction (XRD). The samples provided by the Naval Air Warfare Center (NAWC) were unidirectional SiC/CAS as follows: (1) as received, (2) uncoated in air, (3) Na2SO4, coated in air and (4) Na2SO4 coated in argon. A heat treatment was conducted at 900 deg C for 100 hours. Experimental observations indicated that the Na2S04 coating in an oxidising environment had severely corroded the silicon fiber resulting in a silica rich, Nepheline, Wollastonite, Rankinite, Albite and glassy phases. In the argon atmosphere fiber degradation was present although less severe than in the oxygen environment. Similar phases of silica rich, Nepheline, Albite, Rankinite, Mullite, Pseudo-Wollastonite and a glassy region were present. Minimal fiber and matrix degradation was observed in the uncoated sample beat treated in air. Calcium aluminosilicate, SiC Fiber reinforced composites.

  3. Investigation of Yb3+-doped alumino-silicate glasses for high energy class diode pumped solid state lasers

    NASA Astrophysics Data System (ADS)

    Körner, Jörg; Hein, Joachim; Tiegel, Mirko; Kuhn, Stefan; Buldt, Joachim; Yue, Fangxin; Seifert, Reinhard; Herrmann, Andreas; Rüssel, Christian; Kaluza, Malte C.

    2015-05-01

    We present a detailed investigation of different compositions of Yb3+-doped alumino-silicate glasses as promising materials for diode-pumped high-power laser applications at 1030 nm due to their beneficial thermo-mechanical properties. To generate comprehensive datasets for emission and absorption cross sections, the spectral properties of the materials were recorded at temperatures ranging from liquid nitrogen to room temperature. It was found that the newly developed materials offer higher emission cross sections at the center laser wavelength of 1030 nm than the so far used alternatives Yb:CaF2 and Yb:FP-glass. This results in a lower saturation fluence that offers the potential for higher laser extraction efficiency. Fluorescence lifetime quenching of first test samples was analyzed and attributed to the hydroxide (OH) concentration in the host material. Applying a sophisticated glass manufacturing process, OH concentrations could be lowered by up to two orders of magnitude, rising the lifetime and the quantum efficiency for samples doped with more than 6.1020 Yb3+ -ions per cm³. First laser experiments showed a broad tuning range of about 60 nm, which is superior to Yb:CaF2 and Yb:FP-glass in the same setup. Furthermore, measurements of the laser induced damage threshold (LIDT) for different coating techniques on doped substrates revealed the appropriateness of the materials for short pulse high-energy laser amplification.

  4. Aluminosilicate melts and glasses at 1 to 3 GPa: Temperature and pressure effects on recovered structural and density changes

    USGS Publications Warehouse

    Bista, S; Stebbins, Jonathan; Hankins, William B.; Sisson, Thomas W.

    2015-01-01

    In the pressure range in the Earth’s mantle where many basaltic magmas are generated (1 to 3 GPa) (Stolper et al. 1981), increases in the coordination numbers of the network-forming cations in aluminosilicate melts have generally been considered to be minor, although effects on silicon and particularly on aluminum coordination in non-bridging oxygen-rich glasses from the higher, 5 to 12 GPa range, are now well known. Most high-precision measurements of network cation coordination in such samples have been made by spectroscopy (notably 27Al and 29Si NMR) on glasses quenched from high-temperature, high-pressure melts synthesized in solid-media apparatuses and decompressed to room temperature and 1 bar pressure. There are several effects that could lead to the underestimation of the extent of actual structural (and density) changes in high-pressure/temperature melts from such data. For non-bridging oxygen-rich sodium and calcium aluminosilicate compositions in the 1 to 3 GPa range, we show here that glasses annealed near to their glass transition temperatures systematically record higher recovered increases in aluminum coordination and in density than samples quenched from high-temperature melts. In the piston-cylinder apparatus used, rates of cooling through the glass transition are measured as very similar for both higher and lower initial temperatures, indicating that fictive temperature effects are not the likely explanation of these differences. Instead, transient decreases in melt pressure during thermal quenching, which may be especially large for high initial run temperatures, of as much as 0.5 to 1 GPa, may be responsible. As a result, the equilibrium proportion of high-coordinated Al in this pressure range may be 50 to 90% greater than previously estimated, reaching mean coordination numbers (e.g., 4.5) that are probably high enough to significantly affect melt properties. New data on jadeite (NaAlSi2O6) glass confirm that aluminum coordination increase

  5. Communication: Dimensionality of the ionic conduction pathways in glass and the mixed-alkali effect.

    PubMed

    Novy, Melissa; Avila-Paredes, Hugo; Kim, Sangtae; Sen, Sabyasachi

    2015-12-28

    A revised empirical relationship between the power law exponent of ac conductivity dispersion and the dimensionality of the ionic conduction pathway is established on the basis of electrical impedance spectroscopic (EIS) measurements on crystalline ionic conductors. These results imply that the "universal" ac conductivity dispersion observed in glassy solids is associated with ionic transport along fractal pathways. EIS measurements on single-alkali glasses indicate that the dimensionality of this pathway D is ∼2.5, while in mixed-alkali glasses, D is lower and goes through a minimum value of ∼2.2 when the concentrations of the two alkalis become equal. D and σ display similar variation with alkali composition, thus suggesting a topological origin of the mixed-alkali effect. PMID:26723583

  6. Thermal history effects on electrical relaxation and conductivity for potassium silicate glass with low alkali concentrations

    NASA Technical Reports Server (NTRS)

    Angel, Paul W.; Hann, Raiford E.; Cooper, Alfred R.

    1993-01-01

    Electrical response measurements from 10 Hz to 100 kHz between 120 and 540 C were made on potassium-silicate glasses with alkali oxide contents of 2, 3, 5 and 10 mol percent. Low alkali content glasses were chosen in order to try to reduce the Coulombic interactions between alkali ions to the point that frozen structural effects from the glass could be observed. Conductivity and electrical relaxation responses for both annealed and quenched glasses of the same composition were compared. Lower DC conductivity (sigma(sub DC)) activation energies were measured for the quenched compared to the annealed glasses. The two glasses with the lowest alkali contents exhibited a non-Arrhenius concave up curvature in the log(sigma(sub DC)) against 1/T plots, which decreased upon quenching. A sharp decrease in sigma(sub DC) was observed for glasses containing K2O concentrations of 5 mol percent or less. The log modulus loss peak (M'') maximum frequency plots against 1/T all showed Arrhenius behavior for both annealed and quenched samples. The activation energies for these plots closely agreed with the sigma(sub DC) activation energies. A sharp increase in activation energy was observed for both series as the potassium oxide concentration decreased. Changes in the electrical response are attributed to structural effects due to different alkali concentrations. Differences between the annealed and quenched response are linked to a change in the distribution of activation energies (DAE).

  7. Effect of alkali addition on DC conductivity and thermal properties of vanadium-bismo-borate glasses

    SciTech Connect

    Khasa, S. Dahiya, M. S.; Agarwal, A.

    2014-04-24

    The DC Conductivity and Differential Thermal Analysis of glasses with composition (30−x)Li{sub 2}O⋅xV{sub 2}O{sub 5}⋅20Bi{sub 2}O{sub 3}⋅50B{sub 2}O{sub 3}(x=15, 10, 5) has been carried out in order to study the effect of replacing the Transition Metal Oxide (TMO) with alkali oxide. A significant increase in the DC conductivity has been observed with increase in alkali content. Again the thermal measurements have shown the decrease in both glass transition temperature (T{sub g}) and crystallization temperature (T{sub x}). The Glass Stability (GS) and Glass Forming Ability (GFA) have also been calculated and these also were found to decrease with increase in alkali oxide content at the cost of TMO.

  8. Effect of Eu3+ concentration on the grating efficiency and ionic conductivity in sodium-magnesium-aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    Hamad, Abdulatif Y.; Wicksted, James P.; Ascio, Robert; Martin, Joel J.; Hunt, Charles; Dixon, George S.

    2002-09-01

    We report a systematic study of a grating formation in which the Eu2O3 in sodium-magnesium-aluminosilicate glasses is varied from 0.76 to 8.11 mol %. The growth, decay, and erasure of the grating are reported as functions of the Eu2O3. The maximum persistent change in the index of refraction was 3 x10-5. The persistent change in the index of refraction was initially a quadratic function of the Eu2O3 and showed a limiting behavior at the highest Eu2O3. The transient change in the index of refraction Deltantran was a quadratic function of Eu2O3 throughout the range of concentrations studied here. The grating buildup rate increased linearly with Deltantran. The results of this study are consistent with the model published recently by Dixon [et al.] Ionic conductivities were also measured to help separate the effect of the Eu3+ on the glass network from its active role in transferring the optical energy into ionic motion.

  9. Crystallization Kinetics of Barium and Strontium Aluminosilicate Glasses of Feldspar Composition

    NASA Technical Reports Server (NTRS)

    Hyatt, Mark J.; Bansal, Narottam P.

    1994-01-01

    Crystallization kinetics of BaO.Al2O3.2SiO2 (BAS) and SrO.Al2O3.2SiO2 (SAS) glasses in bulk and powder forms have been studied by non-isothermal differential scanning calorimetry (DSC). The crystal growth activation energies were evaluated to be 473 and 451 kJ/mol for bulk samples and 560 and 534 kJ/mol for powder specimens in BAS and SAS glasses, respectively. Development of crystalline phases on thermal treatments of glasses at various temperatures has been followed by powder x-ray diffraction. Powder samples crystallized at lower temperatures than the bulk and the crystallization temperature was lower for SAS glass than BAS. Crystallization in both glasses appeared to be surface nucleated. The high temperature phase hexacelsian, MAl2Si2O8 (M = Ba or Sr), crystallized first by nucleating preferentially on the glass surface. Also, monoclinic celsian does not nucleate directly in the glass, but is formed at higher temperatures from the transformation of the metastable hexagonal phase. In SAS the transformation to monoclinic celsian occurred rapidly after 1 h at 1100 C. In contrast, in BAS this transformation is sluggish and difficult and did not go to completion even after 10 h heat treatment at 1400 C. The crystal growth morphologies in the glasses have been observed by optical microscopy. Some of the physical properties of the two glasses are also reported.

  10. Alkali ion migration between stacked glass plates by corona discharge treatment

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Keiga; Suzuki, Toshio; Ikeda, Hiroshi; Sakai, Daisuke; Funatsu, Shiro; Uraji, Keiichiro; Yamamoto, Kiyoshi; Harada, Kenji; Nishii, Junji

    2015-05-01

    Corona discharge reflects the spatial migration of alkali ions over a gap between two glass plates. This study examined stacked glass plates containing different alkali ions treated with the corona discharge plasma generated by applied voltage of 4.5 kV at 200 °C. Protons generated at the anode electrode penetrate into the potassium-ion-containing upper glass plate, which is located 5 mm below the anode electrode. Potassium ions intruded into the lower glass plate containing sodium ions placed on the cathode electrode, even over a 1 mm gap separating the plates. Finally, the sodium ion discharged on the cathode electrode. The hydrogen atmosphere was effective at inhibiting the potassium ion reaction with ambient gases during the spatial migration between the two glass plates.

  11. PLUTONIUM SOLUBILITY IN HIGH-LEVEL WASTE ALKALI BOROSILICATE GLASS

    SciTech Connect

    Marra, J.; Crawford, C.; Fox, K.; Bibler, N.

    2011-01-04

    The solubility of plutonium in a Sludge Batch 6 (SB6) reference glass and the effect of incorporation of Pu in the glass on specific glass properties were evaluated. A Pu loading of 1 wt % in glass was studied. Prior to actual plutonium glass testing, surrogate testing (using Hf as a surrogate for Pu) was conducted to evaluate the homogeneity of significant quantities of Hf (Pu) in the glass, determine the most appropriate methods to evaluate homogeneity for Pu glass testing, and to evaluate the impact of Hf loading in the glass on select glass properties. Surrogate testing was conducted using Hf to represent between 0 and 1 wt % Pu in glass on an equivalent molar basis. A Pu loading of 1 wt % in glass translated to {approx}18 kg Pu per Defense Waste Processing Facility (DWPF) canister, or about 10X the current allowed limit per the Waste Acceptance Product Specifications (2500 g/m{sup 3} of glass or about 1700 g/canister) and about 30X the current allowable concentration based on the fissile material concentration limit referenced in the Yucca Mountain Project License Application (897 g/m{sup 3}3 of glass or about 600 g Pu/canister). Based on historical process throughput data, this level was considered to represent a reasonable upper bound for Pu loading based on the ability to provide Pu containing feed to the DWPF. The task elements included evaluating the distribution of Pu in the glass (e.g. homogeneity), evaluating crystallization within the glass, evaluating select glass properties (with surrogates), and evaluating durability using the Product Consistency Test -- Method A (PCT-A). The behavior of Pu in the melter was evaluated using paper studies and corresponding analyses of DWPF melter pour samples.The results of the testing indicated that at 1 wt % Pu in the glass, the Pu was homogeneously distributed and did not result in any formation of plutonium-containing crystalline phases as long as the glass was prepared under 'well-mixed' conditions. The

  12. Structure of glasses containing transition metal ions. Progress report, February 1, 1979-January 31, 1980

    SciTech Connect

    White, W B; Furukawa, T; Tsong, I S.T.; Fox, K; Herman, J S; Houser, C; Nelson, C

    1980-02-01

    New normal coordinate calculations were used to relate the vibrational frequencies of silicate glasses to Si-O force constants. These appear to account for the observed frequency shifts with degree of silica polymerization. Raman spectroscopy has been used to elucidate the structure of sodium borosilicate glasses and of sodium aluminosilicate glasses. Structures of compositionally complex glasses can be understood if spectra are measured on many glasses spaced at small compositional intervals. Optical absorption spectra were used to investigate the structural setting of iron in alkali silicate glasses. Research on the alkali-hydrogen exchange in alkali silicate glasses was completed and additional work on ternary glasses is under way. A series of appendices present completed work on the structural investigations of alkali borosilicate glasses, on the structural setting of transition metal ions in glasses, and on the diffusion of hydrogen in alkali silicate glasses.

  13. Crystallization and properties of Sr-Ba aluminosilicate glass-ceramic matrices

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Hyatt, Mark J.; Drummond, Charles H., III

    1991-01-01

    Powders of roller quenched (Sr,Ba)O-Al2O3-2SiO2 glasses of various compositions were uniaxially pressed into bars and hot isostatically pressed at 1350 C for 4 hours or cold isostatically pressed and sintered at different temperatures between 800 to 1500 C for 10 or 20 hours. Densities, flexural strengths, and linear thermal expansion were measured for three compositions. The glass transition and crystallization temperatures were determined by Differential Scanning Calorimetry (DSC). The liquidus and crystallization temperature from the melt were measured using high temperature Differential Thermal Analysis (DTA). Crystalline phases formed on heat treatment of the glasses were identified by powder X ray diffraction. In Sr containing glasses, the monoclinic celsian phase always crystallized at temperatures above 1000 C. At lower temperatures, the hexagonal analog formed. The temperature for orthorhombic to hexagonal structural transformation increased monotonically with SrO content, from 327 C for BaO-Al2O3-2SiO2 to 758 C for SrO-Al2O3-2SiO2. These glass powders can be sintered to almost full densities and monoclinic celsian phase at a relatively low temperature of 1100 C.

  14. On the Electron Paramagnetic Resonance Studies in Mixed Alkali Borate Glasses

    SciTech Connect

    Padmaja, G.; Reddy, T. Goverdhan; Kistaiah, P.

    2011-10-20

    Mixed alkali effect in oxide based glasses is one of the current research activity and studies on the behavior of spectroscopic parameters in these systems are quite important to understand the basic nature of this phenomenon. EPR studies of mixed alkali glasses Li{sub 2}O-K{sub 2}O-ZnO-B{sub 2}O{sub 3} doped with Fe{sup 3+} and Mn{sup 2+} were carried out at room temperature. The EPR spectra show typical resonances of d{sup 5} system (Fe{sup 3+} and Mn{sup 2+}) in all the measured glass specimens. Evaluated hyperfine constant, number of paramagnetic centers and paramagnetic susceptibility values show deviation from the linearity with the progressive substitution of the Li ion with K in glass network.

  15. Relations among nonbridging oxygen, optical properties, optical basicity, and color center formation in CaO-MgO aluminosilicate glasses

    SciTech Connect

    Novatski, A.; Steimacher, A.; Medina, A. N.; Bento, A. C.; Baesso, M. L.; Andrade, L. H. C.; Lima, S. M.; Guyot, Y.; Boulon, G.

    2008-11-01

    In this study the relations among nonbridging oxygen (NBO), optical properties, optical basicity, and color center formation in CaO-MgO aluminosilicate glasses were studied. Samples containing (in mol %) 35.9-57.5 of CaO, 16-27.7 of Al{sub 2}O{sub 3}, 7.9-41.6 of SiO{sub 2}, and 6.5-6.9 of MgO were measured by optical absorption and excitation, luminescence, and Raman spectroscopy. The results showed that when the SiO{sub 2} content was increased, the absorption edge shifted toward lower wavelengths and the bonds between O{sup 2-} ions and cations became more covalent. These observations were confirmed by Raman results that showed a decrease in the number of NBO per silicon tetrahedron as a function of SiO{sub 2} content. The results indicate that the effects of higher NBO concentration are the narrowing of the band gap energy and the delocalization of O{sup 2-} electrons, which facilitates the O{sup 2-} electrons to be trapped by anion vacancies and, consequently, forming color centers. The relationship between color center formation and SiO{sub 2} content was confirmed by optical spectroscopic measurements under UV radiation.

  16. Electrical behavior of aluminosilicate glass-ceramic sealants and their interaction with metallic solid oxide fuel cell interconnects

    NASA Astrophysics Data System (ADS)

    Goel, Ashutosh; Tulyaganov, Dilshat U.; Kharton, Vladislav V.; Yaremchenko, Aleksey A.; Ferreira, José M. F.

    A series of alkaline-earth aluminosilicate glass-ceramics (GCs) were appraised with respect to their suitability as sealants for solid oxide fuel cells (SOFCs). The parent composition with general formula Ca 0.9MgAl 0.1La 0.1Si 1.9O 6 was modified with Cr 2O 3 and BaO. The addition of BaO led to a substantial decrease in the total electrical conductivity of the GCs, thus improving their insulating properties. BaO-containing GCs exhibited higher coefficient of thermal expansion (CTE) in comparison to BaO-free GCs. An extensive segregation of oxides of Ti and Mn, components of the Crofer22 APU interconnect alloy, along with negligible formation of BaCrO 4 was observed at the interface between GC/interconnects diffusion couples. Thermal shock resistance and gas-tightness of GC sealants in contact with yttria-stabilized zirconia electrolyte (8YSZ) was evaluated in air and water. Good matching of CTE and strong, but not reactive, adhesion to the solid electrolyte and interconnect, in conjunction with a high level of electrical resistivity, are all advantageous for potential SOFC applications.

  17. Electrical conduction in alkali borate glasses; a unique dependence on the concentration of modifier ions

    NASA Astrophysics Data System (ADS)

    Doweidar, H.; Moustafa, Y. M.; El-Damrawi, G. M.; Ramadan, R. M.

    2008-01-01

    The electrical conduction of Li2O-B2O3, Na2O-B2O3 and K2O-B2O3 glasses seems, at first sight, to be dominated by the activation energy. Regardless of the size of the alkali ion, there is a unique dependence of conductivity, at a certain temperature, on the alkali-alkali distance and thus on N (the number of ions per cm3). The linear dependence of logσ on N-3/2 for all types of alkali ions reveals that N is the basic parameter that determines the conductivity at a certain temperature. A derived semi-empirical relation can be used to calculate the conductivity as a function of N and temperature.

  18. Method of producing a silicon carbide fiber reinforced strontium aluminosilicate glass-ceramic matrix composite

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P. (Inventor)

    1995-01-01

    A SrO-Al2O3-2SrO2 (SAS) glass ceramic matrix is reinforced with CVD SiC continuous fibers. This material is prepared by casting a slurry of SAS glass powder into tapes. Mats of continuous CVD-SiC fibers are alternately stacked with the matrix tapes. This tape-mat stack is warm-pressed to produce a 'green' composite. Organic constituents are burned out of the 'green' composite, and the remaining interim material is hot pressed.

  19. Silicon carbide fiber reinforced strontium aluminosilicate glass-ceramic matrix composite

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam (Inventor)

    1992-01-01

    A SrO-Al2O3 - 2SrO2 (SAS) glass ceramic matrix is reinforced with CVD SiC continuous fibers. This material is prepared by casting a slurry of SAS glass powder into tapes. Mats of continuous CVD-SiC fibers are alternately stacked with the matrix tapes. This tape-mat stack is warm-pressed to produce a 'green' composite. Organic constituents are burned out of the 'green' composite, and the remaining interim material is hot pressed.

  20. Modifier interaction and mixed-alkali effect in bond constraint theory applied to ternary alkali metaphosphate glasses

    NASA Astrophysics Data System (ADS)

    Poletto Rodrigues, Bruno; Deubener, Joachim; Wondraczek, Lothar

    2016-05-01

    Introducing an interaction parameter γ, we implement modifier interaction and the mixed-alkali effect into bond constraint theory, and apply this extension for simplistic property prediction on ternary phosphate glasses. The severity of the mixed alkali effect results from the interplay of two simultaneous contributions: Bond constraints on the modifier species soften or stiffen with decreasing or increasing γ, respectively. When the modifier size is not too dissimilar the decrease in γ reflects that the alkali ions can easily migrate between different sites, forcing the network to continuously re-accommodate for any subsequent distortions. With increasing size difference, migration becomes increasingly difficult without considerable network deformation. This holds even for smaller ions, where the sluggish dynamics of the larger constituent result in blocking of the fast ion movement, leading to the subsequent increase in γ. Beyond a certain size difference in the modifier pair, a value of γ exceeding unity may indicate the presence of steric hindrance due to the large surrounding modifiers impeding the phosphate network to re-accommodate deformation.

  1. Crystallization and properties of Sr-Ba aluminosilicate glass-ceramic matrices

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Hyatt, Mark J.; Drummond, Charles H., III

    1991-01-01

    Powders of roller quenched (Sr,Ba)O-Al2O3-2SiO2 glasses of various compositions were uniaxially pressed into bars and hot isostatically pressed at 1350 C for 4 hours or cold isostatically pressed and sintered at different temperatures between 800 to 1500 C for 10 or 20 hours. Densities, flexural strengths, and linear thermal expansion were measured for three compositions. The glasss transition and crystallization temperatures were determined by Differential Scanning Calorimetry (DSC). The liquidus and crystallization temperature from the melt were measured using high temperature Differential Thermal Analysis (DTA). Crystalline phases formed on heat treatment of the glasses were identified by powder x ray diffraction. In Sr containing glasses, the monoclinic celsian phase always crystallized at temperatures above 1000 C. At lower temperatures, the hexagonal analog formed. The temperature for orthorhombic to hexagonal structure transformation increased monotonically with SrO content, from 327 C for BaO-Al2O3-2SiO2 to 758 C for SrO-Al2O3-2SiO2. These glass powders can be sintered to almost full densities and monoclinic celsian phase at a relatively low temperature of 1100 C.

  2. EXEFS study on local structure of aluminosilicate glasses quenched from high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Yokota, I.; Urakawa, S.; Yoshino, T.

    2011-12-01

    Silicate melts play an important role in chemical evolution of planetary mantle during early magma ocean as well as subsequent long history. Movement of silicate melt in the mantle is controlled by its viscosity and density that are related to the melt structure. Therefore, the structural study of silicate melts under pressure is fundamental to understand the magma-related phenomena within the planets. Pressure-induced structure change in silicate melts has been studied mainly by spectroscopy of quenched glasses such as NMR and XAFS. Here we report the first results of application of the extended x-ray emission fine structure (EXEFS) to the structure analysis of the quenched silicate glass. The EXEFS arises from the radiative Auger effect and has the same structure as the XAFS. The EXEFS can be measured using a wavelength dispersive electron microprobe, so that it does not require bulk sample. We measured the EXEFS spectra of Al, Si and Mg for the Ca3Al2Si6O18 (CAS) and Mg3Al2Si6O18 (MAS) composition glasses quenched from melts at 8 GPa and 6 GPa, respectively, using the JEOL JXA8230 microprobe. The EXEFS yields the same spectrum as the XANES, of which the main peak position includes information of nearest neighbor coordination environment. We observed the Al-EXEFS peak for CAS glasses shifting with quench pressure, indicating the increase of the coordination number of Al with pressure. This observation is consistent with the Al NMR studies (e.g., Allward et al. 2005). On the other hand, the Si-EXEFS spectra show no detectable change in the main peak position, meaning nearly constant coordination number of Si. Although the EXEFS method is time consuming due to its low signal intensity, it can be applied to the high-pressure quench glasses even though they include crystalline phases.

  3. Functionalized Amorphous Aluminosilicates

    NASA Astrophysics Data System (ADS)

    Mesgar, Milad

    Alkali treated aluminosilicate (geopolymer) was functionalized by surfactant to increase the hydrophobicity for making Pickering emulsion for the first part of this work. In the first part of this study, alkali treated metakaolin was functionalized with cetyltrimethylammonium bromide ((C16H33)N(CH 3)3Br, CTAB). The electrostatic interaction between this quaternary ammonium and the surface of the aluminosilicate which has negative charge has taken place. The particles then were used to prepare Pickering emulsion. The resulting stable dispersions, obtained very fast at very simple conditions with low ratio of aluminosilicate to liquid phase. In the second part, the interaction between geopolymer and glycerol was studied to see the covalent grafting of the geopolymer for making geopolymer composite. The composite material would be the basis material to be used as support catalyst, thin coating reagent and flame retardant material and so on, Variety of techniques, Thermogravimetric (TGA), Particle-induced X-ray emission (PIXE), FTIR, Solid state NMR, Powder X-ray diffraction (PXRD), BET surface area, Elemental analysis (CHN), TEM, SEM and Optical microscopy were used to characterize the functionalized geopolymer.

  4. Spectroscopic properties of Er{sup 3+}- and Yb{sup 3+}-doped soda-lime silicate and aluminosilicate glasses

    SciTech Connect

    Hehlen, M.P.; Cockroft, N.J.; Gosnell, T.R.; Bruce, A.J.

    1997-10-01

    A spectroscopic investigation of an extensive series of Er{sup 3+}-doped and Er{sup 3+},Yb{sup 3+}-codoped soda-lime-silicate (SL) and aluminosilicate (AS) glasses is presented. Compared to SL glasses, 4f transitions in AS glasses show higher oscillator strengths, larger inhomogeneous broadening, and smaller crystal-field splittings of the respective excited-state multiplets. The Er{sup 3+} excited-state relaxation dynamics is adequately described by a combination of the Judd-Ofelt model and the energy-gap law. With the exception of {sup 4}I{sub 13/2}, multiphonon relaxation is dominant for all excited states, making it possible to efficiently pump the 1.55 {mu}m {sup 4}I{sub 13/2}{r_arrow}{sup 4}I{sub 15/2} emission by excitation of {sup 4}I{sub 11/2} at around 980 nm. The absolute {sup 4}I{sub 13/2} luminescence quantum yield, for low 980-nm excitation density ({approximately}5W/cm{sup 2}), {eta}, is {approximately}0.9 at 0.4 mol{percent} Er{sub 2}O{sub 3} and drops to about 0.65 upon increasing Er{sub 2}O{sub 3} to 1.2 mol{percent}, indicating the onset of energy-transfer processes. Samples with high OH{sup {minus}} impurity concentration suffer from significantly higher quenching of {sup 4}I{sub 13/2} luminescence at higher Er{sup 3+} concentrations. Energy migration to the minority of Er{sup 3+} ions coordinated to OH{sup {minus}}, followed by efficient multiphonon relaxation accounts for this effect. At low excitation densities, the strong near-infrared absorption of Yb{sup 3+} in combination with efficient Yb{r_arrow}Er energy transfer increases the {sup 4}I{sub 13/2} population density in Yb{sup 3+},Er{sup 3+}-codoped samples by up to 2 orders of magnitude compared to equivalent samples without Yb{sup 3+}. (Abstract Truncated)

  5. Sodium sulfate corrosion of silicon carbide fiber-reinforced lithium aluminosilicate glass-ceramic matrix composites. Master's thesis

    SciTech Connect

    Maldia, L.C.

    1993-12-01

    Sodium sulfate hot corrosion of a SiC fiber-reinforced lithium aluminosilicate (LAS) glass-ceramic matrix composite was studied using Scanning Electron Microscope (SEM) and X-ray Diffraction (XRD). Changes in the microstructural chemical composition of the specimens were investigated. The samples provided by Naval Air Warfare Center (NAWC), Warminster, PA were grouped as follows: (1) as-received, (2) Na2SO4 salt-coated and heat-treated in oxygen, (3) noncoated and heat-treated in oxygen, (4) Na2SO4. Salt-coated and heat-treated in argon, and (5) noncoated and heat-treated in argon. Heat treatment was performed by NAWC for 100 hours at 900 deg C. Experimental data obtained indicated that the presence of Na2SO4 in an oxidative environment resulted in rapid corrosion of the matrix and SiC fibers and in the latter rings of SiO2 replaced what had previously been SiC. There was very limited degradation of the fibers and matrix exposed at the surface in the noncoated sample heat-treated in oxygen and in the salt-coated sample heat-treated in argon. A significant reduction in the amount of mullite in the matrices of all heat-treated samples was observed. Mullite dissolved into either the glassy phase or into the Beta-spodumene matrix. Lastly, the presence of distinct magnesium silicate crystalline phases in the salt-coated and heat-treated in oxygen sample implies that the MgO at the surface reacted with the SiO2 in the matrix.

  6. Optical and spectroscopic properties of soda lime alumino-silicate glasses doped with erbium and silver

    NASA Astrophysics Data System (ADS)

    Carmo, A. P.; Bell, M. J. V.; Da Costa, Z. M.; Anjos, V.; Barbosa, L. C.; Chillcce, E. F.; Giehl, J. M.; Pontuschka, W. M.

    2011-10-01

    Spectroscopic properties of Ag/Er co-doped soda lime silicate glasses have been studied with the aim of assessing the effective role of silver as a sensitizer for erbium. Changes in spectroscopic properties of Er 3+ as a function of silver addition to the base composition have been measured. Transmission electron microscopy (TEM), absorption as well as photoluminescence measurements in the visible and infrared spectral region, particularly 4I 13/2 → 4I 15/2 transition of the Er 3+ ion were performed; excitation wavelengths in the range from 325 to 808 nm were used. Enhancement of the Er 3+ luminescence at 1.54 μm was observed when Ag was added.

  7. NMR studies of bond arrangements in alkali phosphate glasses

    SciTech Connect

    Alam, T.M.; Brow, R.K.

    1998-01-01

    Solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy has become a powerful tool for the investigation of local structure and medium range order in glasses. Previous {sup 31}P MAS NMR studies have detailed the local structure for a series of phosphate glasses. Phosphate tetrahedra within the glass network are commonly described using the Q{sup n} notation, where n = 0, 1, 2, 3 and represents the number of bridging oxygens attached to the phosphate. Using {sup 31}P MAS NMR different phosphate environments are readily identified and quantified. In this paper, the authors present a brief description of recent one dimensional (1D) {sup 6}Li, {sup 7}Li and {sup 31}P MAS experiments along with two-dimensional (2D) {sup 31}P exchange NMR experiments for a series of lithium ultraphosphate glasses. From the 2D exchange experiments the connectivities between different Q{sup n} phosphate tetrahedra were directly measured, while the 1D experiments provided a measure of the P-O-P bond angle distribution and lithium coordination number as a function of Li{sub 2}O concentration.

  8. Interfacial interactions between an alkali-free borosilicate viscous sealing glass and aluminized ferritic stainless steel

    NASA Astrophysics Data System (ADS)

    Hsu, Jen-Hsien; Kim, Cheol-Woon; Brow, Richard K.

    2014-03-01

    An alkali-free, alkaline earth borosilicate glass (designated G73) has been developed as a viscous sealant for use with solid oxide fuel cells (SOFC). In this work, the interfacial interactions that occur between this viscous sealant and aluminized ferritic stainless steel (SS441) under SOFC operational conditions are described. YSZ/glass/aluminized SS441 sandwich seals were held at 800 °C in air for up to 1000 h, and the interfaces were analyzed using analytical scanning electron microscopy (ASEM). Interfacial reactions were also characterized by X-ray diffraction (XRD) analyses of heat-treated mixtures of glass and alumina powders. The results show that the glass reacted with aluminum from the steel to form BaAl2Si2O8 crystals at the glass/metal interface and that the aluminum concentration in the aluminized steel was significantly depleted with time.

  9. Structure, biodegradation behavior and cytotoxicity of alkali-containing alkaline-earth phosphosilicate glasses.

    PubMed

    Kansal, Ishu; Reddy, AlluAmarnath; Muñoz, Francisco; Choi, Seong-Jun; Kim, Hae-Won; Tulyaganov, Dilshat U; Ferreira, José M F

    2014-11-01

    We report on the effect of sodium on the structure, chemical degradation and bioactivity of glasses in the CaO-MgO-SiO2-P2O5-CaF2 system. The (29)Si and (31)P magic angle spinning-nuclear magnetic resonance spectroscopy of melt-quenched glasses with varying Na2O/MgO ratios exhibit a silicate glass network with the dominance of Q(2)(Si) units and phosphorus mainly forming orthophosphate species. Sodium incorporation in the glasses did not induce a significant structural change in the silicate network, while it did influence the phosphate environment due to its lower ionic field strength in comparison with that of magnesium. The apatite forming ability of glasses has been investigated by immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1h and 7 days while their chemical degradation has been studied in Tris-HCl in accordance with ISO-10993-14. Increasing Na(+)/Mg(2+) ratio caused a decrease in the chemical durability of glasses and in the apatite forming ability especially during initial steps of interaction between glass and SBF solution. The cellular responses were observed in vitro on bulk glass samples using mouse-derived pre-osteoblastic MC3T3-E1 cell line. The preliminary study suggested that the increasing alkali-concentration in glasses led to cytotoxicity in the cell culture medium. PMID:25280692

  10. Raman Analysis of Perrhenate and Pertechnetate in Alkali Salts and Borosilicate Glasses

    SciTech Connect

    Gassman, Paul L.; McCloy, John S.; Soderquist, Chuck Z.; Schweiger, Michael J.

    2014-01-03

    Sodium borosilicate glasses containing various concentrations of rhenium or technetium were fabricated, and their vibrational spectra studied using a Raman microscope. Spectra were interpreted with reference to new high resolution measurements of alkali pertechnetates and perrhenates NaReO4, KReO4, NaTcO4, and KTcO4. At low concentrations of ReO4- or TcO4-, glass spectra show weak peaks superimposed on a dominant spectrum of glass characteristic of silicate and borate network vibrations. At high concentrations, sharp peaks characteristic of crystal field splitting and C4h symmetry dominate the spectra of glasses, indicating alkali nearby tetrahedral Re or Tc. Often peaks indicative of both the K and Na pertechnetates/ perrhenates are evident in the Raman spectrum, with the latter being favored at high additions of the source chemical, since Na is more prevalent in the glass and ion exchange takes place. These results have significance to immobilization of nuclear waste containing radioactive 99Tc in glass for ultimate disposal.

  11. Alkali-silica reactivity of expanded glass granules in structure of lightweight concrete

    NASA Astrophysics Data System (ADS)

    Bumanis, G.; Bajare, D.; Locs, J.; Korjakins, A.

    2013-12-01

    Main component in the lightweight concrete, which provides its properties, is aggregate. A lot of investigations on alkali silica reaction (ASR) between cement and lightweight aggregates have been done with their results published in the academic literature. Whereas expanded glass granules, which is relatively new product in the market of building materials, has not been a frequent research object. Therefore lightweight granules made from waste glass and eight types of cement with different chemical and mineralogical composition were examined in this research. Expanded glass granules used in this research is commercially available material produced by Penostek. Lightweight concrete mixtures were prepared by using commercial chemical additives to improve workability of concrete. The aim of the study is to identify effect of cement composition to the ASR reaction which occurs between expanded glass granules and binder. Expanded glass granules mechanical and physical properties were determined. In addition, properties of fresh and hardened concrete were determined. The ASR test was processed according to RILEM AAR-2 testing recommendation. Tests with scanning electron microscope and microstructural investigations were performed for expanded glass granules and hardened concrete specimens before and after exposing them in alkali solution.

  12. On the induction of homogeneous bulk crystallization in Eu-doped calcium aluminosilicate glass by applying simultaneous high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Muniz, R. F.; de Ligny, D.; Le Floch, S.; Martinet, C.; Rohling, J. H.; Medina, A. N.; Sandrini, M.; Andrade, L. H. C.; Lima, S. M.; Baesso, M. L.; Guyot, Y.

    2016-06-01

    From initial calcium aluminosilicate glass, transparent glass-ceramics have been successfully synthesized under simultaneous high pressure and temperature (SHPT). Possible homogeneous volumetric crystallization of this glassy system, which was not achieved previously by means of conventional heat treatment, has been put in evidence with a SHPT procedure. Structural, mechanical, and optical properties of glass and glass-ceramic obtained were investigated. Raman spectroscopy and X-ray diffraction allowed to identify two main crystalline phases: merwinite [Ca3Mg(SiO4)2] and diopside [CaMgSi2O6]. A Raman scanning profile showed that the formation of merwinite is quite homogeneous over the bulk sample. However, the sample surface also contains significant diopside crystals. Instrumented Berkovich nanoindentation was applied to determine the effect of SHPT on hardness from glass to glass-ceramic. For Eu-doped samples, the broadband emission due to 4f65d1 → 4f7 transition of Eu2+ was studied in both host systems. Additionally, the 5D0 → 7FJ transition of Eu3+ was used as an environment probe in the pristine glass and the glass-ceramic.

  13. Alkali-free bioactive glasses for bone tissue engineering: a preliminary investigation.

    PubMed

    Goel, Ashutosh; Kapoor, Saurabh; Rajagopal, Raghu Raman; Pascual, Maria J; Kim, Hae-Won; Ferreira, José M F

    2012-01-01

    An alkali-free series of bioactive glasses has been designed and developed in the glass system CaO-MgO-SiO(2)-P(2)O(5)-CaF(2) along the diopside (CaMgSi(2)O(6))-fluorapatite (Ca(5)(PO(4))(3)F)-tricalcium phosphate (3CaO·P(2)O(5)) join. The silicate network in all the investigated glasses is predominantly coordinated in Q(2) (Si) units, while phosphorus tends to remain in an orthophosphate (Q(0)) environment. The in vitro bioactivity analysis of glasses has been made by immersion of glass powders in simulated body fluid (SBF) while chemical degradation has been studied in Tris-HCl in accordance with ISO-10993-14. Some of the investigated glasses exhibit hydroxyapatite formation on their surface within 1-12 h of their immersion in SBF solution. The sintering and crystallization kinetics of glasses has been investigated by differential thermal analysis and hot-stage microscopy, respectively while the crystalline phase evolution in resultant glass-ceramics has been studied in the temperature range of 800-900°C using powder X-ray diffraction and scanning electron microscopy. The alkaline phosphatase activity and osteogenic differentiation for glasses have been studied in vitro on sintered glass powder compacts using rat bone marrow mesenchymal stem cells. The as-designed glasses are ideal candidates for their potential applications in bone tissue engineering in the form of bioactive glasses as well as glass/glass-ceramic scaffolds. PMID:21925626

  14. Alkali-free bioactive glasses for bone tissue engineering: A preliminary investigation

    SciTech Connect

    Goel, Ashutosh; Kapoor, Saurabh; Rajagopal, Raghu R.; Pascual, Maria J.; Kim, Hae-Won; Ferreira, Jose M.

    2011-08-25

    An alkali-free series of bioactive glasses has been designed and developed in the glass system CaO-MgO-SiO2-P2O5-CaF2 along diopside (CaMgSi2O6) – fluorapatite [Ca5(PO4)3F] – tricalcium phosphate (3CaO•P2O5) join. The silicate network in all the investigated glasses is predominantly coordinated in Q2 (Si) units while phosphorus tends to remain in orthophosphate (Q0) environment. The in vitro bioactivity analysis of glasses has been made by immersion of glass powders in simulated body fluid (SBF) while chemical degradation has been studied in Tris-HCl in accordance with ISO-10993-14. Some of the investigated glasses exhibit hydroxyapatite (HA) formation on their surface with in 1-12 h of their immersion in SBF solution. The sintering and crystallization kinetics of glasses has been investigated by differential thermal analysis (DTA) and hot-stage microscopy (HSM), respectively while the crystalline phase evolution in resultant glass-ceramics (GCs) has been studied in the temperature range of 800-900 oC using powder X-ray diffraction (XRD) and scanning electron microscope (SEM). The cell growth and osteogenic differentiation for glasses has been studied in vitro on sintered glass powder compacts using rat bone marrow mesenchymal stem cells. The as designed glasses are ideal candidates for their potential applications in bone tissue engineering in the form of bioactive glasses as well as glass/GC scaffolds.

  15. Coupled ion redistribution and electronic breakdown in low-alkali boroaluminosilicate glass

    SciTech Connect

    Choi, Doo Hyun; Randall, Clive Furman, Eugene Lanagan, Michael

    2015-08-28

    Dielectrics with high electrostatic energy storage must have exceptionally high dielectric breakdown strength at elevated temperatures. Another important consideration in designing a high performance dielectric is understanding the thickness and temperature dependence of breakdown strengths. Here, we develop a numerical model which assumes a coupled ionic redistribution and electronic breakdown is applied to predict the breakdown strength of low-alkali glass. The ionic charge transport of three likely charge carriers (Na{sup +}, H{sup +}/H{sub 3}O{sup +}, Ba{sup 2+}) was used to calculate the ionic depletion width in low-alkali boroaluminosilicate which can further be used for the breakdown modeling. This model predicts the breakdown strengths in the 10{sup 8}–10{sup 9 }V/m range and also accounts for the experimentally observed two distinct thickness dependent regions for breakdown. Moreover, the model successfully predicts the temperature dependent breakdown strength for low-alkali glass from room temperature up to 150 °C. This model showed that breakdown strengths were governed by minority charge carriers in the form of ionic transport (mostly sodium) in these glasses.

  16. Structural, dielectric and AC conductivity properties of Co2+ doped mixed alkali zinc borate glasses

    NASA Astrophysics Data System (ADS)

    Madhu, B. J.; Banu, Syed Asma; Harshitha, G. A.; Shilpa, T. M.; Shruthi, B.

    2013-02-01

    The Co2+ doped 19.9ZnO+5Li2CO3+25Na2CO3+50B2O3 (ZLNB) mixed alkali zinc borate glasses have been prepared by a conventional melt quenching method. The structural (XRD & FT-IR), dielectric and a.c. conductivity (σac) properties have been investigated. Amorphous nature of these glasses has been confirmed from their XRD pattern. The dielectric properties and electrical conductivity (σac) of these glasses have been studied from 100Hz to 5MHz at the room temperature. Based on the observed trends in the a.c. conductivities, the present glass samples are found to exhibit a non-Debye behavior.

  17. Nepheline crystallization in boron-rich alumino-silicate glasses as investigated by multi-nuclear NMR, Raman, & Mössbauer spectroscopies

    SciTech Connect

    Mccloy, John S.; Washton, Nancy M.; Gassman, Paul L.; Marcial, Jose; Weaver, Jamie L.; Kukkadapu, Ravi K.

    2015-02-01

    A spectroscopic study was conducted on 6 complex simulant nuclear waste glasses using multi-nuclear NMR, Raman and Mössbauer spectroscopies to explore the role of glass-forming elements Si, Al, B, along with Na and Fe and to understand their connectivity with the goal of understanding melt structure precursors to deleterious feldspathoid nepheline-like crystals formation. NMR showed the appearance of two sites for Al, Si, and Na in the samples which crystallized significant amounts of nepheline, and B speciation changed, typically resulting in more B(IV) after nepheline crystallization. Raman spectroscopy suggested a major part of the glass structure is composed of metaborate chains or rings, thus significant numbers of non-bridging oxygens and a separation of the borate from the alumino-silicate network. Mössbauer combined with Fe redox chemical measurements showed that Fe plays a minor role in these glasses, mostly as Fe3+, but that iron oxide spinel forms with nepheline in all cases. Models of the glass network, speciation of B, and allocation of non-bridging oxygens were computed. The Yun-Dell-Bray model failed to predict the observed high concentration of NBO necessary to explain the metaborate features in the Raman spectra, and it largely over-estimated B(IV) fraction. The model assuming Na-Al-Si moieties and using experimental B(IV) fraction predicted a large amount of NBO consistent with Raman spectra. An alternative notation for appreciating the glass network is suggested and then used to investigate the changes the glass due to crystallization of sodium nepheline and the residual glass network. From a theoretical standpoint, it may be preferred to picture nuclear waste glasses by the Lebedev theory of glass structure where “microcrystallites” of ordered nuclei (or embryos) exist in the matrix of more disordered glass.

  18. Crystallization of LiAlSiO4 Glass in Hydrothermal Environments at Gigapascal Pressures-Dense Hydrous Aluminosilicates.

    PubMed

    Spektor, Kristina; Fischer, Andreas; Häussermann, Ulrich

    2016-08-15

    High-pressure hydrothermal environments can drastically reduce the kinetic constraints of phase transitions and afford high-pressure modifications of oxides at comparatively low temperatures. Under certain circumstances such environments allow access to kinetically favored phases, including hydrous ones with water incorporated as hydroxyl. We studied the crystallization of glass in the presence of a large excess of water in the pressure range of 0.25-10 GPa and at temperatures from 200 to 600 °C. The p and T quenched samples were analyzed by powder X-ray diffraction, scanning electron microscopy, and IR spectroscopy. At pressures of 0.25-2 GPa metastable zeolite Li-ABW and stable α-eucryptite are obtained at low and high temperatures, respectively, with crystal structures based on tetrahedrally coordinated Al and Si atoms. At 5 GPa a new, hydrous phase of LiAlSiO4, LiAlSiO3(OH)2 = LiAlSiO4·H2O, is produced. Its crystal structure was characterized from single-crystal X-ray diffraction data (space group P21/c, a = 9.547(3) Å, b = 14.461(5) Å, c = 5.062(2) Å, β = 104.36(1)°). The monoclinic structure resembles that of α-spodumene (LiAlSi2O6) and constitutes alternating layers of chains of corner-condensed SiO4 tetrahedra and chains of edge-sharing AlO6 octahedra. OH groups are part of the octahedral Al coordination and extend into channels provided within the SiO4 tetrahedron chain layers. At 10 GPa another hydrous phase of LiAlSiO4 with presently unknown structure is produced. The formation of hydrous forms of LiAlSiO4 shows the potential of hydrothermal environments at gigapascal pressures for creating truly new materials. In this particular case it indicates the possibility of generally accessing pyroxene-type aluminosilicates with crystallographic amounts of hydroxyl incorporated. This could also have implications to geosciences by representing a mechanism of water storage and transport in the depths of the Earth. PMID:27482770

  19. Specific heat and transport {open_quotes}anomalies{close_quotes} in mixed alkali glasses

    SciTech Connect

    Green, P.F.; Brow, R.K.; Hudgens, J.J.

    1998-11-01

    We show that changes in the relative mole fractions of Li{sub 2}O and Na{sub 2}O in alkali metaphosphate glasses lead to {open_quotes}anomalies{close_quotes} in the specific heat and structural relaxations. The heat capacity change between the liquid and glassy states, {Delta}c{sub p}(T{sub g}), at the calorimetric glass transition temperature, T{sub g}, exhibits a minimum when the mole fractions of Li{sub 2}O and Na{sub 2}O are comparable. Moreover, systematic changes in the temperature dependence of the viscosity, {eta}, i.e., changes in the {open_quotes}fragility{close_quotes} of the system, accompany these changes in mole fraction. This observed dependence of the {open_quotes}fragility{close_quotes} on the mixed alkali ion composition occurs in the absence of apparent changes in the covalent network connectivity which normally accounts for this behavior in glasses. {copyright} {ital 1998 American Institute of Physics.}

  20. Structural and optical investigations of Eu3+ ions in lead containing alkali fluoroborate glasses

    NASA Astrophysics Data System (ADS)

    Deva Prasad Raju, B.; Madhukar Reddy, C.

    2012-06-01

    Lead containing alkali fluoroborate glasses (LAFB) with molar composition of 20PbO + 5CaO + 5ZnO + 10AF + 59B2O3 + 1Eu2O3 (where A = Li, Na and K) were prepared and investigated by the TG-DTA, FT-Raman, optical absorption, fluorescence and decay curve analysis. The influence of alkali content on the structure of borate glasses was investigated by FT-Raman spectroscopy. The thermal properties of the glasses have been studied by TG-DTA analysis. Judd-Ofelt intensity parameters are derived from the absorption spectra and also from the emission spectra under various constraints. The effect of thermalization on the oscillator strengths of the absorption transitions originating from the ground (7F0) and the first excited (7F1) states of Eu3+ ions have been discussed. The J-O intensity parameters obtained by applying thermal correction to 7F0 → 5D2 and 7F6 absorption oscillator strengths were used to calculate the various spectroscopic properties. The predicted values of radiative lifetime (τR) and luminescence intensity branching ratio (βR) are compared with the measured values for 5D0 level. The decay profiles were found to be single exponential in all the three glasses. The spectroscopic properties confirm the potentiality of present LAFB glasses doped with Eu3+ ions as laser host materials to produce an intense red luminescence at 612 nm corresponding to 5D0 → 7F2 emission level and have significant importance in the development of emission rich optical systems.

  1. Preliminary study on calcium aluminosilicate glass as a potential host matrix for radioactive 90Sr--an approach based on natural analogue study.

    PubMed

    Sengupta, Pranesh; Fanara, Sara; Chakraborty, Sumit

    2011-06-15

    Given the environmental-, safety- and security risks associated with sealed radioactive sources it is important to identify suitable host matrices for (90)Sr that is used for various peaceful applications. As SrO promotes phase separation within borosilicate melt, aluminosilicate bulk compositions belonging to anorthite-wollastonite-gehlenite stability field are studied in this work. Tests for their homogeneity, microstructural characteristics and resistance to phase separation narrowed the choice down to the composition CAS11 (CaO=35 wt%, Al(2)O(3)=20 wt%, SiO(2)=45 wt%). We find that up to 30 wt% SrO can be loaded in this glass without phase separation (into Ca, Sr-rich and Sr-poor, Si-rich domains). Leaching behaviour of the glasses differs depending on the content and distribution of Sr. In general, the elemental leach rates determined from conventional PCT experimental procedure yield values better than 10(-7)gcm(-2)day(-1) for both CAS11 base glass as well as SrO doped glass. It was noted that leach rates calculated on the basis of Ca(2+) and Sr(2+) were of the same order and bit higher compared to those calculated on the basis of Si(4+) and Al(3+). During accelerated leaching tests, zeolite and zeolite+epidote were found to have developed on CAS11 base glass and SrO doped glasses respectively. The Sr bulk diffusion coefficients is found to vary from ∼ 10(-15) to 10(-13)cm(2)/s at temperature intervals as high as 725-850°C. Based on the experimental observations, it is suggested that CAS11 glass can be used as host matrix of (90)Sr for various applications of radioactive Sr-pencils. PMID:21477923

  2. Quantification of the boron speciation in alkali borosilicate glasses by electron energy loss spectroscopy

    PubMed Central

    Cheng, Shaodong; Yang, Guang; Zhao, Yanqi; Peng, MingYing; Skibsted, Jørgen; Yue, Yuanzheng

    2015-01-01

    Transmission electron microscopy and related analytical techniques have been widely used to study the microstructure of different materials. However, few research works have been performed in the field of glasses, possibly due to the electron-beam irradiation damage. In this paper, we have developed a method based on electron energy loss spectroscopy (EELS) data acquisition and analyses, which enables determination of the boron speciation in a series of ternary alkali borosilicate glasses with constant molar ratios. A script for the fast acquisition of EELS has been designed, from which the fraction of BO4 tetrahedra can be obtained by fitting the experimental data with linear combinations of the reference spectra. The BO4 fractions (N4) obtained by EELS are consistent with those from 11B MAS NMR spectra, suggesting that EELS can be an alternative and convenient way to determine the N4 fraction in glasses. In addition, the boron speciation of a CeO2 doped potassium borosilicate glass has been analyzed by using the time-resolved EELS spectra. The results clearly demonstrate that the BO4 to BO3 transformation induced by the electron beam irradiation can be efficiently suppressed by doping CeO2 to the borosilicate glasses. PMID:26643370

  3. Investigation of luminescence and spectroscopic properties of Nd3+ions in cadmium alkali borate glasses

    NASA Astrophysics Data System (ADS)

    Mohan, Shaweta; Thind, Kulwant Singh

    2016-07-01

    Neodymium doped cadmium alkali borate glasses having composition 20CdOsbnd 20R2Osbnd 59.5H3BO3sbnd 0.5Nd2O3; (R = Li, Na and K) were prepared by conventional melt-quenching technique. The amorphous nature of the glasses was confirmed by X-ray diffraction studies. The physical properties such as density, refractive index, molar volume, rare earth ion concentration etc. were determined. Optical absorption and fluorescence spectra were recorded. The Judd-Ofelt theory was applied on the optical absorption spectra of the glasses to evaluate the three phenomenological intensity parameters Ω2, Ω4 and Ω6. These parameters were in turn used to predict the radiative properties such as the radiative transition probability (A), radiative lifetime (τR) and branching ratio (βR) for the fluorescent levels of Nd3+ ion in the present glass series. The lasing efficiency of the prepared glasses has been characterized by the spectroscopic quality factor (Ω4/Ω6), the value of which is in the range of 0.2-1.5, typical for Nd3+ in different laser hosts. The variation of Ω2 with the change in alkali oxide has been attributed to the changes in the asymmetry of the ligand field at the rare earth ion site. The shift of the hypersensitive bands, study of the oscillator strengths and the variation of the spectral profile of the transition 4I9/2 → 4F7/2 + 4S3/2 indicate a maximum covalency of Ndsbnd O bond for glass with potassium ions. From the fluorescence spectra, peak wavelength (λp), effective line widths (Δλeff) and stimulated emission cross-section (σp) have been obtained for the three transitions 4F3/2 → 4I9/2,4F3/2 → 4I11/2 and4F3/2 → 4I13/2 of Nd3+ ion. The relatively high values of σp obtained for Nd3+ in present glass system suggest that these materials can be considered as suitable candidates for laser applications. The glass with potassium ions shows the highest value of the stimulated emission cross-section.

  4. Glass corrosion in natural environment

    NASA Technical Reports Server (NTRS)

    Thorpe, Arthur N.

    1989-01-01

    A series of studies of the effects of solutes which appear in natural aqueous environments, specifically Mg and Al, under controlled conditions, permit characterization of the retardation of silicate glass leaching in water containing such solutes. In the case of Mg the interaction with the glass appears to consist of exchange with alkali ions present in the glass to a depth of several microns. The effect of Al can be observed at much lower levels, indicating that the mechanism in the case of Al involves irreversible formation of aluminosilicate species at the glass surface.

  5. Fluorescence investigation of Ho3+ in Yb3+ sensitized mixed-alkali bismuth gallate glasses.

    PubMed

    Lin, H; Zhang, Y Y; Pun, E Y B

    2008-12-15

    Efficient 2.0 microm infrared and visible upconversion emissions have been observed in Ho3+/Yb3+ co-doped mixed-alkali bismuth gallate (LKBBG) glasses having a maximum-phonon energy of 673 cm(-1). The Judd-Ofelt parameters Omega2, Omega4 and Omega6 of Ho3+ indicate that there is a high asymmetry and strong covalent environment in LKBBG glasses. The large absorption and emission cross-sections of Yb3+ confirm that it is a suitable sensitizer for capturing and transferring pump energy to Ho3+. The emission cross-section profile for the 5I7-->5I8 transition is derived using the reciprocity method and the peak value is 5.54 x 10(-21)cm2, which is much larger than the value in fluorozircoaluminate glasses. LKBBG glasses exhibit low maximum-phonon energy and large refractive index, and it is possible to achieve an effective 1.66 microm U-band emission of Ho3+ under 900 nm laser radiation. PMID:18586553

  6. An alkali-free barium borosilicate viscous sealing glass for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Hsu, Jen-Hsien; Kim, Cheol-Woon; Brow, Richard K.; Szabo, Joe; Crouch, Ray; Baird, Rob

    2014-12-01

    An alkali-free, alkaline earth borosilicate glass (designated G102) has been developed as a viscous sealant for use with solid oxide fuel cells (SOFCs). The glass possesses the requisite viscosity, electrical resistivity, and thermal and chemical stability under SOFC operating conditions to act as a reliable sealant. Sandwich seals between aluminized stainless steel and a YSZ/NiO-YSZ bilayer survived 148 thermal cycles (800 °C to room temperature) in both oxidizing and reducing atmospheres at a differential pressure of ∼3.4 kPa (0.5 psi) without failure. For sandwich seals that were held at 800 °C for up to 2280 h in air, G102 resisted crystallization, there were limited interactions at the G102/YSZ interface, but BaAl2Si2O8 crystals formed at the glass/metal interface because of the reaction between the glass and the aluminized steel. Sandwich seals that were intentionally cracked by thermal shock resealed to became hermetic upon reheating to temperatures as low as 744 °C.

  7. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: thermal cycle stability and chemical compatibility

    SciTech Connect

    Chou, Y. S.; Thomsen, Edwin C.; Williams, Riley T.; Choi, Jung-Pyung; Canfield, Nathan L.; Bonnett, Jeff F.; Stevenson, Jeffry W.; Shyam, Amit; Lara-Curzio, E.

    2011-03-01

    An alkali silicate glass (SCN-1) is currently being evaluated as a candidate sealing glass for solid oxide fuel (SOFC) applications. The glass containing ~17 mole% alkalis (K2O and Na2O) remains vitreous and compliant during SOFC operation, unlike conventional SOFC sealing glasses, which experience substantial devitrification after the sealing process. The non-crystallizing compliant sealing glass has lower glass transition and softening temperatures since the microstructure remains glassy without significant crystallite formation, and hence can relieve or reduce residual stresses and also has the potential for crack healing. Sealing approaches based on compliant glass will also need to satisfy all the mechanical, thermal, chemical, physical, and electrical requirements for SOFC applications, not only in bulk properties but also at sealing interfaces. In this first of a series of papers we will report the thermal cycle stability of the glass when sealed between two SOFC components, i.e., a NiO/YSZ anode supported YSZ bilayer and a coated ferritic stainless steel interconnect material. High temperature leak rates were monitored versus thermal cycles between 700-850oC using back pressures ranging from 0.2 psi to 1.0 psi. Isothermal stability was also evaluated in a dual environment consisting of flowing dilute H2 fuel versus ambient air. In addition, chemical compatibility at the alumina and YSZ interfaces was examined with scanning electron microscopy and energy dispersive spectroscopy. The results shed new light on the topic of SOFC glass seal development.

  8. NMR studies of Phase Transitions in Alkali Metal Films on Glass Substrates

    NASA Astrophysics Data System (ADS)

    Ishikawa, K.; Patton, B.; Jau, Y.-Y.; Happer, W.

    2006-05-01

    We report NMR spectra of thin ^87Rb films on glass in an investigation of the ``curing'' process which is commonly observed in alkali cells. The cells were cycled in temperature over a range of 5 C to 170 C and the rubidium solid-liquid phase transition was studied. The spectra of these two phases are resolvable at 9.4 T because of their different Knight shifts. Hysteresis in the observed phases confirmed reports of a curing phenomenon, and after time a supercooled liquid Rb peak could be detected at temperatures far below the predicted freezing point of 39 C. Moreover, a third NMR peak was observed at temperatures below the melting point whose frequency varied with temperature and spanned the solid and liquid frequency ranges. To our knowledge, this is the first study to characterize this additional resonance. We have also performed analogous measurements on ^133Cs films.

  9. Structure of hydrous aluminosilicate glasses along the diopside anorthite join: A comprehensive one- and two-dimensional 1H and 27Al NMR study

    NASA Astrophysics Data System (ADS)

    Xue, Xianyu; Kanzaki, Masami

    2008-05-01

    We have taken a systematic approach utilizing advanced solid-state NMR techniques to gain new insights into the controversial issue concerning the dissolution mechanisms of water in aluminosilicate melts (glasses). A series of quenched anhydrous and hydrous (˜2 wt% H 2O) glass samples along the diopside (Di, CaMgSi 2O 6)—anorthite (An, CaAl 2Si 2O 8) join with varying An components (0, 20, 38, 60, 80, and 100 mol %) have been studied. A variety of NMR techniques, including one-dimensional (1D) 1H and 27Al MAS NMR, and 27Al → 1H cross-polarization (CP) MAS NMR, as well as two-dimensional (2D) 1H double-quantum (DQ) MAS NMR, 27Al triple-quantum (3Q) MAS NMR, and 27Al → 1H heteronuclear correlation NMR (HETCOR) and 3QMAS/HETCOR NMR, have been applied. These data revealed the presence of SiOH, free OH ((Ca,Mg)OH) and AlOH species in the hydrous glasses, with the last mostly interconnected with Si and residing in the more polymerized parts of the structure. Thus, there are no fundamental differences in water dissolution mechanisms for Al-free and Al-bearing silicate melts (glasses), both involving two competing processes: the formation of SiOH/AlOH that is accompanied by the depolymerization of the network structure, and the formation of free OH that has an opposite effect. The latter is more important for depolymerized compositions corresponding to mafic and ultramafic magmas. Aluminum is dominantly present in four coordination (Al IV), but a small amount of five-coordinate Al (Al V) is also observed in all the anhydrous and hydrous glasses. Furthermore, six-coordinate Al (Al VI) is also present in most of the hydrous glasses. As Al of higher coordinations are favored by high pressure, Al VIOH and Al VOH may become major water species at higher pressures corresponding to those of the Earth's mantle.

  10. Probing silicon and aluminium chemical environments in silicate and aluminosilicate glasses by solid state NMR spectroscopy and accurate first-principles calculations

    NASA Astrophysics Data System (ADS)

    Gambuzzi, Elisa; Pedone, Alfonso; Menziani, Maria Cristina; Angeli, Frédéric; Caurant, Daniel; Charpentier, Thibault

    2014-01-01

    Silicon and aluminium chemical environments in silicate and aluminosilicate glasses with compositions 60SiO2·20Na2O·20CaO (CSN), 60SiO2·20Al2O3·20CaO (CAS), 78SiO2·11Al2O3·11Na2O (NAS) and 60SiO2·10Al2O3·10Na2O·20CaO (CASN) have been investigated by 27Al and 29Si solid state magic angle spinning (MAS) and multiple quantum MAS (MQMAS) nuclear magnetic resonance (NMR) experiments. To interpret the NMR data, first-principles calculations using density functional theory were performed on structural models of these glasses. These models were generated by Shell-model molecular dynamics (MD) simulations. The theoretical NMR parameters and spectra were computed using the gauge including projected augmented wave (GIPAW) method and spin-effective Hamiltonians, respectively. This synergetic computational-experimental approach offers a clear structural characterization of these glasses, particularly in terms of network polymerization, chemical disorder (i.e. Si and Al distribution in second coordination sphere) and modifier cation distributions. The relationships between the local structural environments and the 29Si and 27Al NMR parameters are highlighted, and show that: (i) the isotropic chemical shift of both 29Si and 27Al increases of about +5 ppm for each Al added in the second sphere and (ii) both the 27Al and 29Si isotropic chemical shifts linearly decrease with the reduction of the average Si/Al-O-T bond angle. Conversely, 27Al and 29Si NMR parameters are much less sensitive to the connectivity with triple bridging oxygen atoms, precluding their indirect detection from 27Al and 29Si NMR.

  11. Physical, structural and spectroscopic investigations of Sm3+ doped ZnO mixed alkali borate glass

    NASA Astrophysics Data System (ADS)

    Sailaja, B.; Joyce Stella, R.; Thirumala Rao, G.; Jaya Raja, B.; Pushpa Manjari, V.; Ravikumar, R. V. S. S. N.

    2015-09-01

    Glass of 20ZnO-15 Li2O-15 Na2O-49.9 B2O3 doped with 0.1 mol% of Sm3+ (ZLNB) was prepared by the melt quenching technique. Physical properties were studied and analysed. The XRD studies confirm the amorphous nature of sample. The FT-IR spectral investigation discloses the BO3, BO4 groups, H and OH bonds. Optical absorption and emission spectra were recorded and characterized. Judd-Ofelt theory was applied to f ↔ f transitions to evaluate Judd-Ofelt intensity parameters (Ωλ). The oscillator strengths and bonding parameters were determined from absorption spectra. The trend observed was Ω4 > Ω6 > Ω2. High value of Ω4 reveals higher rigidity and covalency around the Sm3+ ion. Low value of Ω2 implies ionic nature of ligands and site symmetry around Sm3+ ion. luminescence data and Judd-Ofelt parameters Ωλ (λ = 2, 4, and 6) were used to evaluate various radiative probabilities like spontaneous radiative emission probabilities (AR), radiative lifetime (τR) and branching ratios (βR) stimulated emission cross section (σe) and CIE colour coordinates were measured, CCT temperature evaluated and the values were used to ascertain potential laser transitions at the optimum mixed alkali effect observed for the glass sample prepared. The preparedness of the material as the efficient laser active material is examined.

  12. Tellurite glass as a waste form for mixed alkali-chloride waste streams: Candidate materials selection and initial testing

    NASA Astrophysics Data System (ADS)

    Riley, Brian J.; Rieck, Bennett T.; McCloy, John S.; Crum, Jarrod V.; Sundaram, S. K.; Vienna, John D.

    2012-05-01

    Tellurite glasses have historically been shown to host large concentrations of halides. They are here considered for the first time as a waste form for immobilizing chloride wastes, such as may be generated in the proposed molten alkali salt electrochemical separations step in nuclear fuel reprocessing. Key properties of several tellurite glasses are determined to assess acceptability as a chloride waste form. TeO2 glasses with other oxides (PbO, Al2O3 + B2O3, WO3, P2O5, or ZnO) were fabricated with and without 10 mass% of a simulated (non-radioactive) mixed alkali, alkaline-earth, and rare earth chloride waste. Measured chemical durability is compared for the glasses, as determined by the product consistency test (PCT), a common standardized chemical durability test often used to validate borosilicate glass waste forms. The glass with the most promise as a waste form is the TeO2-PbO system, as it offers good halide retention, a low sodium release (by PCT) comparable with high-level waste silicate glass waste forms, and a high storage density.

  13. Thorium and cerium chemical behaviour in ion-irradiated alkali-borosilicate glasses

    NASA Astrophysics Data System (ADS)

    Trocellier, P.; Haddi, A.; Poissonnet, S.; Bonnaillie, P.; Serruys, Y.

    2006-08-01

    Simple alkali-borosilicate glasses containing SiO2-B2O3-Li2O-Na2O and only one or two transition metal oxides (CeO2 and/or ThO2) have been synthesized by melting the stoichiometric powder mixture at 1100 °C in a platinum crucible. Thorium and cerium were used as chemical analogs of minor actinides (Pu and Am). Th is a purely tetravalent element, although Ce can be tetravalent or trivalent. Glass samples were submitted to aqueous leaching tests at 90 °C in deionised water for one week, with or without having previously been ion-irradiated. The irradiation experiments were conducted in the nuclear energy loss regime. Kr ions supplied by a 1 MV electrostatic Van de Graaff accelerator, were used to produce displacement cascades in the first hundreds of nanometers beneath the sample's surfaces. The leached samples were then characterized by scanning electron microscopy (SEM), electron microprobe analysis (EMA) and ion beam analytical (IBA) methods: Rutherford backscattering spectrometry and elastic recoil detection analysis (RBS and ERDA), proton-induced X-ray or gamma ray emission (PIXE and PIGE). Th and Ce are shown to be enriched in the near surface region of leached glasses due to the extremely low solubility of their hydroxides. The effect of surface damage on the chemical behaviour of Th and Ce is then detailed. The possibility for Ce(IV) to be reduced as Ce(III) during ion-irradiation just before leaching and its consequences on the relative solubility of corresponding chemical species is discussed in terms of hydroxide solubility thermodynamical equilibria.

  14. Studies on the preparation and plasma spherodization of yttrium aluminosilicate glass microspheres for their potential application in liver brachytherapy

    NASA Astrophysics Data System (ADS)

    Sreekumar, K. P.; Saxena, S. K.; Kumar, Yogendra; Thiyagarajan, T. K.; Dash, Ashutosh; Ananthapadmanabhan, P. V.; Venkatesh, Meera

    2010-02-01

    Plasma spheroidization exploits the high temperature and high enthalpy available in the thermal plasma jet to melt irregularly shaped powder particles and quench them to get dense spherical particles. Plasma spheroidization is a versatile process and can be applied to metals, ceramics, alloys and composites to obtain fine spherical powders. Radioactive microspheres incorporated with high energetic beta emitting radioisotopes have been reported to be useful in the palliative treatment of liver cancer. These powders are to be prepared in closer range of near spherical morphology in the size range 20-35 microns. Inactive glass samples were prepared by heating the pre-calculated amount of glass forming ingredients in a recrystallized alumina crucible. The glass was formed by keeping the glass forming ingredients at 1700°C for a period of three hours to form a homogeneous melt. After cooling, the glass was recovered from the crucible by crushing and was subsequently powdered mechanically with the help of mortar and pestle. This powder was used as the feed stock for plasma spheroidization using an indigenously developed 40 kW plasma spray system. Experiments were carried out at various operating parameters. The operating parameters were optimised to get spheroidised particles. The powder was sieved to get the required size range before irradiation.

  15. Effects of Fiber Content on Mechanical Properties of CVD SiC Fiber-Reinforced Strontium Aluminosilicate Glass-Ceramic Composites

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.

    1996-01-01

    Unidirectional CVD SiC(f)(SCS-6) fiber-reinforced strontium aluminosilicate (SAS) glass-ceramic matrix composites containing various volume fractions, approximately 16 to 40 volume %, of fibers were fabricated by hot pressing at 1400 C for 2 h under 27.6 MPa. Monoclinic celsian, SrAl2Si2O8, was the only crystalline phase formed, with complete absence of the undesired hexacelsian phase, in the matrix. Room temperature mechanical properties were measured in 3-point flexure. The matrix microcracking stress and the ultimate strength increased with increase in fiber volume fraction, reached maximum values for V(sub f) approximately equal to 0.35, and degraded at higher fiber loadings. This degradation in mechanical properties is related to the change in failure mode, from tensile at lower V(sub f) to interlaminar shear at higher fiber contents. The extent of fiber loading did not have noticeable effect on either fiber-matrix debonding stress, or frictional sliding stress at the interface. The applicability of micromechanical models in predicting the mechanical properties of the composites was also examined. The currently available theoretical models do not appear to be useful in predicting the values of the first matrix cracking stress, and the ultimate strength of the SCS-6/SAS composites.

  16. Mechanisms of optical losses in the 5D4 and 5D3 levels in Tb3+ doped low silica calcium aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    dos Santos, J. F. M.; Terra, I. A. A.; Astrath, N. G. C.; Guimarães, F. B.; Baesso, M. L.; Nunes, L. A. O.; Catunda, T.

    2015-02-01

    Trivalent Tb-doped materials exhibit strong emission in the green and weak emission in the UV-blue levels. Usually, this behavior is attributed to the cross relaxation (CR) process. In this paper, the luminescence properties of Tb3+-doped low silica calcium aluminosilicate glasses are analyzed for UV (λexc = 325 nm) and visible (488 nm) excitations. Under 325 nm excitation, the intensity of green luminescence increases proportionally to Tb3+ concentration. However, the blue luminescence intensity is strongly reduced with the increase of concentration from 0.5-15.0 wt. %. In the case of 488 nm excitation, a saturation behavior of the green emission is observed at intensities two orders of magnitude smaller than expected for bleaching of the ground state population. Using a rate equation model, we showed that this behavior can be explained by an excited state absorption cross section two orders of magnitude larger than the ground state absorption. The blue emission is much weaker than expected from our rate equations (325 nm and 488 nm excitation). We concluded that only the CR process cannot explain the overall feature of measured luminescence quenching in the wide range of Tb3+ concentrations. Cooperative upconversion from a pair of excited ions (5D3:5D3 or 5D3:5D4) and other mechanisms involving upper lying states (4f5d, charge transfer, host matrix, defects, etc.) may play a significant role.

  17. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: Thermal cycle stability and chemical compatibility

    NASA Astrophysics Data System (ADS)

    Chou, Yeong-Shyung; Thomsen, E. C.; Williams, R. T.; Choi, J.-P.; Canfield, N. L.; Bonnett, J. F.; Stevenson, J. W.; Shyam, A.; Lara-Curzio, E.

    2011-03-01

    An alkali silicate glass (SCN-1) is currently being evaluated as a candidate sealing glass for solid oxide fuel cell (SOFC) applications. The glass containing ∼17 mole% alkalis (K2O and Na2O) remains vitreous and compliant during SOFC operation, unlike conventional SOFC sealing glasses, which experience substantial devitrification after the sealing process. The non-crystallizing compliant sealing glass has lower glass transition and softening temperatures since the microstructure remains glassy without significant crystallite formation, and hence can relieve or reduce residual stresses and also has the potential for crack healing. Sealing approaches based on compliant glass will also need to satisfy all the mechanical, thermal, chemical, physical, and electrical requirements for SOFC applications, not only in bulk properties but also at sealing interfaces. In this first of a series of papers we will report the thermal cycle stability of the glass when sealed between two SOFC components, i.e., a NiO/YSZ anode supported YSZ bilayer and a coated ferritic stainless steel interconnect material. High temperature leak rates were monitored versus thermal cycles between 700 and 850 °C using back pressures ranging from 1.4 to 6.8 kPa (0.2-1.0 psi). Isothermal stability was also evaluated in a dual environment consisting of flowing dilute H2 fuel versus ambient air. In addition, chemical compatibility at the alumina and YSZ interfaces was examined with scanning electron microscopy and energy dispersive spectroscopy. The results shed new light on the topic of SOFC glass seal development.

  18. Homogeneity of bismuth-distribution in bismuth-doped alkali germanate laser glasses towards superbroad fiber amplifiers.

    PubMed

    Zhao, Yanqi; Wondraczek, Lothar; Mermet, Alain; Peng, Mingying; Zhang, Qinyuan; Qiu, Jianrong

    2015-05-01

    Compared to rare-earth doped glasses, bismuth-doped glasses hold promise for super-broadband near-infrared (NIR) photoemission and potential applications in optical amplification. However, optically active bismuth centers are extremely sensitive to the properties of the surrounding matrix, and also to processing conditions. This is strongly complicating the exploitation of this class of materials, because functional devices require a very delicate adjustment of the redox state of the bismuth species, and its distribution throughout the bulk of the material. It also largely limits some of the conventional processing routes for glass fiber, which start from gas phase deposition and may require very high processing temperature. Here, we investigate the influence of melting time and alkali addition on bismuth-related NIR photoluminescence from melt-derived germanate glasses. We show that the effect of melting time on bismuth-related absorption and NIR photoemission is primarily through bismuth volatilization. Adding alkali oxides as fluxing agents, the melt viscosity can be lowered to reduce either the glass melting temperature, or the melting time, or both. At the same time, however, alkali addition also leads to increasing mean-field basicity, what may reduce the intensity of bismuth-related NIR emission. Preferentially using Li2O over Na2O or K2O presents the best trade-off between those above factors, because its local effect may be adverse to the generally assumed trend of the negative influence of more basic matrix composition. This observation provides an important guideline for the design of melt-derived Bi-doped glasses with efficient NIR photoemission and high optical homogeneity. PMID:25969328

  19. Alkali Silicate Glass Coatings for Mitigating the Risks of Tin Whiskers

    NASA Astrophysics Data System (ADS)

    Hillman, Dave; Wilcoxon, Ross; Lower, Nate; Grossman, Dan

    2015-12-01

    Alkali silicate glass (ASG) coatings were investigated as a possible method for inhibiting tin whisker initiation and growth. The aqueous-based ASG formulations used in this study were deposited with equipment and conditions that are typical of those used to apply conventional conformal coatings. Processes for controlling ASG coating properties were developed, and a number of ASG-based coating combinations were applied to test components with pure tin surfaces. Coatings were applied both in a laboratory environment at Rockwell Collins and in a manufacturing environment at Plasma Ruggedized Solutions. Testing in elevated humidity/temperature environments and subsequent inspection of the test articles identified coating combinations that inhibited tin whisker growth as well as other material combinations that actually accelerated tin whisker growth. None of the coatings evaluated in this study, including conventional acrylic and Parylene conformal coatings, completely prevented the formation of tin whiskers. Two of the coatings were particularly effective at reducing the risks of whisker growth, albeit through different mechanisms. Parylene conformal coating almost, but not completely, eliminated whisker formation, and only a few tin whiskers were found on these surfaces during the study. A composite of ASG and alumina nanoparticles inhibited whisker formation to a lesser degree than Parylene, but did disrupt whisker growth mechanisms so as to inhibit the formation of long, and more dangerous, tin whiskers. Additional testing also demonstrated that the conformal coatings had relatively little effect on the dielectric loss of a stripline test structure operating at frequencies over 30 GHz.

  20. Role of glass structure in defining the chemical dissolution behavior, bioactivity and antioxidant properties of zinc and strontium co-doped alkali-free phosphosilicate glasses.

    PubMed

    Kapoor, Saurabh; Goel, Ashutosh; Tilocca, Antonio; Dhuna, Vikram; Bhatia, Gaurav; Dhuna, Kshitija; Ferreira, José M F

    2014-07-01

    We investigated the structure-property relationships in a series of alkali-free phosphosilicate glass compositions co-doped with Zn(2+) and Sr(2+). The emphasis was laid on understanding the structural role of Sr(2+) and Zn(2+) co-doping on the chemical dissolution behavior of glasses and its impact on their in vitro bioactivity. The structure of glasses was studied using molecular dynamics simulations in combination with solid state nuclear magnetic resonance spectroscopy. The relevant structural properties are then linked to the observed degradation behavior, in vitro bioactivity, osteoblast proliferation and oxidative stress levels. The apatite-forming ability of glasses has been investigated by X-ray diffraction, infrared spectroscopy and scanning electron microscopy-energy-dispersive spectroscopy after immersion of glass powders/bulk in simulated body fluid (SBF) for time durations varying between 1h and 14 days, while their chemical degradation has been studied in Tris-HCl in accordance with ISO 10993-14. All the glasses exhibit hydroxyapatite formation on their surface within 1-3h of their immersion in SBF. The cellular responses were observed in vitro on bulk glass samples using human osteosarcoma MG63 cell line. The dose-dependent cytoprotective effect of glasses with respect to the concentration of zinc and strontium released from the glasses is also discussed. PMID:24709542

  1. Chemical Vapor Deposited SiC (SCS-0) Fiber-Reinforced Strontium Aluminosilicate Glass-Ceramic Composites

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.

    1997-01-01

    Unidirectional SrO Al2O3 2SiO2 glass-ceramic matrix composites reinforced with uncoated Chemical Vapor Deposited (CVD) SiC (SCS-0) fibers have been fabricated by hot-pressing under appropriate conditions using the glass-ceramic approach. Almost fully dense composites having a fiber volume fraction of 0.24 have been obtained. Monoclinic celsian, SrAl2Si2O8, was the only crystalline phase observed in the matrix by x-ray diffraction. No chemical reaction was observed between the fiber and the matrix after high temperature processing. In three-point flexure, the composite exhibited a first matrix cracking stress of approx. 231 +/- 20 MPa and an ultimate strength of 265 +/- 17 MPa. Examination of fracture surfaces revealed limited short length fiber pull-out. From fiber push-out, the fiber/matrix interfacial debonding and frictional strengths were evaluated to be approx. 17.5 +/- 2.7 MPa and 11.3 +/- 1.6 MPa, respectively. Some fibers were strongly bonded to the matrix and could not be pushed out. The micromechanical models were not useful in predicting values of the first matrix cracking stress as well as the ultimate strength of the composites.

  2. Ionic transport in mixed-alkali glasses: hop through the distinctly different conduction pathways of low dimensionality

    NASA Astrophysics Data System (ADS)

    Rim, Young-Hoon; Kim, Mac; Kim, Jeong Eun; Yang, Yong Suk

    2013-02-01

    A feature common to various solids, including single-alkali (SA) and mixed-alkali (MA) glasses, is a frequency-dependent ionic conductivity that shows the power law and the linear behavior with frequency. In spite of the advances made, the origin of this behavior continues to be controversial. We report our measurements of the conductivity of a series of MA borate glasses (Li1-xAx)2B4O7 (A = Na, K, Rb, Cs; 0 ⩽ x ⩽ 1.0) in the frequency range of 100 Hz-15 MHz and in the temperature range from 300 K to less than the glass transition temperature Tg . Using a self-similar spatial structure model, we show that the real process of ionic transport in the SA and the MA glass systems can be described by the fractional kinetic equations containing non-integer integration/differentiation operators. In the procedure of a systematic deduction of the ionic transport in glass systems, we obtained two important insights. Firstly, the time-dependent conductivity σ(t) ˜ exp (t/τ c)α reproduces the empirical expression of mean square displacement of the mobile ions ˜tα as a first approximation of ions moving through the fractal pathway and leads to the universal power-law behavior at frequency scales. Secondly, the modified fractional Rayleigh equation with a repulsive interaction provides a quantitative explanation for experimental findings on the SA and the MA glasses. Investigations on the power-law exponent β in the SA and the MA borate glasses indicate that the ions move through the different branches of the fractal structured conduction pathways due to the structural character, associated with a site mismatch effect, and Coulomb blockade by the randomly distributed ions.

  3. Effect of Li 2O content on physical and structural properties of vanadyl doped alkali zinc borate glasses

    NASA Astrophysics Data System (ADS)

    Raghavendra Rao, T.; Rama Krishna, Ch.; Udayachandran Thampy, U. S.; Venkata Reddy, Ch.; Reddy, Y. P.; Sambasiva Rao, P.; Ravikumar, R. V. S. S. N.

    2011-05-01

    The effect of Li 2O content in vanadyl doped 20ZnO+ xLi 2O+(30- x)Na 2O+50B 2O 3 (5≤ x≥25) glasses has been studied with respect to their physical and structural properties. The absence of sharp peaks in XRD spectra of these glass samples confirms the amorphous nature. The physical parameters like density, refractive index, ionic concentration and electronic polarizability vary non-linearly with x mol% depending on the diffusivities of alkali ions. EPR and optical absorption spectra reveal that the resonance signals are characteristics of VO 2+ ions in tetragonally compressed octahedral site. Spin-Hamiltonian, crystal field, tetragonal field and bonding parameters are found to be in good agreement with the other reported glass systems. The tetragonal distortion ( g⊥- g∥) and Dt reveals that their values vary non-linearly with Li 2O content and reaches a minimum at x=10 mol%. An anomaly of character has been observed in all the properties of vanadyl doped glass systems, which gives a clear indication of mixed alkali effect.

  4. Characterization of Cr3+ doped mixed alkali ions effect in zinc borate glasses - Physical and spectroscopic investigations

    NASA Astrophysics Data System (ADS)

    Rama Sundari, G.; Pushpa Manjari, V.; Raghavendra Rao, T.; Satish, D. V.; Rama Krishna, Ch.; Venkata Reddy, Ch.; Ravikumar, R. V. S. S. N.

    2014-06-01

    The physical and structural properties of Cr3+ doped 19.9 ZnO + xLi2O + (30 - x) Na2O + 50B2O3 (5 ⩽ x ⩽ 25) (ZLNB) glasses have been studied. Powder X-ray diffraction patterns indicated the amorphous nature of the glass samples. The physical parameters of all the glasses were also evaluated with respect to the composition. They exhibit the non-linearity providing the evidence for mixed alkali ions effect. The infrared spectra of the glasses in the range 400-4000 cm-1 showed the presence of BO3 and BO4 local structures in all the glass systems. No boroxol ring formation was observed in the structure of these glasses. Optical absorption and electron paramagnetic resonance studies were carried out at room temperature. From the optical absorption data various optical parameters such as optical band gap, Urbach energy were evaluated. Crystal field and Racah parameters are evaluated from optical absorption spectra. The EPR spectra of Cr3+ doped ZLNB glasses exhibited resonance signals at g = 4.066 and g = 1.9779 characteristic of Cr3+ ions. The evaluated bonding parameters suggest the covalent nature.

  5. High thermal neutron flux effects on structural and macroscopic properties of alkali-borosilicate glasses used as neutron guide substrate

    NASA Astrophysics Data System (ADS)

    Boffy, R.; Peuget, S.; Schweins, R.; Beaucour, J.; Bermejo, F. J.

    2016-05-01

    The behaviour of four alkali-borosilicate glasses under homogeneous thermal neutron irradiation has been studied. These materials are used for the manufacturing of neutron guides which are installed in most facilities as devices to transport neutrons from intense sources such as nuclear reactors or spallation sources up to scientific instruments. Several experimental techniques such as Raman, NMR, SANS and STEM have been employed in order to understand the rather different macroscopic behaviour under irradiation of materials that belong to a same glass family. The results have shown that the remarkable glass shrinking observed for neutron doses below 0.5 ·1018 n/cm2 critically depends upon the presence of domains where silicate and borate network do not mix.

  6. [Raman active vibrations of aluminosilicates].

    PubMed

    Pan, Feng; Yu, Xue-hui; Mo, Xuan-xue; You, Jing-lin; Wang, Chen; Chen, Hui; Jiang, Guo-chang

    2006-10-01

    Raman spectra of aluminosilicate minerals, namely kyanite, andalusite, and sillimanite and K2O-Al2O3-SiO2 glasses were recorded. Four alumino-silicon tetrahedral model clusters were calculated by self-consistent (SCF) molecular orbital ab-ini-tio calculation of the quantum chem (QC) method. The result shows a decrease tendency in Raman frequencies in the 800-1200 cm(-1) frequency region with increase in four-coordinated Al content, which is assigned to the Si--Onb symmetry stretching vibrations. The Raman spectra in the 700-800 cm(-1) frequency region is attributed to Al-Onb symmetry stretching vibrations. PMID:17205741

  7. Identifying glass compositions in fly ash

    NASA Astrophysics Data System (ADS)

    Aughenbaugh, Katherine; Stutzman, Paul; Juenger, Maria

    2016-01-01

    In this study, four Class F fly ashes were studied with a scanning electron microscope; the glassy phases were identified and their compositions quantified using point compositional analysis with k-means clustering and multispectral image analysis. The results showed that while the bulk oxide contents of the fly ashes were different, the four fly ashes had somewhat similar glassy phase compositions. Aluminosilicate glasses (AS), calcium aluminosilicate glasses (CAS), a mixed glass, and, in one case, a high iron glass were identified in the fly ashes. Quartz and iron crystalline phases were identified in each fly ash as well. The compositions of the three main glasses identified, AS, CAS, and mixed glass, were relatively similar in each ash. The amounts of each glass were varied by fly ash, with the highest calcium fly ash containing the most of calcium-containing glass. Some of the glasses were identified as intermixed in individual particles, particularly the calcium-containing glasses. Finally, the smallest particles in the fly ashes, with the most surface area available to react in alkaline solution, such as when mixed with portland cement or in alkali-activated fly ash, were not different in composition than the large particles, with each of the glasses represented. The method used in the study may be applied to a fly ash of interest for use as a cementing material in order to understand its potential for reactivity.

  8. Element specificity of ortho-positronium annihilation for alkali-metal loaded SiO{sub 2} glasses

    SciTech Connect

    Sato, K.; Hatta, T.

    2015-03-07

    Momentum distributions associated with ortho-positronium (o-Ps) pick-off annihilation photon are often influenced by light elements, as, e.g., carbon, oxygen, and fluorine. This phenomenon, so-called element specificity of o-Ps pick-off annihilation, has been utilized for studying the elemental environment around the open spaces. To gain an insight into the element specificity of o-Ps pick-off annihilation, the chemical shift of oxygen 1s binding energy and the momentum distributions associated with o-Ps pick-off annihilation were systematically investigated for alkali-metal loaded SiO{sub 2} glasses by means of X-ray photoelectron spectroscopy and positron-age-momentum correlation spectroscopy, respectively. Alkali metals introduced into the open spaces surrounded by oxygen atoms cause charge transfer from alkali metals to oxygen atoms, leading to the lower chemical shift for the oxygen 1s binding energy. The momentum distribution of o-Ps localized into the open spaces is found to be closely correlated with the oxygen 1s chemical shift. This correlation with the deepest 1s energy level evidences that the element specificity of o-Ps originates from pick-off annihilation with orbital electrons, i.e., dominantly with oxygen 2p valence electrons and s electrons with lower probability.

  9. Structure of glasses containing transition metal ions. Progress report, February 1, 1980-January 31, 1981

    SciTech Connect

    White, W.B.; Fox, K.; Herman, J.S.; Houser, C.; Nelson, C.

    1981-01-01

    This research is concerned with the structure and properties of insulator glasses, particularly as these are modified by transition metal ions in solution. This progress report spans a one-year period and describes the status of the work two-thirds into the sixth contract year. Work on the host glasses has been concentrated on the alkali borosilicate, alkali aluminosilicate and alkali-gallia-silicate glasses. The main interest here is the structure setting for aluminum. The optical absorption spectra of nickel and iron in a variety of glasses have been examined. Utilization of luminescence in addition to optical absorption spectra has permitted the identification of several iron arrangements in glass. The investigation of diffusion processes, particularly hydrogen diffusion, by sputter-induced photon spectrometry (SIPS) has moved from qualitative demonstration to quantitative calculation.

  10. DEVELOPMENT OF GLASS COMPOSITIONS TO IMMOBILIZE ALKALI, ALKALINE EARTH, LANTHANIDE AND TRANSITION METAL FISSION PRODUCTS FROM NUCLEAR FUEL REPROCESSING

    SciTech Connect

    Marra, J.; Billings, A.

    2009-06-24

    The Advanced Fuel Cycle Initiative (AFCI) waste management strategy revolves around specific treatment of individual or groups of separated waste streams. A goal for the separations processes is to efficiently manage the waste to be dispositioned as high level radioactive waste. The Advanced Fuel Cycle Initiative (AFCI) baseline technology for immobilization of the lanthanide (Ln) and transition metal fission product (TM) wastes is vitrification into a borosilicate glass. A current interest is to evaluate the feasibility of vitrifying combined waste streams to most cost effectively immobilize the wastes resulting from aqueous fuel reprocessing. Studies showed that high waste loadings are achievable for the Ln only (Option 1) stream. Waste loadings in excess of 60 wt % (on a calcined oxide basis) were demonstrated via a lanthanide borosilicate (LaBS) glass. The resulting glasses had excellent relative durability as determined by the Product Consistency Test (PCT). For a combined Ln and TM waste stream glass (Option 2), noble metal solubility was found to limit waste loading. However, the measured PCT normalized elemental releases for this glass were at least an order of magnitude below that of Environmental Assessment (EA) glass. Current efforts to evaluate the feasibility of vitrifying combined Ln, TM, alkali (Cs is the primary radionuclide of concern) and alkaline earth (Sr is the primary radionuclide of concern) wastes (Option 3) have shown that these approaches are feasible. However, waste loading limitations with respect to heat load (Cs/Sr loading), molybdenum solubility and/or noble metal solubility will likely be realized and must be considered in determining the cost effectiveness of these approaches.

  11. Effect of SiO2 and Al2O3 addition on the density, Tg and CTE of mixed alkali - alkaline earth borate glass

    NASA Astrophysics Data System (ADS)

    Deshpande, A. M.; Deshpande, V. K.

    2009-07-01

    Mixed alkali — alkaline earth borate glasses, with the addition of silica and alumina, have been studied for their density, Tg and CTE with a view of exploring the applicability of these glasses in glass to metal sealing applications. It has been observed that silica addition results in an increase in density and Tg while the alumina addition decreases the density and Tg. The variation in CTE exhibits minima with the addition of both, silica and alumina. An attempt is made here to explain the observed variations in the properties on the basis of different mass of the additives, number of non bridging oxygens (NBOs) and other changes in the glass network.

  12. Microprobes aluminosilicate ceramic membranes

    DOEpatents

    Anderson, Marc A.; Sheng, Guangyao

    1993-01-01

    Methods have been developed to make mixed alumina-silicate and aluminosilicate particulate microporous ceramic membranes. One method involves the making of separate alumina and silica sols which are then mixed. Another method involves the creation of a combined sol with aluminosilicate particles. The resulting combined alumina and silica membranes have high surface area, a very small pore size, and a very good temperature stability.

  13. Investigation of emulsified, acid and acid-alkali catalyzed mesoporous bioactive glass microspheres for bone regeneration and drug delivery.

    PubMed

    Miao, Guohou; Chen, Xiaofeng; Dong, Hua; Fang, Liming; Mao, Cong; Li, Yuli; Li, Zhengmao; Hu, Qing

    2013-10-01

    Acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were successfully synthesized via combination of sol-gel and water-in-oil (W/O) micro-emulsion methods. The structural, morphological and textural properties of mesoporous bioactive glass microspheres (MBGMs) were characterized by various techniques. Results show that both MBGMs-A and MBGMs-B exhibit regularly spherical shape but with different internal porous structures, i.e., a dense microstructure for MBGMs-A and internally porous structure for MBGMs-B. (29)Si NMR data reveal that MGBMs have low polymerization degree of silica network. The in vitro bioactivity tests indicate that the apatite formation rate of MBGMs-B was faster than that of MBGMs-A after soaking in simulated body fluid (SBF) solution. Furthermore, the two kinds of MBGMs have similar storage capacity of alendronate (AL), and the release behaviors of AL could be controlled due to their unique porous structure. In conclusion, the microspheres are shown to be promising candidates as bone-related drug carriers and filling materials of composite scaffold for bone repair. PMID:23910338

  14. Structure of Alkali Borate Glasses at High Pressure: B and Li K-Edge Inelastic X-Ray Scattering Study

    SciTech Connect

    Lee, Sung Keun; Eng, Peter J.; Mao, Ho-kwang; Meng, Yue; Shu, Jinfu

    2008-06-16

    We report the first in situ boron K-edge inelastic x-ray scattering (IXS) spectra for alkali borate glasses (Li{sub 2}B{sub 4}O{sub 7}) at high pressure up to 30 GPa where pressure-induced coordination transformation from three-coordinated to four-coordinated boron was directly probed. Coordination transformation (reversible upon decompression) begins around 5 GPa and the fraction of four-coordinated boron increases with pressure from about 50% (at 1 atm) to more than 95% (at 30 GPa) with multiple densification mechanisms, evidenced by three distinct pressure ranges for (d{sup [4]}B/dP){sub T}. The lithium K-edge IXS spectrum for Li-borate glasses at 5 GPa shows IXS features similar to that at 1 atm, suggesting that the Li environment does not change much with pressure up to 5 GPa. These results provide improved understanding of the structure of low-z glass at high pressure.

  15. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: the effect of protective alumina coating on electrical stability in dual environment

    SciTech Connect

    Chou, Y. S.; Choi, Jung-Pyung; Stevenson, Jeffry W.

    2012-12-01

    An alkali-containing silicate glass was recently proposed as a potential sealant for solid oxide fuel cells (SOFC). The glass contains appreciable amount of alkalis and retains its glassy microstructure at elevated temperatures over time. It is more compliant as compared to conventional glass-ceramics sealants and could potentially heal cracks during thermal cycling. In previous papers the thermal cycle stability, thermal stability and chemical compatibility were reported with yttria-stabilized zirconia (YSZ) electrolyte and YSZ-coated ferritic stainless steel interconnect. In this paper, we report the electrical stability of the compliant glass with aluminized AISI441 interconnect material under DC load in dual environment at 700-800oC. Apparent electrical resistivity was measured with a 4-point method for the glass sealed between two aluminized AISI441 metal coupons as well as plain AISI441 substrates. The results showed good electrical stability with the aluminized AISI441 substrate, while unstable behavior was observed for un-coated substrates. In addition, interfacial microstructure was examined with scanning electron microscopy and correlated with the measured resistivity results. Overall, the alumina coating demonstrated good chemical stability with the alkali-containing silicate sealing glass under DC loading.

  16. The Structural Role of Zr within Alkali Borosilicate Glasses for Nuclear Waste Immobilisation

    SciTech Connect

    A Connelly; N Hyatt; K Travis; R Hand; E Maddrell; R Short

    2011-12-31

    Zirconium is a key constituent element of High Level nuclear Waste (HLW) glasses, occurring both as a fission product and a fuel cladding component. As part of a wider research program aimed at optimizing the solubility of zirconium in HLW glasses, we have investigated the structural chemistry of zirconium in such materials using X-ray Absorption Spectroscopy (XAS). Zirconium K-edge XAS data were acquired from several inactive simulant and simplified waste glass compositions, including a specimen of blended Magnox/UO{sub 2} fuel waste glass. These data demonstrate that zirconium is immobilized as (octahedral) six-fold coordinate ZrO{sub 6} species in these glasses, with a Zr-O contact distance of 2.09 {angstrom}. The next nearest neighbors of the Zr species are Si at 3.42 {angstrom} and possibly Na at 3.44 {angstrom}, no next nearest neighbor Zr could be resolved.

  17. Determination of the valence band structure of an alkali phosphorus oxynitride glass: A synchrotron XPS study on LiPON

    NASA Astrophysics Data System (ADS)

    Schwöbel, André; Precht, Ruben; Motzko, Markus; Carrillo Solano, Mercedes A.; Calvet, Wolfram; Hausbrand, René; Jaegermann, Wolfram

    2014-12-01

    Lithium phosphorus oxynitride (LiPON) is a solid state electrolyte commonly used in thin film batteries (TFBs). Advanced TFBs face the issue of detrimental electrode-electrolyte interlayer formation, related to the electronic structure of the interface. In this contribution, we study the valence band structure of LiPON using resonant photoemission and synchrotron photoemission with variable excitation energies. The identification of different valence band features is done according to the known valence band features of meta- and orthophosphates. Additionally we compare our results with partial density of states simulations from literature. We find that the valence band structure is similar to the known metaphosphates with an additional contribution of nitrogen states at the top of the valence band. From the results we conclude that synchrotron X-ray photoemission (XPS) is a useful tool to study the valence band structure of nitridated alkali phosphate glasses.

  18. Study of bi-alkali photocathode growth on glass by X-ray techniques for fast timing response photomultipliers

    NASA Astrophysics Data System (ADS)

    Xie, Junqi; Demarteau, Marcel; Wagner, Robert; Ruiz-Oses, Miguel; Liang, Xue; Ben-Zvi, Ilan; Attenkofer, Klaus; Schubert, Susanne; Smedley, John; Wong, Jared; Padmore, Howard; Woll, Arthur

    2014-03-01

    Bi-alkali antimonide photocathode is an essential component in fast timing response photomultipliers. Real-time in-situ grazing incidence x-ray diffraction and post-growth x-ray reflectivity measurement were performed to study the photocathode deposition process on glass substrate. Grazing incidence x-ray diffraction patterns show the formation of Sb crystalline, dissolution of crystalline phase Sb by the application of K vapor and reformation of refined crystal textures. XRR result exhibits that the film thickness increases ~ 4.5 times after K diffusion and almost have no change after Cs diffusion. Further investigation is expected to understand the photocathode growth process and provide guidelines for photocathode development.

  19. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: Combined stability in isothermal ageing and thermal cycling with YSZ coated ferritic stainless steels

    SciTech Connect

    Chou, Y. S.; Thomsen, Edwin C.; Choi, Jung-Pyung; Stevenson, Jeffry W.

    2012-01-01

    An alkali-containing silicate glass (SCN-1) is currently being evaluated as a candidate sealing glass for solid oxide fuel cell (SOFC) applications. The glass contains about 17 mole% alkalis (K+Na) and has low glass transition and softening temperatures. It remains vitreous and compliant around 750-800oC after sealing without substantial crystallization, as contrary to conventional glass-ceramic sealants, which experience rapid crystallization after the sealing process. The glassy nature and low characteristic temperatures can reduce residual stresses and result in the potential for crack healing. In a previous study, the glass was found to have good thermal cycle stability and was chemically compatible with YSZ coating during short term testing. In the current study, the compliant glass was further evaluated in a more realistic way in that the sealed glass couples were first isothermally aged for 1000h followed by thermal cycling. High temperature leakage was measured. The chemical compatibility was also investigated with powder mixtures at 700 and 800oC to enhance potential interfacial reaction. In addition, interfacial microstructure was examined with scanning electron microscopy and evaluated with regard to the leakage and chemical compatibility results.

  20. Multilevel Tunnelling Systems and Fractal Clustering in the Low-Temperature Mixed Alkali-Silicate Glasses

    PubMed Central

    2013-01-01

    The thermal and dielectric anomalies of window-type glasses at low temperatures (T < 1 K) are rather successfully explained by the two-level systems (2LS) standard tunneling model (STM). However, the magnetic effects discovered in the multisilicate glasses in recent times, magnetic effects in the organic glasses, and also some older data from mixed (SiO2)1−x(K2O)x and (SiO2)1−x(Na2O)x glasses indicate the need for a suitable extension of the 2LS-STM. We show that—not only for the magnetic effects, but also for the mixed glasses in the absence of a field—the right extension of the 2LS-STM is provided by the (anomalous) multilevel tunnelling systems (ATS) proposed by one of us for multicomponent amorphous solids. Though a secondary type of TS, different from the standard 2LS, was invoked long ago already, we clarify their physical origin and mathematical description and show that their contribution considerably improves the agreement with the experimental data. In spite of dealing with low-temperature properties, our work impinges on the structure and statistical physics of glasses at all temperatures. PMID:23861652

  1. Coordination and valence state of transition metal ions in alkali-borate glasses

    NASA Astrophysics Data System (ADS)

    Terczyńska-Madej, A.; Cholewa-Kowalska, K.; Łączka, M.

    2011-10-01

    Borate glasses of the 20R 2O·80B 2O 3 type, where R = Li, Na and K, were colored by doping with transition metal ions (Co, Ni, Cr and Mn). The glasses were obtained by melting at the temperature of 1150 °C. For these glasses optical absorption in UV-VIS-NIR range were recorded. Analysis of the spectra allows to be determined the coordination and oxidation states of the doping transition metal ions. Changes of their coordination or oxidation are presented as a function of the optical basicity Λ after Duffy. Cobalt and nickel are present in examined borate glasses as divalent ions (Co 2+, Ni 2+) in octahedral coordination mainly, but the tetrahedral coordination state of cobalt is also possible. Chromium and manganese are present in the borate glasses in various oxidation state, though Cr 3+ and Mn 3+ ions in the octahedral coordination are probably dominant. A decrease of the electronegativity of the modifiers (Li → Na → K) and an increase of the glass matrix basicity cause a shift of the oxidation/reduction equilibrium towards higher valences of the transition metals (Cr 6+, Mn 3+).

  2. Multilevel tunnelling systems and fractal clustering in the low-temperature mixed alkali-silicate glasses.

    PubMed

    Jug, Giancarlo; Paliienko, Maksym

    2013-01-01

    The thermal and dielectric anomalies of window-type glasses at low temperatures (T < 1 K) are rather successfully explained by the two-level systems (2LS) standard tunneling model (STM). However, the magnetic effects discovered in the multisilicate glasses in recent times, magnetic effects in the organic glasses, and also some older data from mixed (SiO₂)(1-x) (K₂O)(x) and (SiO₂)(1-x) (Na₂O)(x) glasses indicate the need for a suitable extension of the 2LS-STM. We show that--not only for the magnetic effects, but also for the mixed glasses in the absence of a field--the right extension of the 2LS-STM is provided by the (anomalous) multilevel tunnelling systems (ATS) proposed by one of us for multicomponent amorphous solids. Though a secondary type of TS, different from the standard 2LS, was invoked long ago already, we clarify their physical origin and mathematical description and show that their contribution considerably improves the agreement with the experimental data. In spite of dealing with low-temperature properties, our work impinges on the structure and statistical physics of glasses at all temperatures. PMID:23861652

  3. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: Combined stability in isothermal ageing and thermal cycling with YSZ coated ferritic stainless steels

    NASA Astrophysics Data System (ADS)

    Chou, Yeong-Shyung; Thomsen, E. C.; Choi, J.-P.; Stevenson, J. W.

    2012-01-01

    An alkali silicate glass (SCN-1) is being evaluated as a candidate sealant for solid oxide fuel cell (SOFC) applications. The glass contains about 17 wt.% alkalis (K + Na) and has low glass transition and softening temperatures. It remains vitreous and compliant after sealing without substantial crystallization, as contrary to conventional glass-ceramic sealant. The glassy nature and low characteristic temperatures can reduce residual stresses and result in the potential for crack healing. In a previous study, the glass was found to have good thermal cycle stability and was chemically compatible with yttria stabilized zirconia (YSZ) coating during short term testing. In this study, the compliant glass was further evaluated in a more realistic way in that the sealed couples were first isothermally aged for 1000 h followed by thermal cycling. High temperature leakage was measured. Chemical compatibility was also investigated with powder mixtures to enhance potential interfacial reaction. In addition, interfacial microstructure was examined with scanning electron microscopy and evaluated with regard to the leakage and chemical compatibility results. Overall the compliant sealing glass showed desirable chemical compatibility with YSZ coated metallic interconnect of minimum reaction and hermetic behavior at 700-750 °C in dual environment.

  4. Structural investigation and electron paramagnetic resonance of vanadyl doped alkali niobium borate glasses.

    PubMed

    Agarwal, A; Sheoran, A; Sanghi, S; Bhatnagar, V; Gupta, S K; Arora, M

    2010-03-01

    Glasses with compositions xNb(2)O(5).(30-x)M(2)O.69B(2)O(3) (where M=Li, Na, K; x=0, 4, 8 mol%) doped with 1 mol% V(2)O(5) have been prepared using normal melt quench technique. The IR transmission spectra of the glasses have been studied over the range 400-4000 cm(-1). The changes caused by the addition of Nb(2)O(5) on the structure of these glasses have been reported. The electron paramagnetic resonance spectra of VO(2+) ions in these glasses have been recorded in X-band (9.14 GHz) at room temperature (300 K). The spin Hamiltonian parameters, dipolar hyperfine coupling parameter and Fermi contact interaction parameter have been calculated. It is observed that the resultant resonance spectra contain hyperfine structures (hfs) due to V(4+) ions which exist as VO(2+) ions in octahedral coordination with a tetragonal compression in the present glasses. The tetragonality of V(4+)O(6) complex decreases with increasing concentration of Nb(2)O(5). The 3d(xy) orbit contracts with increase in Nb(2)O(5):M(2)O ratio. Values of the theoretical optical basicity, Lambda(th), have also been reported. PMID:20060775

  5. On the structure of defect centers in γ-irradiated alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    Cases, R.; Griscom, D. L.

    1984-02-01

    An EPR study after room temperature γ-irradiation on potassium silicate glasses of two chemical compositions and different 17O and 29Si isotopic enrichments has been carried out. Isochronal anneal experiments on 17O-enriched samples have confirmed the model for the trapped-hole center HC 1 as comprising a trapped hole on a pure 2p π orbital of a single nonbridging oxygen. Besides the well known HC 1 and HC 2 EPR spectra, new resonances have been isolated and identified as due to three types of oxygen-related defects (interstitial O 2- ions; O 2- bonded to the glass network; and interstitial ozonide ions O 3-). Using 29Si-enriched samp simulations a 370 G doublet has been demonstrated to arise from an E'-like defect for which a tentative model is given. The formation of all these defects by irradiation depends on chemical composition of the glass.

  6. Silicate species of water glass and insights for alkali-activated green cement

    SciTech Connect

    Jansson, Helén; Bernin, Diana; Ramser, Kerstin

    2015-06-15

    Despite that sodium silicate solutions of high pH are commonly used in industrial applications, most investigations are focused on low to medium values of pH. Therefore we have investigated such solutions in a broad modulus range and up to high pH values (∼14) by use of infrared (IR) spectroscopy and silicon nuclear magnetic resonance ({sup 29}Si-NMR). The results show that the modulus dependent pH value leads to more or less charged species, which affects the configurations of the silicate units. This in turn, influences the alkali-activation process of low CO{sub 2} footprint cements, i.e. materials based on industrial waste or by-products.

  7. Silicate species of water glass and insights for alkali-activated green cement

    NASA Astrophysics Data System (ADS)

    Jansson, Helén; Bernin, Diana; Ramser, Kerstin

    2015-06-01

    Despite that sodium silicate solutions of high pH are commonly used in industrial applications, most investigations are focused on low to medium values of pH. Therefore we have investigated such solutions in a broad modulus range and up to high pH values (˜14) by use of infrared (IR) spectroscopy and silicon nuclear magnetic resonance (29Si-NMR). The results show that the modulus dependent pH value leads to more or less charged species, which affects the configurations of the silicate units. This in turn, influences the alkali-activation process of low CO2 footprint cements, i.e. materials based on industrial waste or by-products.

  8. Dependence of the mixed alkali effect on temperature and total alkali oxide content in y[xLi{sub 2}O.(1-x)Na{sub 2}O].(1-y)B{sub 2}O{sub 3} glasses

    SciTech Connect

    Gao Yong . E-mail: yonggao@uni-muenster.de

    2005-11-15

    The complex conductivity spectra of mixed alkali borate glasses of compositions y [xLi{sub 2}O.(1-x)Na{sub 2}O].(1-y)B{sub 2}O{sub 3} (with x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0; y=0.1, 0.2, 0.3) in a frequency range between 10{sup -2}Hz and 3MHz and at temperatures ranging from 298 to 573K have been studied. For each glass composition the conductivities show a transition from the dc values into a dispersive regime where the conductivity is found to increase continuously with frequency, tending towards a linear frequency dependence at sufficiently low temperatures. Mixed alkali effects (MAEs) in the dc conductivity and activation energy are identified and discussed. It has been for the first time found that the strength of the MAE in the logarithm of the dc conductivity linearly increases with the total alkali oxide content, y, and the reciprocal temperature, 1/T.

  9. Luminescent properties of bismuth centres in aluminosilicate optical fibres

    SciTech Connect

    Bulatov, Lenar I; Mashinskii, Valerii M; Dvoirin, Vladislav V; Dianov, Evgenii M; Kustov, Evgenii F

    2010-02-28

    The shape and spectral position of the luminescence bands of bismuth-doped aluminosilicate glass fibres are shown to depend on excitation power and wavelength. This indicates that the red and IR luminescence bands are composed of several components. The absorption and radiative transitions involved are identified, and a diagram of energy levels and transitions is obtained for four modifications of a bismuth centre in different environments in the aluminosilicate glass network. The effect of local environment on the optical properties of the bismuth centres is examined. (optical fibres and waveguides)

  10. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: the effect of protective YSZ coating on electrical stability in dual environment

    SciTech Connect

    Chou, Y. S.; Thomsen, Edwin C.; Choi, Jung-Pyung; Stevenson, Jeffry W.

    2012-03-15

    Recently, compliant sealing glass has been proposed as a potential candidate sealant for solid oxide fuel cell (SOFC) applications. In a previous paper, the thermal stability and chemical compatibility were reported for a compliant alkali-containing silicate glass sealed between anode supported YSZ bi-layer and YSZ-coated stainless steel interconnect. In this paper, we will report the electrical stability of the compliant glass under a DC load and dual environment at 700-800 degrees C. Apparent electrical resistivity was measured with a 4-point method for the glass sealed between two plain SS441 metal coupons or YSZ-coated aluminized substrates. The results showed instability with plain SS441 at 800 degrees C, but stable behavior of increasing resistivity with time was observed with the YSZ coated SS441. In addition, results of interfacial microstructure analysis with scanning electron microscopy will be correlated with the measured resistivity results. Overall, the YSZ coating demonstrated chemically stability with the alkali-containing compliant silicate sealing glass under electrical field and dual environments.

  11. Mixed Alkali Effect in (40-x)K2O-xLi2O-10Na2O-50B2O3 Glasses - Physical and Optical Absorption Studies

    NASA Astrophysics Data System (ADS)

    Samee, M. A.; Ahmmad, Shaikh Kareem; Taqiullah, Sair. Md.; Edukondalu, A.; Bale, Shashidhar; Rahman, Syed

    So far only a handful of publications have been concerned with the study of the mixed alkali effect in borate glasses containing three types of alkali ions. In the present work, the mixed alkali effect (MAE) has been investigated in the glass system (40-x) K2O-x Li2O -10Na2O-50B2O3.(0≤x≤40 mol%) through density and modulated DSC studies. The density and glass transition temperature of the present glasses varies non-linearly exhibiting mixed alkali effect. We report the mixed alkali effect in the present glasses through optical properties. From the absorption edge studies, the various values of optical band gap (Eo) and Urbach energy (ΔE) have been evaluated. The values of Eo and ΔE show non-linear behavior with compositional parameter showing the mixed alkali effect. The band gap energy based average electronic polarizability of oxide ions αO2-(Eo), optical basicity A(Eo), and Yamashita-Kurosawa’s interaction parameter A(Eo) have been examined to check the correlations among them and bonding character. Based on good correlation among electronic polarizability of oxide ions, optical basicity and interaction parameter, the present K2O- Li2O-Na2O-B2O3 glasses are classified as normal ionic (basic) oxides.

  12. Chemical constraints on fly ash glass compositions

    SciTech Connect

    John H. Brindle; Michael J. McCarthy

    2006-12-15

    The major oxide content and mineralogy of 75 European fly ashes were examined, and the major element composition of the glass phase was obtained for each. Correlation of compositional trends with the glass content of the ash was explored. Alkali content was deduced to have a major influence on glass formation, and this in turn could be related to the probable chemistry of clay minerals in the source coals. Maximal glass content corresponded to high aluminum content in the glass, and this is in accordance with the theoretical mechanism of formation of aluminosilicate glasses, in which network-modifying oxides are required to promote tetrahedral coordination of aluminum in glass chain structures. Iron oxide was found to substitute for alkali oxides where the latter were deficient, and some indications of preferred eutectic compositions were found. The work suggests that the proportion of the glass phase in the ash can be predicted from the coal mineralogy and that the utility of a given ash for processing into geopolymers or zeolites is determined by its source. 23 refs., 7 figs., 1 tab.

  13. Entropy and structure of silicate glasses and melts

    USGS Publications Warehouse

    Richet, P.; Robie, R.A.; Hemingway, B.S.

    1993-01-01

    Low-temperature adiabatic Cp measurements have been made on NaAlSi2O6, MgSiO3, Ca3Al2Si3O12 and Ca1.5Mg1.5Al2Si3O12 glasses. Above about 50 K, these and previous data show that the heat capacity is an additive function of composition to within ??1% throughout the investigated glassforming part of the system CaO-MgO-Al2O3-SiO2. In view of the determining role of oxygen coordination polyhedra on the low-temperature entropy, this is interpreted as indicating that Si and Al are tetrahedrally coordinated in all these glasses, in agreement with structural data; whereas Ca and Mg remain octahedrally coordinated. In contrast, heat capacities and entropies are not additive functions of composition for alkali aluminosilicates, indicating increases in the coordination numbers of alkali elements from about six to nine when alumina is introduced. A thermochemical consequence of additivity of vibrational entropies of glasses is that entropies of mixing are essentially configurational for calcium and magnesium aluminosilicate melts. For alkali-bearing liquids, it is probable that vibrational entropies contribute significantly to entropies of mixing. At very low temperatures, the additive nature of the heat capacity with composition is less well followed, likely as a result of specific differences in medium-range order. ?? 1993.

  14. Multi-phase glass-ceramics as a waste form for combined fission products: alkalis, alkaline earths, lanthanides, and transition metals

    SciTech Connect

    Crum, Jarrod V.; Turo, Laura A.; Riley, Brian J.; Tang, Ming; Kossoy, Anna

    2012-04-01

    In this study, multi-phase silicate-based glass-ceramics were investigated as an alternate waste form for immobilizing non-fissionable products from used nuclear fuel. Currently, borosilicate glass is the waste form selected for immobilization of this waste stream, however, the low thermal stability and solubility of MoO{sub 3} in borosilicate glass translates into a maximum waste loading in the range of 15-20 mass%. Glass-ceramics provide the opportunity to target durable crystalline phases, e.g., powellite, oxyapatite, celsian, and pollucite, that will incorporate MoO{sub 3} as well as other waste components such as lanthanides, alkalis, and alkaline earths at levels 2X the solubility limits of a single-phase glass. In addition a glass-ceramic could provide higher thermal stability, depending upon the properties of the crystalline and amorphous phases. Glass-ceramics were successfully synthesized at waste loadings of 42, 45, and 50 mass% with the following glass additives: B{sub 2}O{sub 3}, Al{sub 2}O{sub 3}, CaO and SiO{sub 2} by slow cooling form from a glass melt. Glass-ceramics were characterized in terms of phase assemblage, morphology, and thermal stability. The targeted phases: powellite and oxyapatite were observed in all of the compositions along with a lanthanide borosilicate, and cerianite. Results of this initial investigation of glass-ceramics show promise as a potential waste form to replace single-phase borosilicate glass.

  15. Evidence for two different shock induced high-pressure events and alkali-vapor metasomatism in Peace River and Tenham (L6) chondrites

    NASA Astrophysics Data System (ADS)

    El Goresy, A.; Wopenka, B.; Chen, M.; Weinbruch, S.; Sharp, T. G.

    1997-03-01

    Smooth grains in the Peace River shocked matrix previously described as maskelynite are not diaplectic glass but a crystalline phase with a stoichiometric composition. They formed upon decompression by inversion of a parental high-pressure polymorph that crystallized from a dense K-rich melt. They are surrounded by radiating cracks that have extensively shattered the neighboring minerals due to volume increase induced by decompression. Similar grains in Tenham turned out to be glass-quenched from a dense alkali-rich melt compositionally unrelated to plagioclase. Expansion of the alkali-bearing aluminosilicate in Peace River and the quenched dense glass in Tenham triggered the second high-pressure event. Neither Peace River nor Tenham contain any maskelynite.

  16. Hot isostatically-pressed aluminosilicate glass-ceramic with natural crystalline analogues for immobilizing the calcined high-level nuclear waste at the Idaho Chemical Processing Plant

    SciTech Connect

    Raman, S.

    1993-12-01

    The additives Si, Al, MgO, P{sub 2}O{sub 5} were mechanically blended with fluorinelsodium calcine in varying proportions. The batches were vacuum sealed in stainless steel canisters and hot isostatically pressed at 20,000 PSI and 1000 C for 4 hours. The resulting suite of glass-ceramic waste forms parallels the natural rocks in microstructural and compositional heterogeneity. Several crystalline phases ar analogous in composition and structure to naturally occurring minerals. Additional crystalline phases are zirconia and Ca-Mg borate. The glasses are enriched in silica and alumina. Approximately 7% calcine elements occur dissolved in this glass and the total glass content in the waste forms averages 20 wt%. The remainder of the calcine elements are partitioned into crystalline phases at 75 wt% calcine waste loading. The waste forms were tested for chemical durability in accordance with the MCC1-test procedure. The leach rates are a function of the relative proportions of additives and calcine, which in turn influence the composition and abundances of the glass and crystalline phases. The DOE leach rate criterion of less than 1 g/m{sup 2}-day is met by all the elements B, Cs and Na are increased by lowering the melt viscosity. This is related to increased crystallization or devitrification with increases in MgO addition. This exploratory work has shown that the increases in waste loading occur by preferred partitioning of the calcine components among crystalline and glass phases. The determination of optimum processing parameters in the form of additive concentration levels, homogeneous blending among the components, and pressure-temperature stabilities of phases must be continued to eliminate undesirable effects of chemical composition, microstructure and glass devitrification.

  17. Intumescence and pore structure of alkali-activated volcanic glasses upon exposure to high temperatures

    NASA Astrophysics Data System (ADS)

    Erdogan, S. T.

    2015-12-01

    Structures formed with ground perlite, a natural volcanic glass, activated with NaOH solutions, are shown to possess the ability to expand up to ~225 % of their original volumes upon exposure to temperatures in the 200-600 °C range. Porous solid with 3-7 MPa compressive strength and ˜450 kg/m3 or higher density are obtained. The observed expansion is believed to occur due to a loss of silanol condensation water, as vapor and is accompanied by an up to ~20 % loss in mass. A drop in pH to near-neutral values supports this idea. The size and total amount of pores in the final solid are controlled by concentration of the NaOH solution and thermal processing conditions. The pores formed are observed to be ~1-10 μm to mm-sized. The ability of perlite-based solids to intumesce over specific temperature ranges could be beneficial in applications where absorption of thermal energy is necessary, such as passive fire protection.

  18. Generation of alkali-free and high-proton concentration layer in a soda lime glass using non-contact corona discharge

    SciTech Connect

    Ikeda, Hiroshi; Sakai, Daisuke; Nishii, Junji; Funatsu, Shiro; Yamamoto, Kiyoshi; Suzuki, Toshio; Harada, Kenji

    2013-08-14

    Formation mechanisms of alkali-free and high-proton concentration surfaces were investigated for a soda lime glass using a corona discharge treatment under an atmospheric pressure. Protons produced by high DC voltage around an anode needle electrode were incorporated into a sodium ion site in the anode side glass. The sodium ion was swept away to the cathode side as a charge carrier. Then it was discharged. The precipitated sodium was transformed to a Na{sub 2}CO{sub 3} powder when the surface contacted with air. The sodium ion in the glass surface layer of the anode side was replaced completely by protons. The concentration of OH groups in the layer was balanced with the amount of excluded sodium ions. The substitution reaction of sodium ions with protons tends to be saturated according to a square root function of time. The alkali depletion layer formation rate was affected by the large difference in mobility between sodium ions and protons in the glass.

  19. Alkali-silica reactions of mortars produced by using waste glass as fine aggregate and admixtures such as fly ash and Li2CO3.

    PubMed

    Topçu, Ilker Bekir; Boğa, Ahmet Raif; Bilir, Turhan

    2008-01-01

    Use of waste glass or glass cullet (GC) as concrete aggregate is becoming more widespread each day because of the increase in resource efficiency. Recycling of wastes is very important for sustainable development. When glass is used as aggregate in concrete or mortar, expansions and internal stresses occur due to an alkali-silica reaction (ASR). Furthermore, rapid loss in durability is generally observed due to extreme crack formation and an increase in permeability. It is necessary to use some kind of chemical or mineral admixture to reduce crack formation. In this study, mortar bars are produced by using three different colors of glass in four different quantities as fine aggregate by weight, and the effects of these glass aggregates on ASR are investigated, corresponding to ASTM C 1260. Additionally, in order to reduce the expansions of mortars, 10% and 20% fly ash (FA) as mineral admixture and 1% and 2% Li(2)CO(3) as chemical admixture are incorporated by weight in the cement and their effects on expansion are examined. It is observed that among white (WG), green (GG) and brown glass (BG) aggregates, WG aggregate causes the greatest expansion. In addition, expansion increases with an increase in amount of glass. According to the test results, it is seen that over 20% FA and 2% Li(2)CO(3) replacements are required to produce mortars which have expansion values below the 0.2% critical value when exposed to ASR. However, usages of these admixtures reduce expansions occurring because of ASR. PMID:17570652

  20. Specialty glass raw materials: Status and developments

    SciTech Connect

    Bauer, R.J.; Gray, S.L.

    1996-12-31

    The authors highlight several key raw materials used in the specialty glass industry. The focus here is to update changes and shifts underway in the worldwide availability and processes that will impact both costs and efficient use of these products. The glass types that use these materials generally are those other than container, float, and fiber glass. Those high-volume consumers of glass raw materials are discussed in a companion paper in this volume. In the specialty glass field, the batch materials involve minerals, and the chemicals derived from them, which are less readily available domestically. These are much more critically defined by specifications of assay, contamination, and particle size, resulting in their being more expensive. They are seldom commodity products. The scope of materials for this fragmented industry includes those for leads, borosilicates, aluminosilicates, opals, sealing and frit glasses, optical glass, ophthalmic glass, cathode ray tubes (CRTs) for TV and display, and glass-ceramics as major segments. They use lead oxides, nearly all the alkalies and alkaline earth portions of the periodic table, as well as rare earths, transition element oxides, phosphates, boron minerals and chemicals, zircon, zinc, most of the halogens, and many of the anions. They often require very special particle size specifications. The requirements for these batch materials are often based on chemistry, the absence of contaminants that impact melting, very wide ranges of the electromagnetic spectrum, glass homogeneity, and freedom from solid and gaseous inclusions down to ppm levels in both size and number.

  1. Mechanisms of optical losses in the {sup 5}D{sub 4} and {sup 5}D{sub 3} levels in Tb{sup 3+} doped low silica calcium aluminosilicate glasses

    SciTech Connect

    Santos, J. F. M. dos; Terra, I. A. A.; Nunes, L. A. O.; Catunda, T.; Astrath, N. G. C.; Guimarães, F. B.; Baesso, M. L.

    2015-02-07

    Trivalent Tb-doped materials exhibit strong emission in the green and weak emission in the UV-blue levels. Usually, this behavior is attributed to the cross relaxation (CR) process. In this paper, the luminescence properties of Tb{sup 3+}-doped low silica calcium aluminosilicate glasses are analyzed for UV (λ{sub exc} = 325 nm) and visible (488 nm) excitations. Under 325 nm excitation, the intensity of green luminescence increases proportionally to Tb{sup 3+} concentration. However, the blue luminescence intensity is strongly reduced with the increase of concentration from 0.5–15.0 wt. %. In the case of 488 nm excitation, a saturation behavior of the green emission is observed at intensities two orders of magnitude smaller than expected for bleaching of the ground state population. Using a rate equation model, we showed that this behavior can be explained by an excited state absorption cross section two orders of magnitude larger than the ground state absorption. The blue emission is much weaker than expected from our rate equations (325 nm and 488 nm excitation). We concluded that only the CR process cannot explain the overall feature of measured luminescence quenching in the wide range of Tb{sup 3+} concentrations. Cooperative upconversion from a pair of excited ions ({sup 5}D{sub 3}:{sup 5}D{sub 3} or {sup 5}D{sub 3}:{sup 5}D{sub 4}) and other mechanisms involving upper lying states (4f5d, charge transfer, host matrix, defects, etc.) may play a significant role.

  2. Influence of ZnO/MgO substitution on sintering, crystallisation, and bio-activity of alkali-free glass-ceramics.

    PubMed

    Kapoor, Saurabh; Goel, Ashutosh; Correia, Ana Filipa; Pascual, Maria J; Lee, Hye-Young; Kim, Hae-Won; Ferreira, José M F

    2015-08-01

    The present study reports on the influence of partial replacement of MgO by ZnO on the structure, crystallisation behaviour and bioactivity of alkali-free bioactive glass-ceramics (GCs). A series of glass compositions (mol%): 36.07 CaO-(19.24-x) MgO-x ZnO-5.61 P2O5-38.49 SiO2-0.59 CaF2 (x=2-10) have been synthesised by melt-quench technique. The structural changes were investigated by solid-state magic angle spinning nuclear magnetic resonance (MAS-NMR), X-ray diffraction and differential thermal analysis. The sintering and crystallisation behaviours of glass powders were studied by hot-stage microscopy and differential thermal analysis, respectively. All the glass compositions exhibited good densification ability resulting in well sintered and mechanically strong GCs. The crystallisation and mechanical behaviour were studied under non-isothermal heating conditions at 850 °C for 1h. Diopside was the primary crystalline phase in all the GCs followed by fluorapatite and rankinite as secondary phases. Another phase named petedunnite was identified in GCs with ZnO content >4 mol. The proliferation of mesenchymal stem cells (MSCs) and their alkaline phosphatase activity (ALP) on GCs was revealed to be Zn-dose dependent with the highest performance being observed for 4 mol% ZnO. PMID:26042713

  3. Sorption of cesium and strontium from mineralized aqueous solutions on natural aluminosilicates modified by ferrocyanides of heavy metals

    SciTech Connect

    Panasyugin, A.S.; Trofimenko, N.E.; Masherova, N.P.; Rat`ko, A.I.; Golikova, N.I.

    1994-03-10

    The sorption behavior of natural aluminosilicates (bentonite and clinoptilolite) and aluminosilicates modified by ferrocyanides of heavy metals has been studied relative to radionuclides {sup 137}Cs and {sup 90}Sr in the presence of various quantities of alkali and alkaline-earth ions (e.g. surface waters). It has been shown that the distribution coefficients of the modified samples may exceed 100 for Sr{sup 2+} and 10,000 for Cs{sup +}; however, with a concentration of mineral background over 1.0 g{center_dot}liter, the competing ions strongly depress the sorption properties of the aluminosilicates.

  4. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  5. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  6. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  7. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  8. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  9. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  10. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  11. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727...) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2727 Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance. This substance is generally recognized...

  12. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  13. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  14. Effect of MoO3 on electron paramagnetic resonance spectra, optical spectra and dc conductivity of vanadyl ion doped alkali molybdo-borate glasses

    NASA Astrophysics Data System (ADS)

    Agarwal, A.; Khasa, S.; Seth, V. P.; Sanghi, S.; Arora, M.

    2014-02-01

    Alkali molybdo-borate glasses having composition xMoO3·(30 - x)M2O·70B2O3 and xMoO3·(70 - x)B2O3·30M2O (M = Li, Na, K) with 0 ⩽ x ⩽ 15 (mol%) doped with 2.0 mol% of V2O5 have been prepared in order to study the influence of MoO3 on electrical conductivity, electron paramagnetic resonance (EPR) and optical spectra. From EPR studies it is observed that V4+ ions in these samples exist as VO2+ ions in octahedral coordination with a tetragonal compression and belong to C4V symmetry. The tetragonal nature and octahedral symmetry of V4+O6 complex increase as well as decrease depending upon the composition of glasses with increase in MoO3 but 3dxy orbit of unpaired electron in the VO2+ ion expands in all the glasses. The decrease in optical band gap suggests that there is an increase in the concentration of non-bridging oxygen's. From the study of optical transmission spectra it is observed that for all the glasses the degree of covalency of the σ-bonding decreases with increase in MoO3 content and the degree of covalency of the π-bonding also varies. These results based on optical spectroscopy are in agreement with EPR findings. It is found that dc conductivity decreases and activation energy increases with increase in MoO3:M2O (M = Li, Na, K) ratio in MoO3·M2O·B2O3 glasses, whereas the conductivity increases and activation energy decreases with increase in MoO3:B2O3 ratio in xMoO3·B2O3·M2O glasses, which is governed by the increase in nonbridging oxygen's. The variation in theoretical optical basicity, Λth is also studied.

  15. The development of a potassium-sulfide glass fiber cell and studies on impurities in alkali metal-sulfur cells

    NASA Technical Reports Server (NTRS)

    Tsang, F. Y.

    1977-01-01

    Potassium sulfur rechargeable cells, having as the electrolyte the thin walls of hollow glass fibers made from permeable glass, were developed. The cells had short lives, probably due to the construction materials and impurities in the potassium. The effect of the impurities in the analogous NA-S system was studied. Calcium, potassium, and NaOH/oxide impurities caused increased resistance or corrosion of the glass fibers. For long lived cell operation, the Na must contain less than 1 ppm Ca and less than a few ppm of hydroxide/oxide. Up to 150 ppm K can be tolerated. After purification of the Na anolyte, cell lifetimes in excess of 1000 deep charge-discharge cycles or over 8 months on continuous cycling at 10-30 percent depth of discharge were obtained.

  16. Mixed alkali effect in Li{sub 2}O-Na{sub 2}O-B{sub 2}O{sub 3} glasses containing Fe{sub 2}O{sub 3}-An EPR and optical absorption study

    SciTech Connect

    Sreekanth Chakradhar, R.P. . E-mail: chakra@cgcri.res.in; Yasoda, B.; Rao, J. Lakshmana . E-mail: jlrao46@yahoo.co.in; Gopal, N.O.

    2006-09-14

    This paper reports the interesting results on mixed alkali effect (MAE) in xLi{sub 2}O-(30-x)Na{sub 2}O-69.5B{sub 2}O{sub 3} (5 {<=} x {<=} 28) glasses containing Fe{sub 2}O{sub 3} studied by electron paramagnetic resonance (EPR) and optical absorption techniques. The EPR spectra in these glasses exhibit three resonance signals at g = 7.60, 4.20 and 2.02. The resonance signal at g = 7.60 has been attributed to Fe{sup 3+} ions in axial symmetry sites whereas the resonance signal at g = 4.20 is due to isolated Fe{sup 3+} ions in rhombic symmetry site. The resonance signal at g = 2.02 is due to Fe{sup 3+} ions coupled by exchange interaction. It is interesting to observe that the number of spins participating in resonance (N) and its paramagnetic susceptibility ({chi}) exhibits the mixed alkali effect with composition. The present study also gives an indication that the size of alkali ions we choose in mixed alkali glasses is also an important contributing factor in showing the mixed alkali effect. It is observed that the variation of N with temperature obeys Boltzmann law. A linear relationship is observed between 1/{chi} and T in accordance with Curie-Weiss law. The paramagnetic Curie temperature ({theta} {sub p}) is negative for the investigated sample, which suggests that the iron ions are antiferromagnetically coupled by negative super exchange interactions at very low temperatures. The optical absorption spectra exhibit only one weak band corresponding to the transition {sup 6}A{sub 1g}(S) {sup {yields}} {sup 4}A{sub 1g}(G); {sup 4}E{sub g}(G) at 446 nm which is a characteristic of Fe{sup 3+} ions in octahedral symmetry.

  17. A structural investigation of the alkali metal site distribution within bioactive glass using neutron diffraction and multinuclear solid state NMR.

    PubMed

    Martin, Richard A; Twyman, Helen L; Rees, Gregory J; Smith, Jodie M; Barney, Emma R; Smith, Mark E; Hanna, John V; Newport, Robert J

    2012-09-21

    The atomic-scale structure of Bioglass and the effect of substituting lithium for sodium within these glasses have been investigated using neutron diffraction and solid state magic angle spinning (MAS) NMR. Applying an effective isomorphic substitution difference function to the neutron diffraction data has enabled the Na-O and Li-O nearest-neighbour correlations to be isolated from the overlapping Ca-O, O-(P)-O and O-(Si)-O correlations. These results reveal that Na and Li behave in a similar manner within the glassy matrix and do not disrupt the short range order of the network former. Residual differences are attributed solely to the variation in ionic radius between the two species. Successful simplification of the 2 < r (Å) < 3 region via the difference method has enabled all the nearest neighbour correlations to be deconvolved. The diffraction data provides the first direct experimental evidence of split Na-O nearest-neighbour correlations in these melt quench bioactive glasses, and an analogous splitting of the Li-O correlations. The observed correlations are attributed to the metal ions bonded either to bridging or to non-bridging oxygen atoms. (23)Na triple quantum MAS (3QMAS) NMR data corroborates the split Na-O correlations. The structural sites present will be intimately related to the release properties of the glass system in physiological fluids such as plasma and saliva, and hence to the bioactivity of the material. Detailed structural knowledge is therefore a prerequisite for optimizing material design. PMID:22868255

  18. Barium aluminosilicate reinforced in situ with silicon nitride

    SciTech Connect

    Richardson, K.K.; Freitag, D.W.; Hunn, D.L.

    1995-10-01

    Advanced ceramic composite materials that exhibit high strength and toughness with good thermal shock resistance are needed for emerging high-temperature engineering applications. A recently developed in situ reinforced barium aluminosilicate glass-ceramic shows promise of meeting many of the requirements for these types of applications with the added benefit of low-cost fabrication through densification by pressureless sintering. The material is toughened through in situ growth of rodlike {beta}-Si{sub 3}N{sub 4} grains resulting from the {alpha}-{beta} silicon nitride phase transformation. Microstructural development and material properties for temperatures up to 1,400 C are discussed. When compared to monolithic barium aluminosilicate, barium aluminosilicate reinforced with 70% by volume of Si{sub 3}N{sub 4} shows a significant increase in flexural strength (from 80 to 565 MPa) and fracture toughness (from 1.8 to 5.74 MPa {center_dot} m{sup 1/2}) with a high resistance to thermal shock.

  19. Mechanism of interface formation in a silicon carbide fiber-reinforced magnesuium aluminosilicate

    SciTech Connect

    Kumar, A.; Knowles, K.M.

    1995-12-01

    The formation of sliding interfacial layers is a major key to the success of fiber-reinforced glass-ceramics. This paper reports the mechanism of formation of fiber-matrix interfaces during oxidizing heat treatments in a SiC fiber-reinforced magnesium aluminosilicate.

  20. Aluminosilicate Precipitation Impact on Uranium

    SciTech Connect

    WILMARTH, WILLIAM

    2006-03-10

    Experiments have been conducted to examine the fate of uranium during the formation of sodium aluminosilicate (NAS) when wastes containing high aluminate concentrations are mixed with wastes of high silicate concentration. Testing was conducted at varying degrees of uranium saturation. Testing examined typical tank conditions, e.g., stagnant, slightly elevated temperature (50 C). The results showed that under sub-saturated conditions uranium is not removed from solution to any large extent in both simulant testing and actual tank waste testing. This aspect was not thoroughly understood prior to this work and was necessary to avoid criticality issues when actual tank wastes were aggregated. There are data supporting a small removal due to sorption of uranium on sites in the NAS. Above the solubility limit the data are clear that a reduction in uranium concentration occurs concomitant with the formation of aluminosilicate. This uranium precipitation is fairly rapid and ceases when uranium reaches its solubility limit. At the solubility limit, it appears that uranium is not affected, but further testing might be warranted.

  1. Spectroscopy and laser action of rhodamine 6G doped aluminosilicate xerogels

    SciTech Connect

    McKiernan, J.M.; Yamanaka, S.A.; Dunn, B.; Zink, J.I. )

    1990-07-26

    Rhodamine 6G (R6G) doped aluminosilicate glass synthesized by the sol-gel method exhibits laser action. Transparent 5 mm {times} 5 mm {times} 10 mm monoliths were used as cast in a simple laser cavity. This new material was pumped at rates of up to 25 Hz and was still active after as many as 40,000 pump pulses. Luminescence and free-running laser spectra are measured. The dependence of the R6G doped aluminosilicate dye laser output on the number of pump pulses and the pump pulse energy is discussed.

  2. Microstructural and phase evolution in metakaolin geopolymers with different activators and added aluminosilicate fillers

    NASA Astrophysics Data System (ADS)

    Sarkar, Madhuchhanda; Dana, Kausik; Das, Sukhen

    2015-10-01

    This work aims to investigate the microstructural and phase evolution of alkali activated metakaolin products with different activators and added aluminosilicate filler phases. The added filler phases have different reactivity to the alkali activated metakaolin system. Microstructural evolution in the alkali activated products has been investigated by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Field Emission Scanning Electron Microscope (FESEM). Variation in strength development in alkali activated metakaolin products was followed by compressive strength measurement test. Microstructural study shows that in case of metakaolin with NaOH activator crystalline sodalite formed in all the product samples irrespective of the added filler phases. The microstructure of these NaOH activated products investigated by FESEM showed crystalline and inhomogeneous morphology. Mixed activator containing both NaOH and sodium silicate in a fixed mass ratio formed predominantly amorphous phase. Microstructure of these samples showed more homogeneity than that of NaOH activated metakaolin products. The study further shows that addition of α-Al2O3 powder, non reactive phase to the alkali activated metakaolin system when used in larger amount increased crystalline phase in the matrix. α-Al2O3 powder addition increased the compressive strength of the product samples for both the activator compositions. Added phase of colloidal silica, reactive to the alkali activated metakaolin system when used in larger amount was found to increase amorphous nature of the matrix. Addition of colloidal silica influenced the compressive strength property differently with different activator compositions.

  3. Alkali Bee

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The alkali bee, Nomia melanderi, is native to deserts and semi-arid desert basins of the western United States. It is a very effective and manageable pollinator for the production of seed in alfalfa (=lucerne) and some other crops, such as onion. It is the world’s only intensively managed ground-n...

  4. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, Raymond D.; McPheeters, Charles C.

    1980-01-01

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  5. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, R.D.; McPheeters, C.C.

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  6. Effect of Zn- and Ca-oxides on the structure and chemical durability of simulant alkali borosilicate glasses for immobilisation of UK high level wastes

    NASA Astrophysics Data System (ADS)

    Zhang, Hua; Corkhill, Claire L.; Heath, Paul G.; Hand, Russell J.; Stennett, Martin C.; Hyatt, Neil C.

    2015-07-01

    Compositional modification of United Kingdom high level nuclear waste (HLW) glasses was investigated with the aim of understanding the impact of adopting a ZnO/CaO modified base glass on the vitrified product phase assemblage, glass structure, processing characteristics and dissolution kinetics. Crystalline spinel phases were identified in the vitrified products derived from the Na2O/Li2O and the ZnO/CaO modified base glass compositions; the volume fraction of the spinel crystallites increased with increasing waste loading from 15 to 20 wt%. The spinel composition was influenced by the base glass components; in the vitrified product obtained with the ZnO/CaO modified base glass, the spinel phase contained a greater proportion of Zn, with a nominal composition of (Zn0.60Ni0.20Mg0.20)(Cr1.37Fe0.63)O4. The addition of ZnO and CaO to the base glass was also found to significantly alter the glass structure, with changes identified in both borate and silicate glass networks using Raman spectroscopy. In particular, these glasses were characterised by a significantly higher Q3 species, which we attribute to Si-O-Zn linkages; addition of ZnO and CaO to the glass composition therefore enhanced glass network polymerisation. The increase in network polymerisation, and the presence of spinel crystallites, were found to increase the glass viscosity of the ZnO/CaO modified base glass; however, the viscosities were within the accepted range for nuclear waste glass processing. The ZnO/CaO modified glass compositions were observed to be significantly more durable than the Na2O/Li2O base glass up to 28 days, due to a combination of the enhanced network polymerisation and the formation of Ca/Si containing alteration layers.

  7. Geopolymers and Related Alkali-Activated Materials

    NASA Astrophysics Data System (ADS)

    Provis, John L.; Bernal, Susan A.

    2014-07-01

    The development of new, sustainable, low-CO2 construction materials is essential if the global construction industry is to reduce the environmental footprint of its activities, which is incurred particularly through the production of Portland cement. One type of non-Portland cement that is attracting particular attention is based on alkali-aluminosilicate chemistry, including the class of binders that have become known as geopolymers. These materials offer technical properties comparable to those of Portland cement, but with a much lower CO2 footprint and with the potential for performance advantages over traditional cements in certain niche applications. This review discusses the synthesis of alkali-activated binders from blast furnace slag, calcined clay (metakaolin), and fly ash, including analysis of the chemical reaction mechanisms and binder phase assemblages that control the early-age and hardened properties of these materials, in particular initial setting and long-term durability. Perspectives for future research developments are also explored.

  8. Alkali element background reduction in laser ICP-MS

    NASA Astrophysics Data System (ADS)

    Magee, C. W., Jr.; Norris, C. A.

    2014-11-01

    Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionization of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary both can easily be applied to the routine operations of an analytical lab.

  9. Alkali element background reduction in laser ICP-MS

    NASA Astrophysics Data System (ADS)

    Magee, C. W., Jr.; Norris, C. A.

    2015-03-01

    Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionisation of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high-alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary, both can easily be applied to the routine operations of an analytical lab.

  10. Dissolution and Separation of Aluminum and Aluminosilicates

    DOE PAGESBeta

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; Felker, Leslie Kevin; Mattus, Catherine H.

    2015-12-19

    The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as amore » function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

  11. Dissolution and Separation of Aluminum and Aluminosilicates

    SciTech Connect

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; Felker, Leslie Kevin; Mattus, Catherine H.

    2015-12-19

    The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.

  12. Phase evolution of Na2O-Al2O3-SiO2-H2O gels in synthetic aluminosilicate binders.

    PubMed

    Walkley, Brant; San Nicolas, Rackel; Sani, Marc-Antoine; Gehman, John D; van Deventer, Jannie S J; Provis, John L

    2016-04-01

    This study demonstrates the production of stoichiometrically controlled alkali-aluminosilicate gels ('geopolymers') via alkali-activation of high-purity synthetic amorphous aluminosilicate powders. This method provides for the first time a process by which the chemistry of aluminosilicate-based cementitious materials may be accurately simulated by pure synthetic systems, allowing elucidation of physicochemical phenomena controlling alkali-aluminosilicate gel formation which has until now been impeded by the inability to isolate and control key variables. Phase evolution and nanostructural development of these materials are examined using advanced characterisation techniques, including solid state MAS NMR spectroscopy probing (29)Si, (27)Al and (23)Na nuclei. Gel stoichiometry and the reaction kinetics which control phase evolution are shown to be strongly dependent on the chemical composition of the reaction mix, while the main reaction product is a Na2O-Al2O3-SiO2-H2O type gel comprised of aluminium and silicon tetrahedra linked via oxygen bridges, with sodium taking on a charge balancing function. The alkali-aluminosilicate gels produced in this study constitute a chemically simplified model system which provides a novel research tool for the study of phase evolution and microstructural development in these systems. Novel insight of physicochemical phenomena governing geopolymer gel formation suggests that intricate control over time-dependent geopolymer physical properties can be attained through a careful precursor mix design. Chemical composition of the main N-A-S-H type gel reaction product as well as the reaction kinetics governing its formation are closely related to the Si/Al ratio of the precursor, with increased Al content leading to an increased rate of reaction and a decreased Si/Al ratio in the N-A-S-H type gel. This has significant implications for geopolymer mix design for industrial applications. PMID:26911317

  13. An investigation of waste glass-based geopolymers supplemented with alumina

    NASA Astrophysics Data System (ADS)

    Christiansen, Mary U.

    An increased consideration of sustainability throughout society has resulted in a surge of research investigating sustainable alternatives to existing construction materials. A new binder system, called a geopolymer, is being investigated to supplement ordinary portland cement (OPC) concrete, which has come under scrutiny because of the CO2 emissions inherent in its production. Geopolymers are produced from the alkali activation of a powdered aluminosilicate source by an alkaline solution, which results in a dense three-dimensional matrix of tetrahedrally linked aluminosilicates. Geopolymers have shown great potential as a building construction material, offering similar mechanical and durability properties to OPC. Additionally, geopolymers have the added value of a considerably smaller carbon footprint than OPC. This research considered the compressive strength, microstructure and composition of geopolymers made from two types of waste glass with varying aluminum contents. Waste glass shows great potential for mainstream use in geopolymers due to its chemical and physical homogeneity as well as its high content of amorphous silica, which could eliminate the need for sodium silicate. However, the lack of aluminum is thought to negatively affect the mechanical performance and alkali stability of the geopolymer system. 39 Mortars were designed using various combinations of glass and metakaolin or fly ash to supplement the aluminum in the system. Mortar made from the high-Al glass (12% Al2O3) reached over 10,000 psi at six months. Mortar made from the low-Al glass (<1% Al2O3) did not perform as well and remained sticky even after several weeks of curing, most likely due to the lack of Al which is believed to cause hardening in geopolymers. A moderate metakaolin replacement (25-38% by mass) was found to positively affect the compressive strength of mortars made with either type of glass. Though the microstructure of the mortar was quite indicative of mechanical

  14. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  15. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  16. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  17. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  18. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... (CONTINUED) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium...

  19. Secondary Ion Mass Spectrometry of Zeolite Materials: Observation of Abundant Aluminosilicate Oligomers Using an Ion Trap

    SciTech Connect

    Groenewold, Gary Steven; Kessinger, Glen Frank; Scott, Jill Rennee; Gianotto, Anita Kay; Appelhans, Anthony David; Delmore, James Edward

    2000-12-01

    Oligomeric oxyanions were observed in the secondary ion mass spectra (SIMS) of zeolite materials. The oxyanions have the general composition AlmSinO2(m+n)H(m-1)- (m + n = 2 to 8) and are termed dehydrates. For a given mass, multiple elemental compositions are possible because (Al + H) is an isovalent and isobaric substitute for Si. Using 18 keV Ga+ as a projectile, oligomer abundances are low relative to the monomers. Oligomer abundance can be increased by using the polyatomic projectile ReO4- (~5 keV). Oligomer abundance can be further increased using an ion trap (IT-) SIMS; in this instrument, long ion lifetimes (tens of ms) and relatively high He pressure result in significant collisional stabilization and increased high-mass abundance. The dehydrates rapidly react with adventitious H2O present in the IT-SIMS to form mono-, di-, and trihydrates. The rapidity of the reaction and comparison to aluminum oxyanion hydration suggest that H2O adds to the aluminosilicate oxyanions in a dissociative fashion, forming covalently bound product ions. In addition to these findings, it was noted that production of abundant oligomeric aluminosilicates could be significantly increased by substituting the countercation (NH4+) with the larger alkali ions Rb+ and Cs+. This constitutes a useful tactic for generating large aluminosilicate oligomers for surface characterization and ion-molecule reactivity studies.

  20. 40 CFR 721.633 - Aluminosilicates, phospho-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... reporting. (1) The chemical substance identified as Aluminosilicates, phospho- (PMN P-98-1275; CAS No... in § 721.125 (a), (b), (c), (d), (f), (g), (h), and (i) are applicable to manufacturers, importers... Section 721.633 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC...

  1. 40 CFR 721.633 - Aluminosilicates, phospho-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... reporting. (1) The chemical substance identified as Aluminosilicates, phospho- (PMN P-98-1275; CAS No... in § 721.125 (a), (b), (c), (d), (f), (g), (h), and (i) are applicable to manufacturers, importers... Section 721.633 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC...

  2. Integrating Sphere Alkali-Metal Vapor Cells

    NASA Astrophysics Data System (ADS)

    McGuyer, Bart; Ben-Kish, Amit; Jau, Yuan-Yu; Happer, William

    2010-03-01

    An integrating sphere is an optical multi-pass cavity that uses diffuse reflection to increase the optical path length. Typically applied in photometry and radiometry, integrating spheres have previously been used to detect trace gases and to cool and trap alkali-metal atoms. Here, we investigate the potential for integrating spheres to enhance optical absorption in optically thin alkali-metal vapor cells. In particular, we consider the importance of dielectric effects due to a glass container for the alkali-metal vapor. Potential applications include miniature atomic clocks and magnetometers, where multi-passing could reduce the operating temperature and power consumption.

  3. Charge-transfer state excitation as the main mechanism of the photodarkening process in ytterbium-doped aluminosilicate fibres

    SciTech Connect

    Bobkov, K K; Rybaltovsky, A A; Vel'miskin, V V; Likhachev, M E; Bubnov, M M; Dianov, E M; Umnikov, A A; Gur'yanov, A N; Vechkanov, N N; Shestakova, I A

    2014-12-31

    We have studied photodarkening in ytterbium-doped fibre preforms with an aluminosilicate glass core. Analysis of their absorption and luminescence spectra indicates the formation of stable Yb{sup 2+} ions in the glass network under IR laser pumping at a wavelength λ = 915 nm and under UV irradiation with an excimer laser (λ = 193 nm). We have performed comparative studies of the luminescence spectra of the preforms and crystals under excitation at a wavelength of 193 nm. The mechanism behind the formation of Yb{sup 2+} ions and aluminium – oxygen hole centres (Al-OHCs), common to ytterbium-doped YAG crystals and aluminosilicate glass, has been identified: photoinduced Yb{sup 3+} charge-transfer state excitation. (optical fibres)

  4. Why neutron guides may end up breaking down? Some results on the macroscopic behaviour of alkali-borosilicate glass support plates under neutron irradiation

    NASA Astrophysics Data System (ADS)

    Boffy, R.; Kreuz, M.; Beaucour, J.; Köster, U.; Bermejo, F. J.

    2015-09-01

    In this paper we report on a first part of a study on the mechanisms leading to brittle fracture in neutron guides made of glass as structural element. Such devices are widely used to deliver thermal and cold neutron beams to experimental lines in most large neutron research facilities. We present results on macroscopic properties of samples of guide glass substrates which are subjected to neutron irradiation at relatively large fluences. The results show a striking dependence of some of the macroscopic properties such as density, shape or surface curvature upon the specific chemical composition of a given glass. The relevance of the present findings for the installation of either replacement guides at the existing facilities or for the deployment of instruments for ongoing projects such as the European Spallation Source is briefly discussed.

  5. Glass/BNNT Composite for Sealing Solid Oxide Fuel Cells

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Hurst, Janet B.; Choi, Sung R.

    2007-01-01

    A material consisting of a barium calcium aluminosilicate glass reinforced with 4 weight percent of boron nitride nanotubes (BNNTs) has shown promise for use as a sealant in planar solid oxide fuel cells (SOFCs).

  6. Super ionic conductive glass

    DOEpatents

    Susman, Sherman; Volin, Kenneth J.

    1984-01-01

    An ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A.sub.1+x D.sub.2-x/3 Si.sub.x P.sub.3-x O.sub.12-2x/3, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

  7. Super ionic conductive glass

    DOEpatents

    Susman, S.; Volin, K.J.

    Described is an ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A/sub 1 + x/D/sub 2-x/3/Si/sub x/P/sub 3 - x/O/sub 12 - 2x/3/, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

  8. Alkali metal nitrate purification

    DOEpatents

    Fiorucci, Louis C.; Morgan, Michael J.

    1986-02-04

    A process is disclosed for removing contaminants from impure alkali metal nitrates containing them. The process comprises heating the impure alkali metal nitrates in solution form or molten form at a temperature and for a time sufficient to effect precipitation of solid impurities and separating the solid impurities from the resulting purified alkali metal nitrates. The resulting purified alkali metal nitrates in solution form may be heated to evaporate water therefrom to produce purified molten alkali metal nitrates suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of purified alkali metal nitrates.

  9. Solubility and solution mechanisms of chlorine in aluminosilicate melts at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Dalou, C.; Mysen, B. O.

    2012-12-01

    We address the effect of alkalies and aluminum on the solution behavior of Cl by combining solubility measurements of Cl and Raman data of Cl-bearing peralkaline aluminosilicate glasses (quenched melt). Six compositions along the join Na2Si3O7(NS3)-Na2(NaAl)3O7 and six compositions along the join K2Si3O7(KS3)-K2(KAl)3O7 were used. In order to isolate potential effects of Al/(Al+Si) from changes on melt polymerization, Al2O3 was exchanged with SiO2 in a charge-balanced form, NaAlO2 and KaAlO2 thus keeping approximately constant NBO/T (0.65 ± 0.02) for all melts (assuming Al3+ in 4-fold coordination in the melts). Starting materials were doped with 5wt% Cl in the form of PdCl2, which releases Cl2 as its gaseous phase during experiment. Samples were synthetized on piston-cylinder apparatus at 1600°C - 1.5 GPa. At the end of the experiments, Pd forms little spheres (1-2 μm) that for most part dissolves into the capsule. Chlorine oversaturation in the melts is ensured by the observation of bubbles in the quenched samples. The Cl solubility in Na-bearing systems is about twice that of the than in K-bearing system and may, therefore, be negatively correlated with ionic radius of the metal cation.. The solubility also decreases with Al/(Al+Si). In NS3 system, it decreases from 4.01 ± 0.13 wt% of Cl in Al-free systems to 1.87 ± 0.19 wt% of Cl for an Al/Al+Si ratio of 0.34. In KS3 system, this decrease is from 2.23 ± 0.08 wt% of Cl in Al-free systems to 0.62 ± 0.05 wt% of Cl for an Al/Al+Si ratio of 0.36. In Al-free systems, preliminary Raman data show the appearance of a peak around 465cm-1, that we assigned to alkali-Cl bonding. The intensity of this 465cm-1 peak increases with Al content confirming the role of Al in Cl solution mechanism.We also identify the molecular Cl peak at 1540cm-1. The peak can be detected only in Al-bearing melts. The Al substitution for Si results in increased abundance of three-dimensional cages on the melt structure into which molecular

  10. Milk-alkali syndrome

    MedlinePlus

    ... this page: //medlineplus.gov/ency/article/000332.htm Milk-alkali syndrome To use the sharing features on this page, please enable JavaScript. Milk-alkali syndrome is a condition in which there ...

  11. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, D.C.; Mailhe, C.C.; De Jonghe, L.C.

    1985-07-10

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  12. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, David C.; Mailhe, Catherine C.; De Jonghe, Lutgard C.

    1986-01-01

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  13. Calcium-magnesium Aluminosilicate (CMAS) Interactions with Advanced Environmental Barrier Coating Material

    NASA Technical Reports Server (NTRS)

    Wiesner, Valerie L.; Bansal, Narottam P.

    2015-01-01

    Particulates, like sand and volcanic ash, threaten the development of robust environmental barrier coatings (EBCs) that protect next-generation silicon-based ceramic matrix composite (CMC) turbine engine components from harsh combustion environments during service. The siliceous particulates transform into molten glassy deposits of calcium-magnesium aluminosilicate (CMAS) when ingested by an aircraft engine operating at temperatures above 1200C. In this study, a sample of desert sand was melted into CMAS glass to evaluate high-temperature interactions between the sand glass and an advanced EBC material. Desert sand glass was added to the surface of hot-pressed EBC substrates, which were then heated in air at temperatures ranging from 1200C to 1500C. Scanning electron microscopy and X-ray energy-dispersive spectroscopy were used to evaluate microstructure and phase compositions of specimens and the CMASEBC interface after heat treatments.

  14. Uranium and Aluminosilicate Surface Precipitation Tests

    SciTech Connect

    Hu, M.Z.

    2002-11-27

    The 2H evaporator at the Savannah River Site has been used to treat an aluminum-rich waste stream from canyon operations and a silicon-rich waste stream from the Defense Waste Processing Facility. The formation of aluminosilicate scale in the evaporator has caused significant operational problems. Because uranium has been found to accumulate in the aluminosilicate solids, the scale deposition has introduced criticality concerns as well. The objective of the tests described in this report is to determine possible causes of the uranium incorporation in the evaporator scale materials. The scope of this task is to perform laboratory experiments with simulant solutions to determine if (1) uranium can be deposited on the surfaces of various sodium aluminosilicate (NAS) forms and (2) aluminosilicates can form on the surfaces of uranium-containing solids. Batch experiments with simulant solutions of three types were conducted: (1) contact of uranium solutions/sols with NAS coatings on stainless steel surfaces, (2) contact of uranium solutions with NAS particles, and (3) contact of precipitated uranium-containing particles with solutions containing aluminum and silicon. The results show that uranium can be incorporated in NAS solids through encapsulation in bulk agglomerated NAS particles of different phases (amorphous, zeolite A, sodalite, and cancrinite) as well as through heterogeneous deposition on the surfaces of NAS coatings (amorphous and cancrinite) grown on stainless steel. The results also indicate that NAS particles can grow on the surfaces of precipitated uranium solids. Particularly notable for evaporator operations is the finding that uranium solids can form on existing NAS scale, including cancrinite solids. If NAS scale is present, and uranium is in sufficient concentration in solution to precipitate, a portion of the uranium can be expected to become associated with the scale. The data obtained to date on uranium-NAS affinity are qualitative. A necessary

  15. Use of precalciners to remove alkali from raw materials in the cement industry. Final report, July 1978-July 1980

    SciTech Connect

    Gartner, E.M.

    1980-07-01

    The objective of this work was to develop an efficient means of removing alkali metal compounds (alkalies) from high-alkali aluminosilicate raw materials of the type commonly used as part of cement raw mixes in order to increase the energy efficiency of cement manufacture. The intention of this project was to determine whether the high-alkali raw materials could be pyroprocessed separately to remove the alkalies before they entered the rotary kiln, where they would be mixed with the other raw feed components. If this could be achieved, considerable savings could be made in the energy required to remove alkalies, compared to conventional methods in which the cement raw mix must be treated as a whole. Two different methods of alkali removal were examined, namely, vaporization of alkalies at relatively low temperatures; and alkali-rich melt separation at relativey high temperatures. The results showed that the removal of alkalies by pyroprocessing of high-alkali raw feed components separate from the other cement raw mix components is not likely to be a practical alternative to the best available conventional precalciner technology. (LCL)

  16. 29Si NMR study of structural ordering in aluminosilicate geopolymer gels.

    PubMed

    Duxson, Peter; Provis, John L; Lukey, Grant C; Separovic, Frances; van Deventer, Jannie S J

    2005-03-29

    A systematic series of aluminosilicate geopolymer gels was synthesized and then analyzed using 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR) in combination with Gaussian peak deconvolution to characterize the short-range ordering in terms of T-O-T bonds (where T is Al or Si). The effect of nominal Na2O/(Na2O + K2O) and Si/Al ratios on short-range network ordering was quantified by deconvolution of the 29Si MAS NMR spectra into individual Gaussian peaks representing different Q4(mAl) silicon centers. The deconvolution procedure developed in this work is applicable to other aluminosilicate gel systems. The short-range ordering observed here indicates that Loewenstein's Rule of perfect aluminum avoidance may not apply strictly to geopolymeric gels, although further analyses are required to quantify the degree of aluminum avoidance. Potassium geopolymers appeared to exhibit a more random Si/Al distribution compared to that of mixed-alkali and sodium systems. This work provides a quantitative account of the silicon and aluminum ordering in geopolymers, which is essential for extending our understanding of the mechanical strength, chemical and thermal stability, and fundamental structure of these systems. PMID:15779981

  17. Calculation of the 13C NMR shieldings of the C0 2 complexes of aluminosilicates

    NASA Astrophysics Data System (ADS)

    Tossell, J. A.

    1995-04-01

    13C NMR shieldings have been calculated using the random-phase-approximation, localized-orbital local-origins version of ab initio coupled Hartree-Fuck perturbation theory for CO 2 and and for several complexes formed by the reaction of CO 2 with molecular models for aluminosilicate glasses, H 3TOT'H3 3-n, T,T' = Si,Al. Two isomeric forms of the CO 2-aluminosilicate complexes have been considered: (1) "CO 2-like" complexes, in which the CO 2 group is bound through carbon to a bridging oxygen and (2) "CO 3-like" complexes, in which two oxygens of a central CO 3 group form bridging bonds to the two TH 3 groups. The CO 2-like isomer of CO 2-H 3SiOSiH 3 is quite weakly bonded and its 13C isotropic NMR shielding is almost identical to that in free CO 2. As Si is progressively replaced by Al in the - H terminated aluminosilicate model, the CO 2-like isomers show increasing distortion from the free CO 2 geometry and their 13C NMR shieldings decrease uniformly. The calculated 13C shielding value for H 3AlO(CO 2)AlH 3-2 is only about 6 ppm larger than that calculated for point charge stabilized CO 3-2. However, for a geometry of H 3SiO(CO 2) AlH 3-1, in which the bridging oxygen to C bond length has been artificially increased to that found in the - OH terminated cluster (OH) 3SiO(CO 2)Al(OH) 3-1, the calculated 13C shielding is almost identical to that for free CO 2. The CO 3-like isomers of the CO 2-aluminosili-cate complexes show carbonate like geometries and 13C NMR shieldings about 4-9 ppm larger than those of carbonate for all T,T' pairs. For the Si,Si tetrahedral atom pair the CO 2-like isomer is more stable energetically, while for the Si,Al and Al,Al cases the CO 3-like isomer is more stable. Addition of Na + ions to the CO 3-2 or H 3AlO(CO 2)AlH 3-2 complexes reduces the 13C NMR shieldings by about 10 ppm. Complexation with either Na + or CO 2 also reduces the 29Si NMR shieldings of the aluminosilicate models, while the changes in 27Al shielding with Na + or CO 2

  18. The Influence of Base Concentration on the Surface Particle of Lithium Aluminosilicate System

    SciTech Connect

    Nazri, I. M.; Asliza, M. A. Sri; Othman, R.

    2008-03-17

    The study of base concentration effect toward surface particles of lithium aluminosilicate glass ceramic system has been done by using NaOH solution. The parent glass with composition of 60% SiO{sub 2}, 31% Li{sub 2}O, 6% Al{sub 2}O{sub 3} and 3% TiO{sub 2} in wt% was prepared by melting process at 1250 deg. C prior to quenching rapidly to room temperature. Sintering and crystallization process on this parent glass were carefully examined by Differential thermal analysis (DTA) and X-Ray Diffraction (XRD). Based on these analyses, the selected crystal has been chosen as a precursor material. There are two controlling parameter involved in this study i.e. NaOH concentration and leaching period. The morphology of the glass ceramic particle was observed by Field Emission Scanning Electron Microscope (FESEM). The result shows that by increasing the basic concentration as well as increasing the soaking leaching period, the tendency of glass ceramic particle to leach out is relatively highs.

  19. Stabilization/solidification of hazardous and radioactive wastes with alkali-activated cements.

    PubMed

    Shi, Caijun; Fernández-Jiménez, A

    2006-10-11

    This paper reviews progresses on the use of alkali-activated cements for stabilization/solidification of hazardous and radioactive wastes. Alkali-activated cements consist of an alkaline activator and cementing components, such as blast furnace slag, coal fly ash, phosphorus slag, steel slag, metakaolin, etc., or a combination of two or more of them. Properly designed alkali-activated cements can exhibit both higher early and later strengths than conventional portland cement. The main hydration product of alkali-activated cements is calcium silicate hydrate (CSH) with low Ca/Si ratios or aluminosilicate gel at room temperature; CSH, tobmorite, xonotlite and/or zeolites under hydrothermal condition, no metastable crystalline compounds such as Ca(OH)(2) and calcium sulphoaluminates exist. Alkali-activated cements also exhibit excellent resistance to corrosive environments. The leachability of contaminants from alkali-activated cement stabilized hazardous and radioactive wastes is lower than that from hardened portland cement stabilized wastes. From all these aspects, it is concluded that alkali-activated cements are better matrix for solidification/stabilization of hazardous and radioactive wastes than Portland cement. PMID:16787699

  20. Structure-Directing Behaviors of Tetraethylammonium Cations toward Zeolite Beta Revealed by the Evolution of Aluminosilicate Species Formed during the Crystallization Process.

    PubMed

    Ikuno, Takaaki; Chaikittisilp, Watcharop; Liu, Zhendong; Iida, Takayuki; Yanaba, Yutaka; Yoshikawa, Takeshi; Kohara, Shinji; Wakihara, Toru; Okubo, Tatsuya

    2015-11-18

    Organic structure-directing agents (OSDAs) have been widely used for the synthesis of zeolites. In most cases, OSDAs are occluded in zeolites as an isolated cation or molecule geometrically fitted within the zeolite cavities. This is not the case for zeolite beta synthesized by using tetraethylammonium (TEA(+)) cation as an OSDA, in which a cluster/aggregate of ca. six TEA(+) cations is occluded intact in the cavity (i.e., the channel intersection) of zeolite beta. The structure direction of TEA(+) in such a nontypical, clustered mode has remained elusive. Here, zeolite beta was hydrothermally synthesized using TEA(+) in the absence of other alkali metal cations in order to focus on the structure-directing behaviors of TEA(+) alone. The solid products formed throughout the hydrothermal synthesis were analyzed by an array of characterization techniques including argon adsorption-desorption, high-energy X-ray total scattering, Raman and solid-state NMR spectroscopy, and high-resolution transmission electron microscopy. It was revealed that the formation of amorphous TEA(+)-aluminosilicate composites and their structural, chemical, and textural evolution toward the amorphous zeolite beta-like structure during the induction period is vital for the formation of zeolite beta. A comprehensive scheme of the formation of zeolite beta is proposed paying attention to the clustered behavior of TEA(+) as follows: (i) the formation of the TEA(+)-aluminosilicate composites after heating, (ii) the reorganization of aluminosilicates together with the conformational rearrangement of TEA(+), yielding the formation of the amorphous TEA(+)-aluminosilicate composites with the zeolite beta-like structure, (iii) the formation of zeolite beta nuclei by solid-state reorganization of such zeolite beta-like, TEA(+)-aluminosilicate composites, and (iv) the subsequent crystal growth. It is anticipated that these findings can provide a basis for broadening the utilization of OSDAs in the

  1. Secondary Waste Form Screening Test Results—Cast Stone and Alkali Alumino-Silicate Geopolymer

    SciTech Connect

    Pierce, Eric M.; Cantrell, Kirk J.; Westsik, Joseph H.; Parker, Kent E.; Um, Wooyong; Valenta, Michelle M.; Serne, R. Jeffrey

    2010-06-28

    PNNL is conducting screening tests on the candidate waste forms to provide a basis for comparison and to resolve the formulation and data needs identified in the literature review. This report documents the screening test results on the Cast Stone cementitious waste form and the Geopolymer waste form. Test results suggest that both the Cast Stone and Geopolymer appear to be viable waste forms for the solidification of the secondary liquid wastes to be treated in the ETF. The diffusivity for technetium from the Cast Stone monoliths was in the range of 1.2 × 10-11 to 2.3 × 10-13 cm2/s during the 63 days of testing. The diffusivity for technetium from the Geopolymer was in the range of 1.7 × 10-10 to 3.8 × 10-12 cm2/s through the 63 days of the test. These values compare with a target of 1 × 10-9 cm2/s or less. The Geopolymer continues to show some fabrication issues with the diffusivities ranging from 1.7 × 10-10 to 3.8 × 10-12 cm2/s for the better-performing batch to from 1.2 × 10-9 to 1.8 × 10-11 cm2/s for the poorer-performing batch. In the future more comprehensive and longer term performance testing will be conducted, to further evaluate whether or not these waste forms will meet the regulation and performance criteria needed to cost-effectively dispose of secondary wastes.

  2. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-04-29

    A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  3. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christopher P; Boldingh, Edwin P

    2013-12-17

    A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  4. Aluminosilicate nanoparticles for catalytic hydrocarbon cracking.

    PubMed

    Liu, Yu; Pinnavaia, Thomas J

    2003-03-01

    Aluminosilicate nanoparticles containing 9.0-20 nm mesopores were prepared through the use of protozeolitic nanoclusters as the inorganic precursor and starch as a porogen. The calcined, porogen-free composition containing 2 mol % aluminum exhibited the porosity, hydrothermal stability, and acidity needed for the cracking of very large hydrocarbons. In fact, the hydrothermal stability of the nanoparticles to pure steam at 800 degrees C, along with the cumene cracking activity, surpassed the analogous performance properties of ultrastable Y zeolite, the main catalyst component of commercial cracking catalysts. The remarkable hydrothermal stability and catalytic reactivity of the new nanoparticles are attributable to a unique combination of two factors, the presence of protozeolitic nanoclusters in the pore walls and the unprecedented pore wall thickness (7-15 nm). In addition, the excellent catalytic longevity of the nanoparticles is most likely facilitated by the small domain size of the nanoparticles that greatly improves access to the acid sites on the pore walls and minimizes the diffusion length of coke precursors out of the pores. PMID:12603109

  5. Electromagnetic and Mechanical Properties of Silica-Aluminosilicates Plasma Sprayed Composite Coatings

    NASA Astrophysics Data System (ADS)

    Cipri, F.; Bartuli, C.; Valente, T.; Casadei, F.

    2007-12-01

    The physico-chemical and thermo-mechanical properties of aluminosilicate ceramics (high-melting point, low thermal expansion coefficient, excellent thermal shock resistance, low-density and good corrosion resistance) make this class of materials a good option for high-temperature structural applications. Al2O3-SiO2 compounds show an excellent refractory behavior allowing a wide use as wear-resistant thermal barrier coatings, in metallurgical and glass plants and in high temperature heat exchangers. Moreover, the low values of thermal expansion coefficient and of complex permittivity allow to extend the use of this ceramic for microelectronic devices, radome for antennas and electromagnetic windows for microwaves and infrared. The present article presents the results of an extensive experimental activity carried out to produce thick aluminosilicate coatings by plasma-spray technique. The APS deposition parameters were optimized on the basis of a surface response approach, as specified by design of experiments (DoE) methodologies. Samples were tested for phase composition, total porosity, microstructure, microhardness, deposition efficiency, fracture toughness, and modulus of rupture. Finally, coatings were characterized for their particularly interesting electromagnetic properties: complex permittivity was measured at microwave frequency using a network analyzer with wave guide.

  6. Alkali metal ionization detector

    DOEpatents

    Bauerle, James E.; Reed, William H.; Berkey, Edgar

    1978-01-01

    Variations in the conventional filament and collector electrodes of an alkali metal ionization detector, including the substitution of helical electrode configurations for either the conventional wire filament or flat plate collector; or, the substitution of a plurality of discrete filament electrodes providing an in situ capability for transferring from an operationally defective filament electrode to a previously unused filament electrode without removing the alkali metal ionization detector from the monitored environment. In particular, the helical collector arrangement which is coaxially disposed about the filament electrode, i.e. the thermal ionizer, provides an improved collection of positive ions developed by the filament electrode. The helical filament design, on the other hand, provides the advantage of an increased surface area for ionization of alkali metal-bearing species in a monitored gas environment as well as providing a relatively strong electric field for collecting the ions at the collector electrode about which the helical filament electrode is coaxially positioned. Alternatively, both the filament and collector electrodes can be helical. Furthermore, the operation of the conventional alkali metal ionization detector as a leak detector can be simplified as to cost and complexity, by operating the detector at a reduced collector potential while maintaining the sensitivity of the alkali metal ionization detector adequate for the relatively low concentration of alkali vapor and aerosol typically encountered in leak detection applications.

  7. The effect of TiO2/aluminosilicate nanocomposite additives on the mechanical and thermal properties of polyacrylic coatings

    NASA Astrophysics Data System (ADS)

    Nosrati, Rahimeh; Olad, Ali

    2015-12-01

    The commercial grade polyacrylic latex was modified in order to prepare a mechanical and thermal improved coating. TiO2/Ag-exchanged-aluminosilicate nanocomposites with montmorillonite, zeolite-A and clinoptilolite aluminosilicates were prepared and used as additive in the matrix of polyacrylic latex to achieve a coating with proper mechanical and thermal properties. X-ray diffraction patterns and FESEM were used to characterize the composition, structure, and morphology of the nanocomposite additives. Polyacrylic coatings modified by TiO2/Ag-exchanged-aluminosilicate nanocomposite additives showed higher adhesion strength and hardness compared to unmodified commercial grade polyacrylic coatings. Differential Scanning Calorimetry (DSC) analysis showed lower glass transition temperature for modified polyacrylic coatings than that of unmodified polyacrylic coatings. The tensile tests were also carried out for unmodified and modified polyacrylic coatings. According to the results, the modified polyacrylic based coating with TiO2/Ag-exchanged-clinoptilolite nanocomposite additive was the best coating considering most of useful properties.

  8. Channel waveguides in glass via silver-sodium field-assisted ion exchange

    NASA Technical Reports Server (NTRS)

    Forrest, K.; Pagano, S. J.; Viehmann, W.

    1986-01-01

    Multimode channel waveguides have been formed in sodium aluminosilicate glass by field-assisted diffusion of Ag(+) ions from vacuum-evaporated Ag films. The two-dimensional refractive index profiles of the waveguides were controlled by varying the diffusion time, the diffusion temperature, and the electric field strength. Estimates of the diffusion rate through a strip aperture were obtained, assuming the electric field was strong 120-240 V/mm. The maximum change in refractive index in the sodium aluminosilicate glasses was estimated near 65 percent of the change in soda-lime silicate glass. The physical properties of the glasses are given in a table.

  9. Carbon dioxide in silica-undersaturated melt Part II: Effect of CO2 on quenched glass structure

    NASA Astrophysics Data System (ADS)

    Morizet, Yann; Paris, Michael; Gaillard, Fabrice; Scaillet, Bruno

    2014-11-01

    Despite CO2 is the second most abundant volatile species implied in magmatic systems, its impact on the molecular structure of aluminosilicate glasses in complex systems is currently not well-constrained. Inasmuch, whether CO2 induces an increase in glass polymerization or not is yet not clear for complex glass compositions. Using the set of nephelinite glass samples investigated in Part I (Morizet et al., 2014), in which the CO2 solubility and speciation have been constrained as a function of the #K (molar K2O/K2O + Na2O), we have conducted a thorough investigation of the change in the silicate network structure associated to CO2 dissolution. The change in silicate structure has been studied as a function of volatiles solubility (CO2 up to 4.5 wt.%, H2O up to 3 wt.%) as well as a function of the #K (between 0 and 0.75) of the glasses. We used 29Si Solid-State NMR for probing the silicon local environment in the quenched glasses. We observe that in such depolymerized nephelinite compositions the exchange between Na and K in volatile-free glasses induces a change in the glass structure attributed to the Mixed Alkali Effect (MAE) invoked in previous works. The observed changes might be related to geometric changes in the glass structure (change in network species bond lengths or angles). The addition of H2O only produces a negligible change in the degree of polymerization being probed by the constant NBO/T (Non-Bridging Oxygen per Tetrahedron) as H2O is added to volatile-free glasses. In contrast, we observed that the addition of CO2 induces a strong change in the glass structure which might be interpreted as an increase in polymerization. Alternatively, considering the identified CO2 dissolution mechanism (mostly as non-bridging carbonates units), the glass structure changes might reflect an apparent glass polymerization through the creation of Si-O-C bonds rather a true polymerization through the creation of Si-O-Si bonds.

  10. Mesostructured silica and aluminosilicate carriers for oxytetracycline delivery systems.

    PubMed

    Berger, D; Nastase, S; Mitran, R A; Petrescu, M; Vasile, E; Matei, C; Negreanu-Pirjol, T

    2016-08-30

    Oxytetracycline delivery systems containing various MCM-type silica and aluminosilicate with different antibiotic content were developed in order to establish the influence of the support structural and textural properties and aluminum content on the drug release profile. The antibiotic molecules were loaded into the support mesochannels by incipient wetness impregnation method using a drug concentrated aqueous solution. The carriers and drug-loaded materials were investigated by small- and wide-angle XRD, FTIR spectroscopy, TEM and N2 adsorption-desorption isotherms. Faster release kinetics of oxytetracycline from uncalcined silica and aluminosilicate supports was observed, whereas higher drug content led to lower delivery rate. The presence of aluminum into the silica network also slowed down the release rate. The antimicrobial assays performed on Staphylococcus aureus clinical isolates showed that the oxytetracycline-loaded materials containing MCM-41-type mesoporous silica or aluminosilicate carriers inhibited the bacterial development. PMID:26861688

  11. Nanoscale encapsulation: the structure of cations in hydrophobic microporous aluminosilicates

    SciTech Connect

    Wasserman, S.R.; Yuchs, S.E.; Giaquinta, D.; Soderholm, L.; Song, Kang

    1996-10-01

    Hydrophobic microporous aluminosilicates, created by organic surface modification of inherently hydrophilic materials such as zeolites and clays, are currently being investigated as storage media for hazardous cations. Use of organic monolayers to modify the surface of an aluminosilicate after introducing an ion into the zeolite/clay reduces the interaction of water with the material. Resulting systems are about 20 times more resistant to leaching of stored ion. XAS spectra from the encapsulated ion demonstrate that byproducts from the organic modifier can complex with the stored cation. This complexation can result in a decreased affinity of the cation for the aluminosilicate matrix. Changing the organic modifier eliminates this problem. XAS spectra also indicate that the reactivity and speciation of the encapsulated ion may change upon application of the hydrophobic layer.

  12. The effect of pore-regulating agents on the ion-exchange properties of ferrocyanide-aluminosilicate sorbents

    SciTech Connect

    Panasyugin, A.S.; Trofimenko, N.E.; Komarov, V.S.; Rat`ko, A.I.; Masherova, N.P.

    1994-08-01

    Among the methods of controlling the adsorptive and structural properties of porous materials is the use of pore-regulating agents, which are introduced at different synthesis stages and subsequently removed by washing or calcination to produce a porous structure characterized by either a peaked or bimodal pore-size distribution. The open porous structure thus produced is accessible to reactant molecules, improves diffusion characteristics, and contributes to an increase in both the intensity and rate of saturation of absorbents. Earlier, the authors studied the ion-exchange properties and the mechanism of formation of ferrocyanide-aluminosilicate sorbents prepared by modifying the surface of clinoptilolite with ferrocyanides of heavy metals. The application of ferrocyanides (FCs) onto the aluminosilicate surface renders diffusion much easier than in the case of pure ferrocyanides and enhances the sorbent selectivity for cesium ions. The purpose of this work is to study the effect of pore-regulation agents that are introduced during preparation of composite sorbents on the ion-exchange properties of these sorbents with respect to alkali ions (Cs{sup +}, Na{sup +}, and Li{sup +}). Analysis of the kinetic curves demonstrates that modification by ferrocyanides in the presence of boric acid causes a decrease in the internal diffusion rates during the exchange of H{sup +} for Li{sup +}, Na{sup +}, and Cs{sup +} by 2.6, 2.1, and 0.2 times respectively. The introduction of pore-regulating agents was found to increase the selectivity of the modified samples for {sup 137}Cs by 1.8-6.7 and 1.5-2.2 times in comparison with the starting clinoptilolite and sorbents prepared without pore-regulating agents. This allow the use of ferrocyanide-aluminosilicate materials as selective sorbents for the {sup 137}Cs ion in the presence of considerable amounts of other ions.

  13. Water in peralkaline aluminosilicate melts to 2 GPa and 1400°C

    NASA Astrophysics Data System (ADS)

    Mysen, Bjorn

    2002-09-01

    The solubility of H 2O in melts along the join CaSi 4O 4-Ca(Ca 0.5Al) 4O 9 (0, 3, and 6 mol% Al 2O 3) has been determined at 0.8 to 2.0 GPa and 1200 to 1400°C and compared with the solubility of H 2O in melts along the joins Na 2Si 4O 9-Na 2(NaAl) 4O 9 and K 2Si 4O 9-K 2(KAl) 4O 9. The H 2O solubility is a positive function of pressure and a negative function of temperature and Al 2O 3 content so that solubility, X H 2O melt (mol%), is X H 2O melt( CAS)=19±2-0.7±0.1•X Al2O3+0.06±0.02•(X Al2O3) 2+13.3±0.2•P( GPa)-0.011±0.001• T( K). In alkali aluminosilicate melts, the solubility is considerably more sensitive to pressure, Al 2O 3, and temperature. The H 2O solubility data in the 0.8- to 2.0-GPa and 1200 to 1400°C pressure and temperature range are consistent with constant activity coefficient of H 2O in the melt. The partial molar volume of H 2O, V¯ H 2O melt, derived from the solubility data, ranges between 12.4 cm 3/mol for Al-free CaSi 4O 9 melt and 10.4 cm 3/mol for CaSi 4O 9 + 6 mol% Al 2O 3. This decrease in V¯ H 2O melt with increasing Al 2O 3 is similar to that reported for H 2O in melts along the two alkali aluminosilicate joins (Na 2Si 4O 9-Na 2(NaAl) 4O 9 and K 2Si 4O 9-K 2(KAl) 4O 9). The V¯ H 2O melt is invariant with temperature in contrast to V¯ H 2O melt along the joins, Na 2Si 4O 9-Na 2(NaAl) 4O 9 and K 2Si 4O 9-K 2(KAl) 4O 9, where in both cases V¯ H 2O melt decreases with increasing temperature.

  14. Synthesis and characterization of aluminosilicate catalyst impregnated by nickel oxide

    NASA Astrophysics Data System (ADS)

    Maulida, Iffana Dani; Sriatun, Taslimah

    2015-09-01

    Aluminosilicate as a catalyst has been synthesized by pore-engineering using CetylTrimethylAmmonium-Bromide (CTAB) as templating agent. It can produce bigger aluminosilicate pore therefore it will be more suitable for bulky molecule. The aims of this research are to synthesize aluminosilicate supported by Nickel, using CTAB surfactant as templating agent for larger pore radius than natural zeolite and characterize the synthesis product, consist of total acid sites and surface area characteristic. This research has been done with following steps. First, making sodium silicate and sodium aluminate. Second, aluminosilicate was synthesized by direct methods, calcined at 550, 650 and 750°C variation temperature, characterized product by X-RD and FTIR spectrometer. Third, NiCl2 was impregnated to the aluminosilicate that has the best cristallinity and main TO4 functional groups product (550 sample). Variation of NiCl2:aluminosilicate (w/w) ratio were 25%:75%, 50%:50% and 75%:25%. Last but not least characterization of catalytic properties was performed. It comprised total acidity test (gravimetric method) and Surface Area Analyzer. The result shows that the product synthesized by direct method at 550oC calcination temperature has the best cristallinity and main functional groups of TO4. The highest total acid sites was 31.6 mmole/g (Imp-A sample). Surface Area Analyzer shows that Imp-B sample has the best pore distribution and highest total pore volume and specific surface area with value 32.424 cc/g and 46.8287 m2/g respectively. We can draw the conclusion that the most potential catalyst is Imp-A sample compared to Imp-B and Imp-C because it has the highest total acid sites. However the most effective catalyst used for product selectivity was Imp-B sample among all samples.

  15. Boron Nitride Nanotubes-Reinforced Glass Composites

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam; Hurst, Janet B.; Choi, Sung R.

    2005-01-01

    Boron nitride nanotubes of significant lengths were synthesized by reaction of boron with nitrogen. Barium calcium aluminosilicate glass composites reinforced with 4 weight percent of BN nanotubes were fabricated by hot pressing. Ambient-temperature flexure strength and fracture toughness of the glass-BN nanotube composites were determined. The strength and fracture toughness of the composite were higher by as much as 90 and 35 percent, respectively, than those of the unreinforced glass. Microscopic examination of the composite fracture surfaces showed pullout of the BN nanotubes. The preliminary results on the processing and improvement in mechanical properties of BN nanotube reinforced glass matrix composites are being reported here for the first time.

  16. Recycling of aluminosilicate waste: Impact onto geopolymer formation

    NASA Astrophysics Data System (ADS)

    Essaidi, N.; Gharzouni, A.; Vidal, L.; Gouny, F.; Joussein, E.; Rossignol, S.

    2015-07-01

    Geopolymers are innovative ecomaterials resulting from the activation of an aluminosilicate source by an alkaline solution. Their properties depend on the used raw materials. This paper focuses on the possibility to obtain geopolymer materials with aluminosilicate laboratory waste. The effect of these additions on the geopolymer properties was studied by FTIR spectroscopy and mechanical test. It was evidenced a slowdown of the polycondensation reaction as well as the compressive strength due to the addition of laboratory waste which decreases the Si/K ratio of mixture.

  17. On-chip fabrication of alkali-metal vapor cells utilizing an alkali-metal source tablet

    NASA Astrophysics Data System (ADS)

    Tsujimoto, K.; Ban, K.; Hirai, Y.; Sugano, K.; Tsuchiya, T.; Mizutani, N.; Tabata, O.

    2013-11-01

    We describe a novel on-chip microfabrication technique for the alkali-metal vapor cell of an optically pumped atomic magnetometer (OPAM), utilizing an alkali-metal source tablet (AMST). The newly proposed AMST is a millimeter-sized piece of porous alumina whose considerable surface area holds deposited alkali-metal chloride (KCl) and barium azide (BaN6), source materials that effectively produce alkali-metal vapor at less than 400 °C. Our experiments indicated that the most effective pore size of the AMST is between 60 and 170 µm. The thickness of an insulating glass spacer holding the AMST was designed to confine generated alkali metal to the interior of the vapor cell during its production, and an integrated silicon heater was designed to seal the device using a glass frit, melted at an optimum temperature range of 460-490 °C that was determined by finite element method thermal simulation. The proposed design and AMST were used to successfully fabricate a K cell that was then operated as an OPAM with a measured sensitivity of 50 pT. These results demonstrate that the proposed concept for on-chip microfabrication of alkali-metal vapor cells may lead to effective replacement of conventional glassworking approaches.

  18. Apparatus enables accurate determination of alkali oxides in alkali metals

    NASA Technical Reports Server (NTRS)

    Dupraw, W. A.; Gahn, R. F.; Graab, J. W.; Maple, W. E.; Rosenblum, L.

    1966-01-01

    Evacuated apparatus determines the alkali oxide content of an alkali metal by separating the metal from the oxide by amalgamation with mercury. The apparatus prevents oxygen and moisture from inadvertently entering the system during the sampling and analytical procedure.

  19. Alkalis and Skin.

    PubMed

    Greenwood, John E; Tan, Jin Lin; Ming, Justin Choong Tzen; Abell, Andrew D

    2016-01-01

    The aim of this editorial is to provide an overview of the chemical interactions occurring in the skin of our patients on contact with alkaline agents. Strongly basic alkali is highly aggressive and will readily hydrolyze (or cleave) key biological molecules such as lipids and proteins. This phenomenon is known as saponification in the case of lipids and liquefactive denaturation for peptides and proteins. A short section on current first-aid concepts is included. A better understanding of the basic science behind alkali burns will make us better teachers and provide an insight into the urgency needed in treating these common and dangerous chemical injuries. PMID:26182072

  20. NOVEL REFRACTORY MATERIALS FOR HIGH ALKALI, HIGH TEMPERATURE ENVIRONMENTS

    SciTech Connect

    Hemrick, James Gordon; Smith, Jeffrey D; O'Hara, Kelley; Rodrigues-Schroer, Angela; Colavito,

    2012-08-01

    A project was led by Oak Ridge National Laboratory (ORNL) in collaboration with a research team comprised of the academic institution Missouri University of Science and Technology (MS&T), and the industrial company MINTEQ International, Inc. (MINTEQ), along with representatives from the aluminum, chemical, glass, and forest products industries. The project was to address the need for new innovative refractory compositions by developing a family of novel MgO-Al 2O3, MgAl2O4, or other similar spinel structured or alumina-based unshaped refractory compositions (castables, gunnables, shotcretes, etc.) utilizing new aggregate materials, bond systems, protective coatings, and phase formation techniques (in-situ phase formation, altered conversion temperatures, accelerated reactions, etc). This family of refractory compositions would then be tailored for use in high-temperature, high-alkaline industrial environments like those found in the aluminum, chemical, forest products, glass, and steel industries. Both practical refractory development experience and computer modeling techniques were used to aid in the design of this new family of materials. The newly developed materials were expected to offer alternative material choices for high-temperature, high-alkali environments that were capable of operating at higher temperatures (goal of increasing operating temperature by 100-200oC depending on process) or for longer periods of time (goal of twice the life span of current materials or next process determined service increment). This would lead to less process down time, greater energy efficiency for associated manufacturing processes (more heat kept in process), and materials that could be installed/repaired in a more efficient manner. The overall project goal was a 5% improvement in energy efficiency (brought about through a 20% improvement in thermal efficiency) resulting in a savings of 3.7 TBtu/yr (7.2 billion ft3 natural gas) by the year 2030. Additionally, new

  1. Alkali metal ion battery with bimetallic electrode

    SciTech Connect

    Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

    2015-04-07

    Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

  2. Methods of recovering alkali metals

    DOEpatents

    Krumhansl, James L; Rigali, Mark J

    2014-03-04

    Approaches for alkali metal extraction, sequestration and recovery are described. For example, a method of recovering alkali metals includes providing a CST or CST-like (e.g., small pore zeolite) material. The alkali metal species is scavenged from the liquid mixture by the CST or CST-like material. The alkali metal species is extracted from the CST or CST-like material.

  3. Replacement of glass in the Nakhla meteorite by berthierine: Implications for understanding the origins of aluminum-rich phyllosilicates on Mars

    NASA Astrophysics Data System (ADS)

    Lee, Martin R.; Chatzitheodoridis, Elias

    2016-09-01

    A scanning and transmission electron microscope study of aluminosilicate glasses within melt inclusions from the Martian meteorite Nakhla shows that they have been replaced by berthierine, an aluminum-iron serpentine mineral. This alteration reaction was mediated by liquid water that gained access to the glasses along fractures within enclosing augite and olivine grains. Water/rock ratios were low, and the aqueous solutions were circumneutral and reducing. They introduced magnesium and iron that were sourced from the dissolution of olivine, and exported alkalis. Berthierine was identified using X-ray microanalysis and electron diffraction. It is restricted in its occurrence to parts of the melt inclusions that were formerly glass, thus showing that under the ambient physico-chemical conditions, the mobility of aluminum and silicon were low. This discovery of serpentine adds to the suite of postmagmatic hydrous silicates in Nakhla that include saponite and opal-A. Such a variety of secondary silicates indicates that during aqueous alteration compositionally distinct microenvironments developed on sub-millimeter length scales. The scarcity of berthierine in Nakhla is consistent with results from orbital remote sensing of the Martian crust showing very low abundances of aluminum-rich phyllosilicates.

  4. Replacement of glass in the Nakhla meteorite by berthierine: Implications for understanding the origins of aluminum-rich phyllosilicates on Mars

    NASA Astrophysics Data System (ADS)

    Lee, Martin R.; Chatzitheodoridis, Elias

    2016-07-01

    A scanning and transmission electron microscope study of aluminosilicate glasses within melt inclusions from the Martian meteorite Nakhla shows that they have been replaced by berthierine, an aluminum-iron serpentine mineral. This alteration reaction was mediated by liquid water that gained access to the glasses along fractures within enclosing augite and olivine grains. Water/rock ratios were low, and the aqueous solutions were circumneutral and reducing. They introduced magnesium and iron that were sourced from the dissolution of olivine, and exported alkalis. Berthierine was identified using X-ray microanalysis and electron diffraction. It is restricted in its occurrence to parts of the melt inclusions that were formerly glass, thus showing that under the ambient physico-chemical conditions, the mobility of aluminum and silicon were low. This discovery of serpentine adds to the suite of postmagmatic hydrous silicates in Nakhla that include saponite and opal-A. Such a variety of secondary silicates indicates that during aqueous alteration compositionally distinct microenvironments developed on sub-millimeter length scales. The scarcity of berthierine in Nakhla is consistent with results from orbital remote sensing of the Martian crust showing very low abundances of aluminum-rich phyllosilicates.

  5. Effect of silicate modulus and metakaolin incorporation on the carbonation of alkali silicate-activated slags

    SciTech Connect

    Bernal, Susan A.; Mejia de Gutierrez, Ruby; Provis, John L.; Rose, Volker

    2010-06-15

    Accelerated carbonation is induced in pastes and mortars produced from alkali silicate-activated granulated blast furnace slag (GBFS)-metakaolin (MK) blends, by exposure to CO{sub 2}-rich gas atmospheres. Uncarbonated specimens show compressive strengths of up to 63 MPa after 28 days of curing when GBFS is used as the sole binder, and this decreases by 40-50% upon complete carbonation. The final strength of carbonated samples is largely independent of the extent of metakaolin incorporation up to 20%. Increasing the metakaolin content of the binder leads to a reduction in mechanical strength, more rapid carbonation, and an increase in capillary sorptivity. A higher susceptibility to carbonation is identified when activation is carried out with a lower solution modulus (SiO{sub 2}/Na{sub 2}O ratio) in metakaolin-free samples, but this trend is reversed when metakaolin is added due to the formation of secondary aluminosilicate phases. High-energy synchrotron X-ray diffractometry of uncarbonated paste samples shows that the main reaction products in alkali-activated GBFS/MK blends are C-S-H gels, and aluminosilicates with a zeolitic (gismondine) structure. The main crystalline carbonation products are calcite in all samples and trona only in samples containing no metakaolin, with carbonation taking place in the C-S-H gels of all samples, and involving the free Na{sup +} present in the pore solution of the metakaolin-free samples. Samples containing metakaolin do not appear to have the same availability of Na{sup +} for carbonation, indicating that this is more effectively bound in the presence of a secondary aluminosilicate gel phase. It is clear that claims of exceptional carbonation resistance in alkali-activated binders are not universally true, but by developing a fuller mechanistic understanding of this process, it will certainly be possible to improve performance in this area.

  6. Chlor-Alkali Technology.

    ERIC Educational Resources Information Center

    Venkatesh, S.; Tilak, B. V.

    1983-01-01

    Chlor-alkali technology is one of the largest electrochemical industries in the world, the main products being chlorine and caustic soda (sodium hydroxide) generated simultaneously by the electrolysis of sodium chloride. This technology is reviewed in terms of electrochemical principles and manufacturing processes involved. (Author/JN)

  7. Structure and mechanical properties of aluminosilicate geopolymer composites with Portland cement and its constituent minerals

    SciTech Connect

    Tailby, Jonathan; MacKenzie, Kenneth J.D.

    2010-05-15

    The compressive strengths and structures of composites of aluminosilicate geopolymer with the synthetic cement minerals C{sub 3}S, beta-C{sub 2}S, C{sub 3}A and commercial OPC were investigated. All the composites showed lower strengths than the geopolymer and OPC paste alone. X-ray diffraction, {sup 29}Si and {sup 27}Al MAS NMR and SEM/EDS observations indicate that hydration of the cement minerals and OPC is hindered in the presence of geopolymer, even though sufficient water was present in the mix for hydration to occur. In the absence of SEM evidence for the formation of an impervious layer around the cement mineral grains, the poor strength development is suggested to be due to the retarded development of C-S-H because of the preferential removal from the system of available Si because geopolymer formation is more rapid than the hydration of the cement minerals. This possibility is supported by experiments in which the rate of geopolymer formation is retarded by the substitution of potassium for sodium, by the reduction of the alkali content of the geopolymer paste or by the addition of borate. In all these cases the strength of the OPC-geopolymer composite was increased, particularly by the combination of the borate additive with the potassium geopolymer, producing an OPC-geopolymer composite stronger than hydrated OPC paste alone.

  8. Analysis of early medieval glass beads - Glass in the transition period

    NASA Astrophysics Data System (ADS)

    Šmit, Žiga; Knific, Timotej; Jezeršek, David; Istenič, Janka

    2012-05-01

    Glass beads from graves excavated in Slovenia and dated archaeologically to the 7th-10th century AD were analysed by the combined PIXE-PIGE method. The results indicate two groups of glass; natron glass made in the Roman tradition and glass made with alkalis from the ash of halophytic plants, which gradually replaced natron glass after c. 800 AD. The alkalis used in the second group of glass seem to be in close relation to a variant of the Venetian white glass that appeared several centuries later. The origin of this glass may be traced to glass production in Mesopotamia and around the Aral Sea. All the mosaic beads with eye decoration, as well as most of the drawn-segmented and drawn-cut beads analysed, are of plant-ash glass, which confirms their supposed oriental origin.

  9. Solid oxide fuel cell having a glass composite seal

    DOEpatents

    De Rose, Anthony J.; Mukerjee, Subhasish; Haltiner, Jr., Karl Jacob

    2013-04-16

    A solid oxide fuel cell stack having a plurality of cassettes and a glass composite seal disposed between the sealing surfaces of adjacent cassettes, thereby joining the cassettes and providing a hermetic seal therebetween. The glass composite seal includes an alkaline earth aluminosilicate (AEAS) glass disposed about a viscous glass such that the AEAS glass retains the viscous glass in a predetermined position between the first and second sealing surfaces. The AEAS glass provides geometric stability to the glass composite seal to maintain the proper distance between the adjacent cassettes while the viscous glass provides for a compliant and self-healing seal. The glass composite seal may include fibers, powders, and/or beads of zirconium oxide, aluminum oxide, yttria-stabilized zirconia (YSZ), or mixtures thereof, to enhance the desirable properties of the glass composite seal.

  10. XANES and Raman spectrometry on glasses and crystals in the CAS system.

    NASA Astrophysics Data System (ADS)

    Neuville, N.; Cormier, C.; Flank, F.; Massiot, M.

    2003-04-01

    XANES and Raman spectrometry on glasses and crystals in the CAS system. DANIEL R. NEUVILLE1, LAURENT CORMIER2 ANNE-MARIE FLANK3 and DOMINIQUE MASSIOT4 1Laboratoire de physico-chimie des fluides géologiques, IPGP-CNRS-UMR7047, 4 place Jussieu, 75252 Paris 2Laboratoire de Minéralogie et de Cristallographie, Universités PARIS 6 et 7, IPGP, UMR CNRS 7590, 4 place Jussieu, 75252 Paris 3Laboratoire pour l’Utilisation du Rayonnement Electromagnétique, Bat. 209D, B.P. 34, 91898, Orsay Cedex France 4UPR 4212, CNRS-CRMHT1d, avenue de la recherche scientifique F-45071 Orléans Cedex 2. Calcium aluminate and aluminosilicate glasses are attractive materials for a wide range of technical applications due to their highly refractory nature, their excellent optical and mechanical properties. The CaO-Al2O3-SiO2 system (CAS) is remarkable since glasses with very few SiO2 content can be synthesized, contrary to alkali or Mg aluminosilicate glasses. We have synthesized more than 40 different glasses in the CAS system using quenching method and 15 glasses using laser heating. These glasses were studied using a Raman spectrometer T64000 from Jobin-Yvon-Dilor company, X-ray absorption spectroscopy at Si, Al, Ca K edges the SA32 and D44 beamlines at LURE and NMR-700MHz. Cormier et al (2000) have shown using X-ray and neutron diffraction that aluminium is in 4-fold coordination in this ternary system. In this present study, we present Raman and XANES obtained at room temperature for these glasses. On the join SiO2-CaAl2O4 glass, we observed a decrease in Raman frequency with increasing CaAl2O4 content for all the bands. In particular, we observed a big decrease in frequency for the T4 band near 1150 cm-1 assigned to T-O0 in T4 units. This decrease suggests that aluminium substitutes principally for Si4+ in the fully polymerized structural units (TO2) according with Neuville and Mysen (1996). On the join SiO2-Ca3Al2O7 (R=CaO/AL2O3=3), we observed a decrease for all bands with

  11. Hydrothermal alkali metal recovery process

    DOEpatents

    Wolfs, Denise Y.; Clavenna, Le Roy R.; Eakman, James M.; Kalina, Theodore

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by treating them with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of an added base to establish a pH during the treatment step that is higher than would otherwise be possible without the addition of the base. During the treating process the relatively high pH facilitates the conversion of water-insoluble alkali metal compounds in the alkali metal residues into water-soluble alkali metal constituents. The resultant aqueous solution containing water-soluble alkali metal constituents is then separated from the residue solids, which consist of the treated particles and any insoluble materials formed during the treatment step, and recycled to the gasification process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preferably, the base that is added during the treatment step is an alkali metal hydroxide obtained by water washing the residue solids produced during the treatment step.

  12. Glasses, ceramics, and composites from lunar materials

    NASA Technical Reports Server (NTRS)

    Beall, George H.

    1992-01-01

    A variety of useful silicate materials can be synthesized from lunar rocks and soils. The simplest to manufacture are glasses and glass-ceramics. Glass fibers can be drawn from a variety of basaltic glasses. Glass articles formed from titania-rich basalts are capable of fine-grained internal crystallization, with resulting strength and abrasion resistance allowing their wide application in construction. Specialty glass-ceramics and fiber-reinforced composites would rely on chemical separation of magnesium silicates and aluminosilicates as well as oxides titania and alumina. Polycrystalline enstatite with induced lamellar twinning has high fracture toughness, while cordierite glass-ceramics combine excellent thermal shock resistance with high flexural strengths. If sapphire or rutile whiskers can be made, composites of even better mechanical properties are envisioned.

  13. Glasses, ceramics, and composites from lunar materials

    NASA Astrophysics Data System (ADS)

    Beall, George H.

    1992-02-01

    A variety of useful silicate materials can be synthesized from lunar rocks and soils. The simplest to manufacture are glasses and glass-ceramics. Glass fibers can be drawn from a variety of basaltic glasses. Glass articles formed from titania-rich basalts are capable of fine-grained internal crystallization, with resulting strength and abrasion resistance allowing their wide application in construction. Specialty glass-ceramics and fiber-reinforced composites would rely on chemical separation of magnesium silicates and aluminosilicates as well as oxides titania and alumina. Polycrystalline enstatite with induced lamellar twinning has high fracture toughness, while cordierite glass-ceramics combine excellent thermal shock resistance with high flexural strengths. If sapphire or rutile whiskers can be made, composites of even better mechanical properties are envisioned.

  14. Simple model potential and model wave functions for (H-alkali)+ and (alkali-alkali)+ ions

    NASA Astrophysics Data System (ADS)

    Patil, S. H.; Tang, K. T.

    2000-07-01

    A simple model potential is proposed to describe the interaction of a valence electron with the alkali core, which incorporates the correct asymptotic behavior in terms of dipolar polarizabilities, and the short-range exchange effects in terms of a hard core adjusted to give the correct energy for the valence electron. Based on this potential, simple wave functions are developed to describe the (H-alkali)+ and (alkali-alkali)+ ions. These wave functions exhibit some important structures of the ions, and provide a universal description of the properties of all (H-alkali)+ and (alkali-alkali)+ ions, in particular, the equilibrium separations of the nuclei and the corresponding dissociation energies. They also allow us to calculate the dipolar polarizabilities of Li2+, Na2+, K2+, Rb2+, and Cs2+.

  15. Alkali-vapor lasers

    NASA Astrophysics Data System (ADS)

    Zweiback, J.; Komashko, A.; Krupke, W. F.

    2010-02-01

    We report on the results from several of our alkali laser systems. We show highly efficient performance from an alexandrite-pumped rubidium laser. Using a laser diode stack as a pump source, we demonstrate up to 145 W of average power from a CW system. We present a design for a transversely pumped demonstration system that will show all of the required laser physics for a high power system.

  16. Developments in alkali-metal atomic magnetometry

    NASA Astrophysics Data System (ADS)

    Seltzer, Scott Jeffrey

    Alkali-metal magnetometers use the coherent precession of polarized atomic spins to detect and measure magnetic fields. Recent advances have enabled magnetometers to become competitive with SQUIDs as the most sensitive magnetic field detectors, and they now find use in a variety of areas ranging from medicine and NMR to explosives detection and fundamental physics research. In this thesis we discuss several developments in alkali-metal atomic magnetometry for both practical and fundamental applications. We present a new method of polarizing the alkali atoms by modulating the optical pumping rate at both the linear and quadratic Zeeman resonance frequencies. We demonstrate experimentally that this method enhances the sensitivity of a potassium magnetometer operating in the Earth's field by a factor of 4, and we calculate that it can reduce the orientation-dependent heading error to less than 0.1 nT. We discuss a radio-frequency magnetometer for detection of oscillating magnetic fields with sensitivity better than 0.2 fT/ Hz , which we apply to the observation of nuclear magnetic resonance (NMR) signals from polarized water, as well as nuclear quadrupole resonance (NQR) signals from ammonium nitrate. We demonstrate that a spin-exchange relaxation-free (SERF) magnetometer can measure all three vector components of the magnetic field in an unshielded environment with comparable sensitivity to other devices. We find that octadecyltrichlorosilane (OTS) acts as an anti-relaxation coating for alkali atoms at temperatures below 170°C, allowing them to collide with a glass surface up to 2,000 times before depolarizing, and we present the first demonstration of high-temperature magnetometry with a coated cell. We also describe a reusable alkali vapor cell intended for the study of interactions between alkali atoms and surface coatings. Finally, we explore the use of a cesium-xenon SERF comagnetometer for a proposed measurement of the permanent electric dipole moments (EDMs

  17. Amorphous and nanostructured silica and aluminosilicate spray-dried microspheres

    NASA Astrophysics Data System (ADS)

    Todea, M.; Turcu, R. V. F.; Frentiu, B.; Tamasan, M.; Mocuta, H.; Ponta, O.; Simon, S.

    2011-08-01

    Amorphous silica and aluminosilicate microspheres with diameters in the 0.1-20 μm range were produced by spray drying method. SEM, TEM and AFM images showed the spherical shape of the obtained particles. Based on thermal analysis data, several heat treatments have been applied on the as-prepared samples in order to check the amorphous state stability of the microspheres and to develop nanosized crystalline phases. As-prepared microspheres remain amorphous up to 1400 °C. By calcination at 1400 °C, cristobalite type nanocrystals are developed on silica sample, while in aluminosilicate sample first are developed mullite type nanocrystals and only after prolonged treatment are developed also cristobalite type nanocrystals. 29Si and 27Al MAS NMR results show that the local order around aluminum and silicon atoms strongly depend on the thermal history of the microspheres.

  18. Chemical and mechanical consequences of environmental barrier coating exposure to calcium-magnesium-aluminosilicate.

    SciTech Connect

    Harder, B.; Ramirez-Rico, J.; Almer, J. D.; Kang, L.; Faber, K.

    2011-06-01

    The success of Si-based ceramics as high-temperature structural materials for gas turbine applications relies on the use of environmental barrier coatings (EBCs) with low silica activity, such as Ba{sub 1-x}Sr{sub x}Al{sub 2}Si{sub 2}O{sub 8} (BSAS), which protect the underlying components from oxidation and corrosion in combustion environments containing water vapor. One of the current challenges concerning EBC lifetime is the effect of sandy deposits of calcium-magnesium-aluminosilicate (CMAS) glass that melt during engine operation and react with the EBC, changing both its composition and stress state. In this work, we study the effect of CMAS exposure at 1300 C on the residual stress state and composition in BSAS-mullite-Si-SiC multilayers. Residual stresses were measured in BSAS multilayers exposed to CMAS for different times using high-energy X-ray diffraction. Their microstructure was studied using a combination of scanning electron microscopy and transmission electron microscopy techniques. Our results show that CMAS dissolves the BSAS topcoat preferentially through the grain boundaries, dislodging the grains and changing the residual stress state in the topcoat to a nonuniform and increasingly compressive stress state with increasing exposure time. The presence of CMAS accelerates the hexacelsian-to-celsian phase transformation kinetics in BSAS, which reacts with the glass by a solution-reprecipitation mechanism. Precipitates have crystallographic structures consistent with Ca-doped celsian and Ba-doped anorthite.

  19. Hard x-ray nanotomography of amorphous aluminosilicate cements.

    SciTech Connect

    Provis, J. L.; Rose, V.; Winarski, R. P.; van Deventer, J. S. J.

    2011-08-01

    Nanotomographic reconstruction of a sample of low-CO{sub 2} 'geopolymer' cement provides the first three-dimensional view of the pore structure of the aluminosilicate geopolymer gel, as well as evidence for direct binding of geopolymer gel onto unreacted fly ash precursor particles. This is central to understanding and optimizing the durability of concretes made using this new class of binder, and demonstrates the value of nanotomography in providing a three-dimensional view of nanoporous inorganic materials.

  20. Alteration of biophysical activity of pulmonary surfactant by aluminosilicate nanoparticles.

    PubMed

    Kondej, Dorota; Sosnowski, Tomasz R

    2013-02-01

    The influence of five different types of aluminosilicate nanoparticles (NPs) on the dynamic surface activity of model pulmonary surfactant (PS) (Survanta) was studied experimentally using oscillating bubble tensiometry. Bentonite, halloysite and montmorillonite (MM) NPs, which are used as fillers of polymer composites, were characterized regarding the size distribution, morphology and surface area. Particle doses applied in the studies were estimated based on the inhalation rate and duration, taking into account the expected aerosol concentration and deposition efficiency after penetration of NPs into the alveolar region. The results indicate that aluminosilicate NPs at concentrations in the pulmonary liquid above 0.1 mg cm(-3) are capable of promoting alterations of the original dynamic biophysical activity of the PS. This effect is indicated by deviation of the minimum surface tension, stability index and the size of surface tension hysteresis. Such response is dependent on the type of NPs present in the system and is stronger when particle concentration increases. It is suggested that interactions between NPs and the PS must be related to the surfactant adsorption on the suspended particles, while in the case of surface-modified clay NPs the additional washout of surface-active components may be expected. It is speculated that observed changes in surface properties of the surfactant may be associated with undesired health effects following extensive inhalation of aluminosilicate NPs in the workplace. PMID:23363039

  1. Capture of alkali during pressurized fluidized-bed combustion using in-bed sorbents

    SciTech Connect

    Mann, M.D.; Ludlow, D.K.

    1997-12-31

    The primary focus of this research was the removal of alkali from PFBC flue gases to a level specified by turbine manufactures. The target level was less than 24 ppbw. Several of the aluminosilicate minerals have the potential to capture alkalis, especially sodium and potassium, under conditions typical of fluid-bed operation. Other goals of this work were to investigate the potential for simultaneously removing SO{sub 2} and Cl from the PFBC gas stream. The initial work focused primarily on one class of sorbents, sodalites, with the goal of determining whether sodalites can be used as an in-bed sorbent to simultaneously remove alkali and sulfur. Thermo gravimetric analysis (TGA) was used to study the mechanism of alkali capture using sodalite. Further testing was performed on a 7.6 cm (3-in.)-diameter pressurized fluid-bed reactor (PFBR). Early results indicated that simultaneous removal of alkali and sulfur and/or chlorine was not practical under the conditions for commercial PFBC operations. Therefore, the focus of the latter part of this work was on sorbents that have been shown to capture alkali in other systems. The effectiveness of bauxite and kaolinite to reduce vapor-phase alkali concentrations was determined. In addition to studying the gettering capability of the sorbent, the impact of the getter on operational performance was evaluated. This evaluation included examining potential agglomeration of bed particles, deposition on heat-transfer surfaces, and the bridging and blinding of ceramic candle filters. The focus of this paper is on the work performed on the PFBR.

  2. Gel nanostructure in alkali-activated binders based on slag and fly ash, and effects of accelerated carbonation

    SciTech Connect

    Bernal, Susan A.; Provis, John L.; Walkley, Brant; San Nicolas, Rackel; Gehman, John D.; Brice, David G.; Kilcullen, Adam R.; Duxson, Peter; Deventer, Jannie S.J. van

    2013-11-15

    Binders formed through alkali-activation of slags and fly ashes, including ‘fly ash geopolymers’, provide appealing properties as binders for low-emissions concrete production. However, the changes in pH and pore solution chemistry induced during accelerated carbonation testing provide unrealistically low predictions of in-service carbonation resistance. The aluminosilicate gel remaining in an alkali-activated slag system after accelerated carbonation is highly polymerised, consistent with a decalcification mechanism, while fly ash-based binders mainly carbonate through precipitation of alkali salts (bicarbonates at elevated CO{sub 2} concentrations, or carbonates under natural exposure) from the pore solution, with little change in the binder gel identifiable by nuclear magnetic resonance spectroscopy. In activated fly ash/slag blends, two distinct gels (C–A–S–H and N–A–S–H) are formed; under accelerated carbonation, the N–A–S–H gel behaves comparably to fly ash-based systems, while the C–A–S–H gel is decalcified similarly to alkali-activated slag. This provides new scope for durability optimisation, and for developing appropriate testing methodologies. -- Highlights: •C-A-S-H gel in alkali-activated slag decalcifies during accelerated carbonation. •Alkali-activated fly ash gel changes much less under CO{sub 2} exposure. •Blended slag-fly ash binder contains two coexisting gel types. •These two gels respond differently to carbonation. •Understanding of carbonation mechanisms is essential in developing test methods.

  3. The interactions of sorbates with gallosilicates and alkali-metal exchanged gallosilicates

    NASA Astrophysics Data System (ADS)

    Limtrakul, J.; Kuno, M.; Treesukol, P.

    1999-11-01

    Structures, energetics and vibrational frequencies of the interaction of adsorbates with H-aluminosilicates (H-AlZ), H-gallosilicates (H-GaZ), alkali-metal exchanged aluminosilicates (X-AlZ) and alkali-metal exchanged gallosilicates (X-GaZ), where X being Li, Na, or K, have been carried out at B3LYP and HF levels of theory with 6-31G(d) as the basis set. The charge compensating alkali-metal ions can affect the catalytically active site (Si-O-T where T=Al or Ga) by weakening the Si-O, Al-O, and Ga-O bonds as compared to their anionic frameworks. Comparing the net stabilization energies, Δ ENSE, of the naked alkali-metal/H 2O adducts with those of the alkali-metal exchanged zeolite/H 2O systems, the latter amounts only to about 50% of the former, which is partly due to the destabilizing role of the negative zeolitic oxygen frameworks surrounding the cations. The interaction of sorbates with the alkali-metal exchanged gallosilicates can be employed to probe the field strength inside the catalytic frameworks as indicated by the plot of the binding energy, Δ E, versus 1/ RX-O w2, with R(X-O w) being the distance between the cationic nucleus and the oxygen atom of the adsorbate. The IR spectra of H 2O adsorbed on Na-AlZ are calculated to be 3584, 3651, and 1686 cm -1. The obtained results are in excellent agreement with the very recent experimental IR spectra of water adsorbed on Na-ZSM-5 of Zecchina et al. (J. Phys. Chem., 100 (1996) 16 484). Other important features, i.e. the correlation between Δ νOH and, Δ E, R(X-O w) , and 1/ RX-O w2, cationic size, demonstrate that the interactions of sorbates with alkali-metal exchanged gallosilicates are well approximated by electrostatic contribution.

  4. Adsorption on Alkali Halides.

    NASA Astrophysics Data System (ADS)

    Urzua Duran, Gilberto Antonio

    1995-01-01

    Using a variety of interionic potentials, I have computed the configurations of adsorbed alkali halides monomers on the (001) surface of selected alkali halides crystals. In the majority of cases studied it is found that the monomer adsorbs perpendicular to the surface with the cation sitting nearly on top of the surface anion. In about ten percent of the cases though the monomer adsorbs tilted from the vertical. In these cases the ion that is closer to the surface can be the cation or the anion. The effect of polarization forces is found to be important. In order to discuss the effects of surface retaxation with adsorbates, I have evaluated the surface relaxation of the alkali halide crystals, using a shell model for the interionic forces. It is found that surface relaxation and rumpling are generally small, especially when the van der Waals forces are included. A theory of the effect of substrate vibrations on the binding of an adsorbed atom is developed. At T = 0 the binding energy is D_0-E, where D_0 is the surface well depth (classical binding energy) and E is the quantum correction. For several simple models, it is found that E is surprisingly model-independent. We compare D _0-E with the binding energies to a rigid substrate, D_0-E_{rs}, and to a vibrationally averaged substrate, D _0-E_{va}. We prove that E_{va}>=q E>=q E_ {rs} and that similar relations hold at finite temperature for the free energy of binding. In most cases E_{rs} is better than E_{va} as an approximation to E.

  5. Energetics of formation of alkali and ammonium cobalt and zinc phosphate frameworks

    SciTech Connect

    Le, So-Nhu; Navrotsky, Alexandra

    2008-01-15

    Alkali and ammonium cobalt and zinc phosphates show extensive polymorphism. Thermal behavior, relative stabilities, and enthalpies of formation of KCoPO{sub 4}, RbCoPO{sub 4}, NH{sub 4}CoPO{sub 4}, and NH{sub 4}ZnPO{sub 4} polymorphs are studied by differential scanning calorimetry, high-temperature oxide melt solution calorimetry, and acid solution calorimetry. {alpha}-KCoPO{sub 4} and {gamma}-KCoPO{sub 4} are very similar in enthalpy. {gamma}-KCoPO{sub 4} slowly transforms to {alpha}-KCoPO{sub 4} near 673 K. The high-temperature phase, {beta}-KCoPO{sub 4}, is 5-7 kJ mol{sup -1} higher in enthalpy than {alpha}-KCoPO{sub 4} and {gamma}-KCoPO{sub 4}. HEX phases of NH{sub 4}CoPO{sub 4} and NH{sub 4}ZnPO{sub 4} are about 3 kJ mol{sup -1} lower in enthalpy than the corresponding ABW phases. There is a strong relationship between enthalpy of formation from oxides and acid-base interaction for cobalt and zinc phosphates and also for aluminosilicates with related frameworks. Cobalt and zinc phosphates exhibit similar trends in enthalpies of formation from oxides as aluminosilicates, but their enthalpies of formation from oxides are more exothermic because of their stronger acid-base interactions. Enthalpies of formation from ammonia and oxides of NH{sub 4}CoPO{sub 4} and NH{sub 4}ZnPO{sub 4} are similar, reflecting the similar basicity of CoO and ZnO. - Graphical abstract: Relationship between enthalpy of formation from oxides and acid-base interaction for cobalt phosphates, zinc phosphates, and aluminosilicates with related frameworks. They exhibit similar trends, but the enthalpies of formation of phosphates are more exothermic than those of aluminosilicates because of stronger acid-base interactions.

  6. Experimental Modeling of Peridotite Melting with Alkali-Carbonate Fluid at P = 3.9 GPa, T=1250°C

    NASA Astrophysics Data System (ADS)

    Kostyuk, Anastasia; Gorbachev, Nikolay; Nekrasov, Alexey

    2014-05-01

    The close association of alkaline and ultramafic rocks with carbonatites, apatite and sulfide mineralization, as well as features of the melt compositions, tell us about the mantle source and the importance of alkaline-carbonate fluids in the genesis of these rocks. Experimental modeling of formation of alkali silicate, carbonate and sulfide melts was carried out in the system peridotite-alkaline-carbonate fluid (K, Na)2CO3 with additives of apatite, nickel-containing pyrrhotite, ilmenite and zircon as accessory minerals at P= 3.9 GPa and T=1250°C. Composition of coexisting melts, phase relationships, behavior of titanium, phosphorus, sulfur and zircon have been studied in this system. Liquidus association of phlogopite-clinopyroxene-zircon-X-phase (not diagnosed titanium and phosphorus-containing aluminosilicate phase) cemented by intergranular silicate glass with inclusions of carbonate and sulphide phases at partial (10%) melting of peridotite. Morphology, composition and relations of silicate glass, carbonate and sulfide globules indicate the existence of immiscible silicate, carbonate and sulfide melts at the experimental conditions. The composition of the silicate melt is phonolite, carbonate melt - significantly calcium composition with an admixture of alkali metal and silicate components. Solubility of zircon in silicate melt reached up to 0.8 wt.% of ZrO2, in coexisting carbonate melt - up to 1.5 wt.%. Absence of ilmenite and apatite in the experimental samples due to their high solubility in the coexisting phases. Concentration of TiO2 and P2O5 in silicate melt reached 2 wt. %. The concentration of TiO2 in the carbonate melt up to 1.7 wt.% and P2O5 up to 14 wt.%. The sulfur concentration in these melts does not exceed 0.2 wt.%. Concentrators of titanium and phosphorus among liquidus minerals were X-phase and phlogopite - 8 wt.% TiO2 and up to 3 wt.% P2O5 in the X-phase; up to 6 wt.% TiO2 and up to 2.5 wt.% of P2O5 in the phlogopite. The distribution

  7. PROCESS OF RECOVERING ALKALI METALS

    DOEpatents

    Wolkoff, J.

    1961-08-15

    A process is described of recovering alkali metal vapor by sorption on activated alumina, activated carbon, dehydrated zeolite, activated magnesia, or Fuller's earth preheated above the vaporization temperature of the alkali metal and subsequent desorption by heating the solvent under vacuum. (AEC)

  8. Preparation of alkali metal dispersions

    NASA Technical Reports Server (NTRS)

    Rembaum, A.; Landel, R. F. (Inventor)

    1968-01-01

    A method is described for producing alkali metal dispersions of high purity. The dispersions are prepared by varying the equilibrium solubility of the alkali metal in a suitable organic solvent in the presence of aromatic hydrocarbons. The equilibrium variation is produced by temperature change. The size of the particles is controlled by controlling the rate of temperature change.

  9. Ionic transport and electrical relaxation in glass

    NASA Astrophysics Data System (ADS)

    Moynihan, C. T.; Barkatt, A.

    1987-09-01

    The basic purpose of the work described was to achieve extensive and quantitative understanding of ionic transport processes in melts and glasses by means of a combination of experimental measurements and theoretical modeling. Two major subjects of the study were the mechanism of dielectric relaxation in ionically conducting glasses and the large retardation of ionic transport in mixed alkali systems.

  10. Purification of alkali metal nitrates

    DOEpatents

    Fiorucci, Louis C.; Gregory, Kevin M.

    1985-05-14

    A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

  11. Impact of Alkali Source on Vitrification of SRS High Level Waste

    SciTech Connect

    LAMBERT, D. P.; MILLER, D. H.; PEELER, D. K.; SMITH, M. E.; STONE, M. E.

    2005-09-08

    The Defense Waste Processing Facility (DWPF) Savannah River Site is currently immobilizing high level nuclear waste sludge by vitrification in borosilicate glass. The processing strategy involves blending a large batch of sludge into a feed tank, washing the sludge to reduce the amount of soluble species, then processing the large ''sludge batch'' through the DWPF. Each sludge batch is tested by the Savannah River National Laboratory (SRNL) using simulants and tests with samples of the radioactive waste to ''qualify'' the batch prior to processing in the DWPF. The DWPF pretreats the sludge by first acidifying the sludge with nitric and formic acid. The ratio of nitric to formic acid is adjusted as required to target a final glass composition that is slightly reducing (the target is for {approx}20% of the iron to have a valence of two in the glass). The formic acid reduces the mercury in the feed to elemental mercury which is steam stripped from the feed. After a concentration step, the glass former (glass frit) is added as a 50 wt% slurry and the batch is concentrated to approximately 50 wt% solids. The feed slurry is then fed to a joule heated melter maintained at 1150 C. The glass must meet both processing (e.g., viscosity and liquidus temperature) and product performance (e.g., durability) constraints The alkali content of the final waste glass is a critical parameter that affects key glass properties (such as durability) as well as the processing characteristics of the waste sludge during the pretreatment and vitrification processes. Increasing the alkali content of the glass has been shown to improve the production rate of the DWPF, but the total alkali in the final glass is limited by constraints on glass durability and viscosity. Two sources of alkali contribute to the final alkali content of the glass: sodium salts in the waste supernate and sodium and lithium oxides in the glass frit added during pretreatment processes. Sodium salts in the waste supernate

  12. Characterisation of frequency doubling in Eu(2+) doped aluminosilicate fibres

    NASA Technical Reports Server (NTRS)

    Driscoll, T. J.; Lawandy, N. M.; Killian, A.; Rienhart, L.; Morse, T. F.

    1991-01-01

    The results of a series of experiments on efficient second-harmonic generation in a fiber with a Eu(2+)-doped aluminosilicate core are reported. The fiber was prepared by the seeding method with CW mode-locked radiation at 1.06 micron and produced ultrastable peak conversion efficiencies of 0.001 during mode-locked readout. Experiments were performed to determine the IR preparation intensity dependence, the stability of the output, and the type of erasure mechanisms which occur. The results are compared with those of germanosilicate fibers and some similarities and differences are discussed.

  13. New nanocomposites based on layered aluminosilicate and guanidine containing polyelectrolytes

    SciTech Connect

    Khashirov, Azamat A.; Zhansitov, Azamat A.; Khashirova, Svetlana Yu.; Zaikov, Genadiy E.

    2014-05-15

    The new functional nanomaterials based on layered aluminosilicate and guanidine containing polyelectrolytes combining high bactericidal activity with an increased ability to bind to heavy metals and organic pollutants were received. To prove the chemical structure of the model compounds (zwitterionic delocalized resonance structures AG/MAG and PAG/PMAG), as well as the presence of such structures in nanocomposites received on their basis and the MMT, IR, {sup 1}H NMR spectroscopy, X-ray diffraction studies and nanoindentation/sclerometry followed by scanning the surface in the area of the indentation were used.

  14. Cesium adsorption on composite ferrocyanide-aluminosilicate adsorbents

    SciTech Connect

    Panasyugin, A.S.; Rat`ko, A.I.; Trofimenko, N.E.

    1995-11-01

    The formation of composite ferrocyanide adsorbents prepared on the basis of clinoptilolite is studied by potentiometric titration, X-ray diffraction analysis, and IR spectroscopy, and the nature of ion-exchanging complex is established. Exchange capacity, selectivity, and hydrolytic stability of the sorbents are characterized. Distribution coefficients with modified samples can be as large as 10000 for {sup 137}Cs; however, with increase of the background salt concentration above 0.17 g l{sup -1}, competing ions have noticeable effect on the adsorption properties of the aluminosilicates.

  15. Analysis of paramagnetic centers for threevalent iron in aluminosilicates

    NASA Astrophysics Data System (ADS)

    Apushkinskaya, D.; Apushkinskiy, E.; Popov, B.; Romanov, V. N.; Saveliev, V.; Sobolevskiy, V.

    2015-09-01

    We present the results of investigation of the defects in fluorine aluminosilicates from the Volyn-field Al2 [SiO4][F,OH]2 by the Electron Paramagnetic Resonance (EPR) method. The studies were carried out on the spectrometer Bruker ER 220D. Three types of EPR spectra of single centers were obtained. Their angular dependence was also investigated. The obtained EPR spectra correspond to the paramagnetic ion Fe3+ in the high-spin state S = 5/2. Three types of paramagnetic centers were found: one with cubic-symmetry and two with orthorhombic- symmetries.

  16. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  17. In situ Brillouin study of sodium alumino silicate glasses under pressure

    NASA Astrophysics Data System (ADS)

    Sonneville, C.; De Ligny, D.; Mermet, A.; Champagnon, B.; Martinet, C.; Henderson, G. H.; Deschamps, T.; Margueritat, J.; Barthel, E.

    2013-08-01

    The in situ elastic and plastic behaviors of sodium aluminosilicate glasses with different degrees of depolymerization were analyzed using Brillouin spectroscopy. The observed elastic anomaly progressively vanished with depolymerization. The densification process appears to be different from that observed in pure silica glass. In the plastic regime of densified glasses hysteresis loops were observed and related to modification of the local silicon environment facilitated by the addition of sodium.

  18. Inorganic glasses, glass-forming liquids and amorphizing solids

    NASA Astrophysics Data System (ADS)

    Greaves, G. N.; Sen, S.

    2007-01-01

    We take familiar inorganic oxide glasses and non-oxide glasses and the liquids from which they derive to review the current understanding of their atomic structure, ranging from the local environments of individual atoms to the long-range order which can cover many interatomic distances. The structural characteristics of important glasses and melts, like silicates, borates, alumino-silicates, halides and chalcogenides, are drawn from the results of recent spectroscopy and scattering experiments. The techniques include Nuclear Magnetic Resonance (NMR) and X-ray Absorption Fine Structure (XAFS), Neutron Scattering (NS) and Small- and Wide-angle X-ray Scattering measurements (SAXS/WAXS), and are often combined with computer simulation experiments in order to obtain detailed images of structure and diffusion in the glassy as well as in the molten state. We then review the current understanding of relaxation in glasses, liquids and polyamorphic states. This includes phenomenological models and theories of relaxation in different dynamical regimes, spectroscopic studies of atomic-scale mechanisms of viscous flow in inorganic glass-formers and the signatures of relaxational behaviour embedded in the low-frequency vibrational dynamics of glasses including the Boson peak and the Two-Level Systems (TLS) that control conformational transformation. We conclude this review by extending concepts of the dynamics of the glass transition from the supercooled liquid in order to understand the solid-state amorphization of crystals under temperature and pressure and to determine the thermodynamic limits of the crystalline and glassy state.

  19. Heterovalent substitutions in garnet and their implications for diffusion of Y+REEs and alkalis (Invited)

    NASA Astrophysics Data System (ADS)

    Carlson, W. D.; Gale, J. D.; Wright, K.

    2013-12-01

    Lattice-dynamics calculations in the static limit suggest that large trivalent ions (Y+REEs) are incorporated into garnet primarily by means of substitutions that introduce menzerite and alkali components. The diffusion mechanisms implied by this finding explain otherwise puzzling aspects of recent determinations of diffusion rates for Y+REEs and Li in natural systems, bolstering confidence in the validity of those rates. Several substitution schemes have been proposed to provide the charge-balance required for incorporation of trivalent Y+REEs substituting for divalent cations in dodecahedral sites in aluminosilicate garnet: (1) YAG components, with tetrahedral Al; (2) vacancy components, with one unoccupied dodecahedral site for each two trivalent ions; (3) alkali components, with dodecahedral Na or Li; (4) menzerite components, with octahedral Mg or Fe; and (5) Y2Li components, with octahedral Li compensating for a pair of Y+REE ions. The relative energetic costs of these substitutions were evaluated in pyrope, almandine, spessartine and grossular by means of lattice-dynamics calculations at T = 0 K and P = 0 GPa, using well-established force-field potentials, and referencing exchange energies to the lattice energies of binary oxides as sources/sinks for the exchanged ions. Energies calculated for the incorporation of menzerite and alkali components are appreciably lower than those for the YAG component, and very substantially lower than those for the other components. Provided that the relative energetic costs are similar at elevated T and P to those in the static limit (testing of this assumption is currently underway), the menzerite and alkali substitutions should predominate in natural aluminosilicate garnets, the YAG substitution should play only a subordinate role, and the other substitutions should be near-negligible. As a result, diffusion mechanisms for Y+REEs in garnet require that motion of these elements must be coupled to transport of either

  20. Considerations of Glass Sealing SOFC Stacks

    SciTech Connect

    Yang, Z Gary; Weil, K. Scott; Meinhardt, Kerry D.; Paxton, Dean M.; Stevenson, Jeffry W.

    2003-08-31

    Due to their TEC matching to PEN components, excellent oxidation resistance, low cost and good fabricability, stainless steels have been used as the interconnect materials in planar SOFC. For being hermetical, the stainless steel interconnect ought to be sealed to YSZ electrolyte and/or another piece of metallic interconnect, usually using a sealing glass. The seal performance, which is critical factor to determine the reliability and durability of SOFC stack, largely depends on the chemical compatibility between the sealing glass and stainless steel. In this work, the ferritic stainless steel 446 and a barium-aluminosilicate base glass have been taken as an example for metallic interconnects and sealing glass, respectively, and the corrosion at the interface of metal and sealing glass has been investigated and understood. The methodology and results of the microscopic analysis and thermodynamic modeling will be presented, and the mechanism of corrosion at the interface will be discussed as well.

  1. Effective Sequestration of Clostridium difficile Protein Toxins by Calcium Aluminosilicate

    PubMed Central

    Pokusaeva, Karina; Carpenter, Robert

    2015-01-01

    Clostridium difficile is a leading cause of antibiotic-associated diarrhea and the etiologic agent responsible for C. difficile infection. Toxin A (TcdA) and toxin B (TcdB) are nearly indispensable virulence factors for Clostridium difficile pathogenesis. Given the toxin-centric mechanism by which C. difficile pathogenesis occurs, the selective sequestration with neutralization of TcdA and TcdB by nonantibiotic agents represents a novel mode of action to prevent or treat C. difficile-associated disease. In this preclinical study, we used quantitative enzyme immunoassays to determine the extent by which a novel drug, calcium aluminosilicate uniform particle size nonswelling M-1 (CAS UPSN M-1), is capable of sequestering TcdA and TcdB in vitro. The following major findings were derived from the present study. First, we show that CAS UPSN M-1 efficiently sequestered both TcdA and TcdB to undetectable levels. Second, we show that CAS UPSN M-1's affinity for TcdA is greater than its affinity for TcdB. Last, we show that CAS UPSN M-1 exhibited limited binding affinity for nontarget proteins. Taken together, these results suggest that ingestion of calcium aluminosilicate might protect gastrointestinal tissues from antibiotic- or chemotherapy-induced C. difficile infection by neutralizing the cytotoxic and proinflammatory effects of luminal TcdA and TcdB. PMID:26149988

  2. MAS-NMR studies of lithium aluminum silicate (LAS) glasses and glass-ceramics having different Li{sub 2}O/Al{sub 2}O{sub 3} ratio

    SciTech Connect

    Ananthanarayanan, A.; Kothiyal, G.P.; Montagne, L.; Revel, B.

    2010-01-15

    Emergence of phases in lithium aluminum silicate (LAS) glasses of composition (wt%) xLi{sub 2}O-71.7SiO{sub 2}-(17.7-x)Al{sub 2}O{sub 3}-4.9K{sub 2}O-3.2B{sub 2}O{sub 3}-2.5P{sub 2}O{sub 5} (5.1<=x<=12.6) upon heat treatment were studied. {sup 29}Si, {sup 27}Al, {sup 31}P and {sup 11}B MAS-NMR were employed for structural characterization of both LAS glasses and glass-ceramics. In glass samples, Al is found in tetrahedral coordination, while P exists mainly in the form of orthophosphate units. B exists as BO{sub 3} and BO{sub 4} units. {sup 27}Al NMR spectra show no change with crystallization, ruling out the presence of any Al containing phase. Contrary to X-ray diffraction studies carried out, {sup 11}B (high field 18.8 T) and {sup 29}Si NMR spectra clearly indicate the unexpected crystallization of a borosilicate phase (Li,K)BSi{sub 2}O{sub 6}, whose structure is similar to the aluminosilicate virgilite. Also, lithium disilicate (Li{sub 2}Si{sub 2}O{sub 5}), lithium metasilicate (Li{sub 2}SiO{sub 3}) and quartz (SiO{sub 2}) were identified in the {sup 29}Si NMR spectra of the glass-ceramics. {sup 31}P NMR spectra of the glass-ceramics revealed the presence of Li{sub 3}PO{sub 4} and a mixed phase (Li,K){sub 3}PO{sub 4} at low alkali concentrations. - Graphical Abstract: The {sup 11}B MAS-NMR spectra of lithium aluminum silicate (LAS) glass-ceramics indicating the formation of Li/KBSiO{sub 6} phase. This phase is isostructural with virgilite and cannot be distinguished in X-ray diffractograms.

  3. Glass viscosity calculation based on a global statistical modelling approach

    SciTech Connect

    Fluegel, Alex

    2007-02-01

    A global statistical glass viscosity model was developed for predicting the complete viscosity curve, based on more than 2200 composition-property data of silicate glasses from the scientific literature, including soda-lime-silica container and float glasses, TV panel glasses, borosilicate fiber wool and E type glasses, low expansion borosilicate glasses, glasses for nuclear waste vitrification, lead crystal glasses, binary alkali silicates, and various further compositions from over half a century. It is shown that within a measurement series from a specific laboratory the reported viscosity values are often over-estimated at higher temperatures due to alkali and boron oxide evaporation during the measurement and glass preparation, including data by Lakatos et al. (1972) and the recently published High temperature glass melt property database for process modeling by Seward et al. (2005). Similarly, in the glass transition range many experimental data of borosilicate glasses are reported too high due to phase separation effects. The developed global model corrects those errors. The model standard error was 9-17°C, with R^2 = 0.985-0.989. The prediction 95% confidence interval for glass in mass production largely depends on the glass composition of interest, the composition uncertainty, and the viscosity level. New insights in the mixed-alkali effect are provided.

  4. Simultaneous high-temperature removal of alkali and particulates in a pressurized gasification system. Seventh quarterly project report, October 1982-December 1982

    SciTech Connect

    Mulik, P.R.; Alvin, M.A.; Bachovchin, D.M.

    1983-01-01

    This program is directed at performing experimental and analytical investigations, deriving system designs, and estimating costs to asertain the feasibility of using aluminosilicate-based getters for controlling alkali in pressurized gasifications systems. Its overall objective is to develop a comprehensive plan for evaluating a scaled-up version of the gettering process as a unit operation or as an integral part of a particulate removal device. This report briefly summarizes efforts previously completed on thermodynamic projections and system performance projections, together with current work on getter selection and qualification. Work on the thermodynamic projections has been completed and includes an update of the data base, development of alkali phase diagrams, and projections for several gasification processes. Getter selection and qualification efforts involved four tests with the leading candidate getter -- emathlite -- on the thermogravimetric analysis (TGA) system. Plans were also formulated for three tests with emathlite on the bench-scale unit, including one with simulated fuel gas containing water vapor and alkali.

  5. Simultaneous high-temperature removal of alkali and particulates in a pressurized gasification system. Final technical progress report, October 1978-October 1980

    SciTech Connect

    Mulik, P.R.; Ciliberti, D.F.; Alvin, M.A.; Ahmed, M.M.; Bachovchin, D.M.; Keairns, D.L.

    1981-02-01

    This final project report summarizes the results of extensive thermodynamic and preliminary experimental studies that have identified the use of aluminosilicate materials for simultaneously removing volatile alkali and particulate released during pressurized gasification of coal. The gettering capacity of three selected materials has been evaluated in a bench-scale reactor operating at 1114 kPa total pressure and 1123 to 1173 K in alkali-laden inert and simulated fuel gas environments. At 1123 K alkali gettering results through insoluble complexes, while at 1173 K saturation of the insoluble complex is completed, with gettering occurring mainly through soluble complexes. The gettering mechanism will be delineated through future thermogravimetric studies in a proposed program extension.

  6. Upgrading platform using alkali metals

    SciTech Connect

    Gordon, John Howard

    2014-09-09

    A process for removing sulfur, nitrogen or metals from an oil feedstock (such as heavy oil, bitumen, shale oil, etc.) The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  7. Applications of high resolution NMR to geochemistry: crystalline, glass, and molten silicates

    SciTech Connect

    Schneider, E.

    1985-11-01

    The nuclear spin interactions and the associated quantum mechanical dynamics which are present in solid state NMR are introduced. A brief overview of aluminosilicate structure is presented and crystalline structure is then reviewed, with emphasis on the contributions made by /sup 29/Si NMR spectroscopy. The local structure of glass aluminosilicates as observed by NMR, is presented with analysis of the information content of /sup 29/Si spectra. A high-temperature (to 1300/sup 0/C) NMR spectroscopic investigation of the local environment and dynamics of molecular motion in molten aluminosilicates is described. A comparison is made of silicate liquid, glass, and crystalline local structure. The atomic and molecular motions present in a melt are investigated through relaxation time (T/sub 1/ and T/sub 2/) measurements as a function of composition and temperature for /sup 23/Na and /sup 29/Si.

  8. SODIUM ALUMINOSILICATE FOULING AND CLEANING OF DECONTAMINATED SALT SOLUTION COALESCERS

    SciTech Connect

    Poirier, M; Thomas Peters, T; Fernando Fondeur, F; Samuel Fink, S

    2008-10-28

    During initial non-radioactive operations at the Modular Caustic Side Solvent Extraction Unit (MCU), the pressure drop across the decontaminated salt solution coalescer reached {approx}10 psi while processing {approx}1250 gallons of salt solution, indicating possible fouling or plugging of the coalescer. An analysis of the feed solution and the 'plugged coalescer' concluded that the plugging was due to sodium aluminosilicate solids. MCU personnel requested Savannah River National Laboratory (SRNL) to investigate the formation of the sodium aluminosilicate solids (NAS) and the impact of the solids on the decontaminated salt solution coalescer. Researchers performed developmental testing of the cleaning protocols with a bench-scale coalescer container 1-inch long segments of a new coalescer element fouled using simulant solution. In addition, the authors obtained a 'plugged' Decontaminated Salt Solution coalescer from non-radioactive testing in the MCU and cleaned it according to the proposed cleaning procedure. Conclusions from this testing include the following: (1) Testing with the bench-scale coalescer showed an increase in pressure drop from solid particles, but the increase was not as large as observed at MCU. (2) Cleaning the bench-scale coalescer with nitric acid reduced the pressure drop and removed a large amount of solid particles (11 g of bayerite if all aluminum is present in that form or 23 g of sodium aluminosilicate if all silicon is present in that form). (3) Based on analysis of the cleaning solutions from bench-scale test, the 'dirt capacity' of a 40 inch coalescer for the NAS solids tested is calculated as 450-950 grams. (4) Cleaning the full-scale coalescer with nitric acid reduced the pressure drop and removed a large amount of solid particles (60 g of aluminum and 5 g of silicon). (5) Piping holdup in the full-scale coalescer system caused the pH to differ from the target value. Comparable hold-up in the facility could lead to less effective

  9. Adsorption of β-galactosidase on silica and aluminosilicate adsorbents

    NASA Astrophysics Data System (ADS)

    Atyaksheva, L. F.; Dobryakova, I. V.; Pilipenko, O. S.

    2015-03-01

    It is shown that adsorption of β-galactosidase of Aspergillus oryzae fungi on mesoporous and biporous silica and aluminosilicate adsorbents and the rate of the process grow along with the diameter of the pores of the adsorbent. It is found that the shape of the adsorption isotherms changes as well, depending on the texture of the adsorbent: the Michaelis constant rises from 0.3 mM for the enzyme in solution to 0.4-0.5 mM for the enzyme on a surface in the hydrolysis of o-nitrophenyl-β-D-galactopyranoside. It is concluded that β-galactosidase displays its maximum activity on the surface of biporous adsorbents.

  10. Glass/Ceramic Composites for Sealing Solid Oxide Fuel Cells

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Choi, Sung R.

    2007-01-01

    A family of glass/ceramic composite materials has been investigated for use as sealants in planar solid oxide fuel cells. These materials are modified versions of a barium calcium aluminosilicate glass developed previously for the same purpose. The composition of the glass in mole percentages is 35BaO + 15CaO + 5Al2O3 + 10B2O3 + 35SiO2. The glass seal was found to be susceptible to cracking during thermal cycling of the fuel cells. The goal in formulating the glass/ ceramic composite materials was to (1) retain the physical and chemical advantages that led to the prior selection of the barium calcium aluminosilicate glass as the sealant while (2) increasing strength and fracture toughness so as to reduce the tendency toward cracking. Each of the composite formulations consists of the glass plus either of two ceramic reinforcements in a proportion between 0 and 30 mole percent. One of the ceramic reinforcements consists of alumina platelets; the other one consists of particles of yttria-stabilized zirconia wherein the yttria content is 3 mole percent (3YSZ). In preparation for experiments, panels of the glass/ceramic composites were hot-pressed and machined into test bars.

  11. Rationale for windshield glass system specification requirements for shuttle orbiter

    NASA Technical Reports Server (NTRS)

    Hayashida, K.; King, G. L.; Tesinsiky, J.; Wittenburg, D. R.

    1972-01-01

    A preliminary procurement specification for the space shuttle orbiter windshield pane, and some of the design considerations and rationale leading to its development are presented. The windshield designer is given the necessary methods and procedures for assuring glass pane structural integrity by proof test. These methods and procedures are fully developed for annealed and thermally tempered aluminosilicate, borosilicate, and soda lime glass and for annealed fused silica. Application of the method to chemically tempered glass is considered. Other considerations are vision requirements, protection against bird impact, hail, frost, rain, and meteoroids. The functional requirements of the windshield system during landing, ferrying, boost, space flight, and entry are included.

  12. Cathodoluminescence Characterization of Maskelynite and Alkali Feldspar in Shergottite (Dhofar 019)

    SciTech Connect

    Kayama, M.; Nakazato, T.; Nishido, H.; Ninagawa, K.; Gucsik, A.

    2009-08-17

    Dhofar 019 is classified as an olivine-bearing basaltic shergottite and consists of subhedral grains of pyroxene, olivine, feldspar mostly converted to maskelynite and minor alkali feldspar. The CL spectrum of its maskelynite exhibits an emission band at around 380 nm. Similar UV-blue emission has been observed in the plagioclase experimentally shocked at 30 and 40 GPa, but not in terrestrial plagioclase. This UV-blue emission is a notable characteristic of maskelynite. CL spectrum of alkali feldspar in Dhofar 019 has an emission bands at around 420 nm with no red emission. Terrestrial alkali feldspar actually consists of blue and red emission at 420 and 710 nm assigned to Al-O{sup -}-Al and Fe{sup 3+} centers, respectively. Maskelynite shows weak and broad Raman spectral peaks at around 500 and 580 cm{sup -1}. The Raman spectrum of alkali feldspar has a weak peak at 520 cm{sup -1}, whereas terrestrial counterpart shows the emission bands at 280, 400, 470, 520 and 1120 cm{sup -1}. Shock pressure on this meteorite transformed plagioclase and alkali feldspar into maskelynite and almost glass phase, respectively. It eliminates their luminescence centers, responsible for disappearance of yellow and/or red emission in CL of maskelynite and alkali feldspar. The absence of the red emission band in alkali feldspar can also be due to the lack of Fe{sup 3+} in the feldspar as it was reported for some lunar feldspars.

  13. Hydrothermal alkali metal catalyst recovery process

    DOEpatents

    Eakman, James M.; Clavenna, LeRoy R.

    1979-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles primarily in the form of water soluble alkali metal formates by treating the particles with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of added carbon monoxide. During the treating process the water insoluble alkali metal compounds comprising the insoluble alkali metal residues are converted into water soluble alkali metal formates. The resultant aqueous solution containing water soluble alkali metal formates is then separated from the treated particles and any insoluble materials formed during the treatment process, and recycled to the gasification process where the alkali metal formates serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. This process permits increased recovery of alkali metal constituents, thereby decreasing the overall cost of the gasification process by reducing the amount of makeup alkali metal compounds necessary.

  14. X-ray microtomography shows pore structure and tortuosity in alkali-activated binders

    SciTech Connect

    Provis, John L.; Myers, Rupert J.; White, Claire E.; Rose, Volker; Deventer, Jannie S.J. van

    2012-06-15

    Durability of alkali-activated binders is of vital importance in their commercial application, and depends strongly on microstructure and pore network characteristics. X-ray microtomography ({mu}CT) offers, for the first time, direct insight into microstructural and pore structure characteristics in three dimensions. Here, {mu}CT is performed on a set of sodium metasilicate-activated fly ash/slag blends, using a synchrotron beamline instrument. Segmentation of the samples into pore and solid regions is then conducted, and pore tortuosity is calculated by a random walker method. Segmented porosity and diffusion tortuosity are correlated, and vary as a function of slag content (slag addition reduces porosity and increases tortuosity), and sample age (extended curing gives lower porosity and higher tortuosity). This is particularly notable for samples with {>=} 50% slag content, where a space-filling calcium (alumino)silicate hydrate gel provides porosity reductions which are not observed for the sodium aluminosilicate ('geopolymer') gels which do not chemically bind water of hydration.

  15. A new titanium-bearing calcium aluminosilicate phase. 1: Meteoritic occurrences and formation in synthetic systems

    NASA Technical Reports Server (NTRS)

    Paque, Julie M.; Beckett, John R.; Barber, David J.; Stolper, Edward M.

    1994-01-01

    A new titanium-bearing calcium aluminosilicate mineral has been identified in coarse-grained calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites. The formula for this phase, which we have temporarily termed 'UNK,' is Ca3Ti(Al,Ti)2(Si,Al)3O14, and it is present in at least 8 of the 20 coarse-grained CAIs from the Allende CV3 chondrite examined as part of this project. The phase occurs in Types A and B1 inclusions as small tabular crystal oriented along two mutually perpendicular planes in melilite. UNK crystallizes from melts in dynamic crystallization experiments conducted in air from four bulk compositions modeled after Types A, B1, B2 and C inclusions. Cooling rates resulting in crystallization of UNK ranged from 0.5 to 200 C/h from maximum (initial) temperatures of 1375 to 1580 C. Only below 1190 C does UNK itself begin to crystallize. To first order, the presence or absence of UNK from individual experiments can be understood in terms of the compositions of residual melts and nucleation probabilities. Compositions of synthetic and meteoritic UNK are very similar in terms of major oxides, differing only in the small amounts of trivalent Ti(7-13% of total Ti) in meteoritic samples. UNK crystallized from the Type A analog is similar texturally to that found in CAIs, although glass, which is typically associated with synthetic UNK, is not observed in the meteoritic occurrences. A low Ti end-member of UNK ('Si-UNK') with a composition near that of Ca3Al2Si4O14 was produced in a few samples from the Type B1 analog. This phase has not been found in the meteoritic inclusions.

  16. A New Titanium-Bearing Calcium Aluminosilicate Phase. 1; Meteoritic Occurrences and Formation in Synthetic Systems

    NASA Technical Reports Server (NTRS)

    Paque, Julie M.; Beckett, John R.; Barber, David J.; Stolper, Edward M.

    1994-01-01

    A new titanium-bearing calcium aluminosilicate mineral has been identified in coarse-grained calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites. The formula for this phase, which we have temporarily termed "UNK," is Ca3Ti(AlTi)2(Si,Al)3O14, and it is present in at least 8 of the 20 coarse-grained CAIs from the Allende CV3 chondrite examined as part of this project. The phase occurs in Types A and B1 inclusions as small tabular crystals oriented along two mutually perpendicular planes in melilite. UNK crystallizes from melts in dynamic crystallization experiments conducted in air from four bulk compositions modeled after Types A, B1, B2 and C inclusions. Cooling rates resulting in crystallization of UNK ranged from 0.5 to 200 C/h from maximum (initial) temperatures of 1375 to 1580 C. Only below 1190 C does UNK itself begin to crystallize. To first order, the presence or absence of UNK from individual experiments can be understood in terms of the compositions of residual melts and nucleation probabilities. Compositions of synthetic and meteoritic LINK are very similar in terms of major oxides, differing only in the small amounts of trivalent Ti (7-13% of total Ti) in meteoritic samples. UNK crystallized from the Type A analog is similar texturally to that found in CAls, although glass, which is typically associated with synthetic UN& is not observed in meteoritic occurrences. A low Ti end-member of UNK ("Si-UNK") with a composition new that of Ca3Al2Si4O14 was produced in a few samples from the Type B1 analog. This phase has not been found in the meteoritic inclusions.

  17. An Electron Microprobe Study of Synthetic Aluminosilicate Garnets

    NASA Astrophysics Data System (ADS)

    Fournelle, J.; Geiger, C. A.

    2010-12-01

    The aluminosilicate garnets represent an important mineral group. Common end-members are given by E3Al2Si3O12, where E=Fe2+ (almandine), Mn2+ (spessartine), Mg (pyrope), and Ca (grossular). End-members have been synthesized, but their exact compositions and stoichiometries are generally unknown. Synthetic aluminosilicate garnet can possibly contain minor Fe3+, Mn3+, F- and OH- and possibly vacancies. Slight atomic disorder over the 3 different cation sites may also occur. Natural crystals are considerably more complex. Electron probe microanalysis (EPMA) provides a method to determine garnet chemistry and stoichiometry. However, accurate determinations are not always a simple matter and uncertainties exist. We have started a study on well-characterized synthetic aluminosilicate garnets in order to i) determine more exactly their compositions and stoichiometries and ii) better understand possible complications in EPMA. Synthetic almandine, spessartine, pyrope, and grossular samples were synthesized under varying conditions both hydrothermally and dry and with different starting materials. A closed thermodynamic system was present and the bulk starting material composition represented the exact stoichiometric end-member garnet that was desired. IR, Raman and Mössbauer spectroscopy in some cases and X-ray diffraction were used to characterize the samples. Synthetic pyrope has been investigated with a SX51 with simple oxide/silicate standards (Fo90 olivine for Mg, wollastonite for Si, and both Al2O3 and kyanite for Al). Previously observed problems were reproduced: low stoichiometry for Al and high for Si and Mg. Fournelle (2007, AGU Fall Mtg) noted chemical peak shifts for Al and Mg Ka in garnets; this effect was eliminated here by proper peaking. Earlier suggestions for issues with mass absorption coefficients were not seen, and Probe for EPMA software demonstrated there was not much difference between the most recent FFAST values vs. the older Heinrich values

  18. Low melting high lithia glass compositions and methods

    DOEpatents

    Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.

    2003-09-23

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste uranium oxides The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

  19. Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

    DOEpatents

    Joshi, Ashok V.; Balagopal, Shekar; Pendelton, Justin

    2011-12-13

    Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

  20. A note on the Raman spectra of water-bearing albite glasses

    NASA Technical Reports Server (NTRS)

    Mcmillan, P. F.; Jakobsson, S.; Holloway, J. R.; Silver, L. A.

    1983-01-01

    The Raman spectra of albite glasses with 4.5 and 6.6 weight percent water have been obtained, and are compared with that of a dry sample. The hydrous glasses show bands near 3600/cm due to O-H stretching, and a previously unreported weak band near 1600/cm due to bending of molecular H2O. Other weak spectral features are discussed, and the effect of dissolved water on the aluminosilicate framework vibrations is considered.

  1. The calcium-alkali syndrome.

    PubMed

    Arroyo, Mariangeli; Fenves, Andrew Z; Emmett, Michael

    2013-04-01

    The milk-alkali syndrome was a common cause of hypercalcemia, metabolic alkalosis, and renal failure in the early 20th century. It was caused by the ingestion of large quantities of milk and absorbable alkali to treat peptic ulcer disease. The syndrome virtually vanished after introduction of histamine-2 blockers and proton pump inhibitors. More recently, a similar condition called the calcium-alkali syndrome has emerged as a common cause of hypercalcemia and alkalosis. It is usually caused by the ingestion of large amounts of calcium carbonate salts to prevent or treat osteoporosis and dyspepsia. We describe a 78-year-old woman who presented with weakness, malaise, and confusion. She was found to have hypercalcemia, acute renal failure, and metabolic alkalosis. Upon further questioning, she reported use of large amounts of calcium carbonate tablets to treat recent heartburn symptoms. Calcium supplements were discontinued, and she was treated with intravenous normal saline. After 5 days, the calcium and bicarbonate levels normalized and renal function returned to baseline. In this article, we review the pathogenesis of the calcium-alkali syndrome as well as the differences between the traditional and modern syndromes. PMID:23543983

  2. SODIUM ALUMINOSILICATE SOLIDS AFFINITY FOR CESIUM AND ACTINIDES

    SciTech Connect

    Peters, T; Bill Wilmarth, B; Samuel Fink, S

    2007-07-31

    Washed sodium-aluminosilicate (NAS) solids at initial concentrations of 3.55 and 5.4 g/L sorb or uptake virtually no cesium over 288 hours, nor do any NAS solids generated during that time. These concentrations of solids are believed to conservatively bound current and near-term operations. Hence, the NAS solids should not have affected measurements of the cesium during the mass transfer tests and there is minimal risk of accumulating cesium during routine operations (and hence posing a gamma radiation exposure risk in maintenance). With respect to actinide uptake, it appears that NAS solids sorb minimal quantities of uranium - up to 58 mg U per kg NAS solid. The behavior with plutonium is less well understood. Additional study may be needed for radioactive operations relative to plutonium or other fissile component sorption or trapping by the solids. We recommend this testing be incorporated in the planned tests using samples from Tank 25F and Tank 49H to extend the duration to bound expected inventory time for solution.

  3. The metapelitic garnet biotite muscovite aluminosilicate quartz (GBMAQ) geobarometer

    NASA Astrophysics Data System (ADS)

    Wu, Chun-Ming; Zhao, Guochun C.

    2007-09-01

    In this contribution we have empirically calibrated the garnet-biotite-muscovite-aluminosilicate-quartz (GBMAQ) barometer using low- to medium-high-pressure, mid-grade metapelites. Application of the barometer suggests that the GBMAQ and GASP barometers show quite similar pressure estimates. Furthermore, metapelites within thermal contact aureole or very limited geographic area show no meaningful pressure diversity determined by the GBMAQ and GASP barometers which is the geological reality. The random error of the GBMAQ barometer is expected to be around ± 0.8 kbar, and this barometer shows no systematic bias with respect to either pressure, or temperature, or Al VI in muscovite, or Fe in biotite, or Fe in garnet. The GBMAQ barometer is thermodynamically consistent with the garnet-biotite geothermometer because they share the same activity models of both garnet and biotite. This barometer is especially useful for assemblages with Ca-poor garnet or Ca-poor plagioclase or plagioclase-absent metapelites. Application of this barometer beyond the calibration ranges, i.e., P- T range and chemical ranges of the minerals, is not encouraged.

  4. Surface functionalization of aluminosilicate nanotubes with organic molecules

    PubMed Central

    Ma, Wei; Yah, Weng On; Otsuka, Hideyuki

    2012-01-01

    Summary The surface functionalization of inorganic nanostructures is an effective approach for enriching the potential applications of existing nanomaterials. Inorganic nanotubes attract great research interest due to their one-dimensional structure and reactive surfaces. In this review paper, recent developments in surface functionalization of an aluminosilicate nanotube, “imogolite”, are introduced. The functionalization processes are based on the robust affinity between phosphate groups of organic molecules and the aluminol (AlOH) surface of imogolite nanotubes. An aqueous modification process employing a water soluble ammonium salt of alkyl phosphate led to chemisorption of molecules on imogolite at the nanotube level. Polymer-chain-grafted imogolite nanotubes were prepared through surface-initiated polymerization. In addition, the assembly of conjugated molecules, 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-yl)ethylphosphonic acid (HT3P) and 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-yl)ethylphosphonic acid 1,1-dioxide (HT3OP), on the imogolite nanotube surface was achieved by introducing a phosphonic acid group to the corresponding molecules. The optical and photophysical properties of these conjugated-molecule-decorated imogolite nanotubes were characterized. Moreover, poly(3-hexylthiophene) (P3HT) chains were further hybridized with HT3P modified imogolite to form a nanofiber hybrid. PMID:22428100

  5. Irradiation study of PNNL synthesized glass-ceramics

    SciTech Connect

    Kossoy-simakov, Anna-eden; Tang, Ming; Valdez, James A; Usov, Igor O; Sickafus, Kurt E

    2011-01-18

    Two types of glass-ceramic were investigated: (1) for immobilization of Ln, alkali, and alkaline earths (GC4); and (2) same as above + high (7%) molybdenum content (Mo7) multiphase specimens. The purpose was to study the radiation stability of PNNL synthesized glass-ceramics and changes in microstructure/phase composition.

  6. Utilization of calcite and waste glass for preparing construction materials with a low environmental load.

    PubMed

    Maeda, Hirotaka; Imaizumi, Haruki; Ishida, Emile Hideki

    2011-11-01

    In this study, porous calcite materials are hydrothermally treated at 200 °C using powder compacts consisting of calcite and glasses composed of silica-rich soda-lime. After treatment, the glasses are converted into calcium aluminosilicate hydrates, such as zeolite phases, which increase their strength. The porosity and morphology of new deposits of hydrothermally solidified materials depend up on the chemical composition of glass. The use of calcite and glass in the hydrothermal treatment plays an important role in the solidification of calcite without thermal decomposition. PMID:21794973

  7. Process for direct conversion of reactive metals to glass

    DOEpatents

    Rajan, John B.; Kumar, Romesh; Vissers, Donald R.

    1990-01-01

    Radioactive alkali metal is introduced into a cyclone reactor in droplet form by an aspirating gas. In the cyclone metal reactor the aspirated alkali metal is contacted with silica powder introduced in an air stream to form in one step a glass. The sides of the cyclone reactor are preheated to ensure that the initial glass formed coats the side of the reactor forming a protective coating against the reactants which are maintained in excess of 1000.degree. C. to ensure the formation of glass in a single step.

  8. Healing of lithographically introduced flaws in glass and glass containing ceramics

    SciTech Connect

    Ackler, H.D.

    1992-12-01

    The morphological evolution of cylindrical pores or channels'' and crack-like cavities in glass and glass-containing ceramics at elevated temperatures was studied. The systems studied were: Coming 7056 alkali borosilicate glass, soda-lime glass (microscope slides), a commercially available 96% Al[sub 2]O[sub 3]with [approx]5--10% intergranular glass, 96% Al[sub 2]O[sub 3] bonded to sapphire, and a model sapphire/glass/sapphire system fabricated by diffusion bonding etched and unetched pieces of sapphire onto which 30--50 nm of SiO[sub 2] had been sputter deposited. These systems span a broad range of glass contents, and permit observation of healing behavior with varying glass content. The results were compared with analytical models and results of similar studies in completely crystalline systems.

  9. Healing of lithographically introduced flaws in glass and glass containing ceramics

    SciTech Connect

    Ackler, H.D.

    1992-12-01

    The morphological evolution of cylindrical pores or ``channels`` and crack-like cavities in glass and glass-containing ceramics at elevated temperatures was studied. The systems studied were: Coming 7056 alkali borosilicate glass, soda-lime glass (microscope slides), a commercially available 96% Al{sub 2}O{sub 3}with {approx}5--10% intergranular glass, 96% Al{sub 2}O{sub 3} bonded to sapphire, and a model sapphire/glass/sapphire system fabricated by diffusion bonding etched and unetched pieces of sapphire onto which 30--50 nm of SiO{sub 2} had been sputter deposited. These systems span a broad range of glass contents, and permit observation of healing behavior with varying glass content. The results were compared with analytical models and results of similar studies in completely crystalline systems.

  10. Progress in Understanding Alkali-Alkali Spin Relaxation

    NASA Astrophysics Data System (ADS)

    Erickson, Christopher J.; Happer, William; Chann, Bien; Kadlecek, Stephen; Anderson, L. W.; Walker, Thad G.

    2000-06-01

    In extensive experiments we have shown that a spin interaction with a relatively long correlation time causes much of the spin relaxation in very dense alkali-metal vapors. The spin relaxation is affected by the pressure of the helium or nitrogen buffer gas, although there is little dependence at pressures above one atmosphere. There are substantial differences in the relaxation rates for different isotopes of the same element, for example ^87Rb and ^85Rb. We have completed extensive modeling of how singlet and triplet dimers and doublet trimers of the alkali-metal atoms could cause spin relaxation in dense alkali-metal vapors. In the case of doublet trimers or triplet dimers, we assume the main coupling to the nuclear spins is through the Fermi Contact interaction with the unpaired electrons. Spin loss to the rotation of the molecule is assumed to occur through the electronic spin-rotation and spin-axis (dipole-dipole) interactions for the triplet dimers. For the singlet dimers, we assume that the nuclear spins couple directly to the rotational angular momentum of the molecule through the electric quadrupole interaction. We account for all of the total nuclear spin states that occur for the dimers and trimers. We have also considered the possibility that the collisional breakup and formation rates of the dimers or trimers could saturate with increasing buffer gas pressure. Such saturation occurs in many other unimolecular reactions and is often ascribed to breakup through activated states.

  11. Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

    NASA Technical Reports Server (NTRS)

    Rampe, E. B.; Bish, D. L.; Chipera, S. J.; Morris, R. V.; Achilles, C. N.; Ming, D W.; Blake, D. F.; Anderson, R. C.; Bristow, T. F.; Crisp, A.; DesMarais, D. J.; Downs, R. T.; Farmer, J. D.; Morookian, J. M.; Morrison, S. M.; Sarrazin, P.; Spanovich, N.; Stolper, E. M.; Treiman, A. H.; Vaniman, D. T.; Yen, A. S.

    2013-01-01

    X-ray diffraction (XRD) data collected of the Rocknest samples by the CheMin instrument on Mars Science Laboratory suggest the presence of poorly crystalline or amorphous materials [1], such as nanophase weathering products or volcanic and impact glasses. The identification of the type(s) of X-ray amorphous material at Rocknest is important because it can elucidate past aqueous weathering processes. The presence of volcanic and impact glasses would indicate that little chemical weathering has occurred because glass is highly susceptible to aqueous alteration. The presence of nanophase weathering products, such as allophane, nanophase iron-oxides, and/or palagonite, would indicate incipient chemical weathering. Furthermore, the types of weathering products present could help constrain pH conditions and identify which primary phases altered to form the weathering products. Quantitative analysis of phases from CheMin data is achieved through Reference Intensity Ratios (RIRs) and Rietveld refinement. The RIR of a mineral (or mineraloid) that relates the scattering power of that mineral (typically the most intense diffraction line) to the scattering power of a separate mineral standard such as corundum [2]. RIRs can be calculated from XRD patterns measured in the laboratory by mixing a mineral with a standard in known abundances and comparing diffraction line intensities of the mineral to the standard. X-ray amorphous phases (e.g., nanophase weathering products) have broad scattering signatures rather than sharp diffraction lines. Thus, RIRs of X-ray amorphous materials are calculated by comparing the area under one of these broad scattering signals with the area under a diffraction line in the standard. Here, we measured XRD patterns of nanophase weathering products (allophane, aluminosilicate gel, and ferrihydrite) mixed with a mineral standard (beryl) in the CheMinIV laboratory instrument and calculated their RIRs to help constrain the abundances of these phases in

  12. Spatial Polarization Profile in an Optically Pumped Alkali Vapor

    NASA Astrophysics Data System (ADS)

    Olsen, Ben; Patton, Brian; Jau, Yuan-Yu; Happer, Will

    2009-05-01

    Spin-Exchange Optical Pumping (SEOP) is a technique used to polarize nuclei in gases, and more recently in solids, in excess of their equilibrium limit. SEOP is achieved by optically pumping an alkali vapor which subsequently transfers angular momentum to the nuclei of interest. The efficiency of SEOP is governed by optical pumping and relaxation of the alkali atoms, relaxation of the target nuclei, and interactions between the alkali and target substance. In this work we investigate the relationship between optical pumping and relaxation in cesium vapor with absorption spectroscopy at high magnetic field (2.7 T). Cesium vapor within a cylindrical glass vapor cell is optically pumped with a strong laser resonant with a D2 transition. The ground-state population of the vapor is measured at various positions along a diameter of the cell with a small, weak D1 laser beam which translates mechanically. The resulting polarization profile elucidates the interplay between optical pumping, diffusion in the buffer gas, and relaxation at the walls of the vapor cell. We report measurements of the spatial polarization profile in vapor cells with bare Pyrex walls and cells coated with paraffin (an anti-relaxation coating) or CsH salt (a target substance for SEOP), and compare them to numerical simulations. Further investigation might yield a new method for characterizing surface relaxation in vapor cells.

  13. Modeling the local structure and energetics of protozeolitic nanoclusters in hydrothermally stable aluminosilicate mesostructures.

    PubMed

    Li, Hong; Mahanti, S D; Pinnavaia, Thomas J

    2005-02-24

    The density functional theory (DFT) method is used to investigate the structure and bonding of silica and aluminosilicate nanoclusters containing five- and six-membered oxygen rings. The clusters, which are derived from the BEA zeolite structure, are considered as models of the protozeolitic clusters that are incorporated into the pore walls of steam stable aluminosilicate mesostructures assembled from zeolite seeds. Two locally different Brønsted acid sites in the aluminosilicate structure are identified for the adsorption of a water molecule. The sterically more open acid site is favored for water binding. The stability of the aluminosilicate structure in the presence of H2O molecule is studied by breaking an Al-O bond and inserting a water molecule into the five-membered ring structure. We find that an excitation energy at least 18 times larger than the room-temperature thermal energy is needed to break the stable five-membered ring structure, implying a high hydrothermal stability and acidity for this aluminosilicate structure. PMID:16851274

  14. Positron-alkali atom scattering

    NASA Technical Reports Server (NTRS)

    Mceachran, R. P.; Horbatsch, M.; Stauffer, A. D.; Ward, S. J.

    1990-01-01

    Positron-alkali atom scattering was recently investigated both theoretically and experimentally in the energy range from a few eV up to 100 eV. On the theoretical side calculations of the integrated elastic and excitation cross sections as well as total cross sections for Li, Na and K were based upon either the close-coupling method or the modified Glauber approximation. These theoretical results are in good agreement with experimental measurements of the total cross section for both Na and K. Resonance structures were also found in the L = 0, 1 and 2 partial waves for positron scattering from the alkalis. The structure of these resonances appears to be quite complex and, as expected, they occur in conjunction with the atomic excitation thresholds. Currently both theoretical and experimental work is in progress on positron-Rb scattering in the same energy range.

  15. Valorization of sugarcane bagasse ash: producing glass-ceramic materials.

    PubMed

    Teixeira, S R; Magalhães, R S; Arenales, A; Souza, A E; Romero, M; Rincón, J M

    2014-02-15

    Some aluminosilicates, for example mullite and wollastonite, are very important in the ceramic and construction industries. The most significant glass-ceramic for building applications has wollastonite as the main crystal phase. In this work we report on the use of sugarcane bagasse ash (SCBA) to produce glass-ceramics with silicates as the major crystalline phases. The glasses (frits) were prepared by mixing ash, limestone (calcium and magnesium carbonates) and potassium carbonate as the fluxing agent. X-ray fluorescence was used to determine the chemical composition of the glasses and their crystallization was assessed by using thermal analysis (DTA/DSC/TGA) and X-ray diffraction. The results showed that glass-ceramic material can be produced with wollastonite as the major phase, at a temperature lower than 900 °C. PMID:24463731

  16. Alkali metal/sulfur battery

    DOEpatents

    Anand, Joginder N.

    1978-01-01

    Alkali metal/sulfur batteries in which the electrolyte-separator is a relatively fragile membrane are improved by providing means for separating the molten sulfur/sulfide catholyte from contact with the membrane prior to cooling the cell to temperatures at which the catholyte will solidify. If the catholyte is permitted to solidify while in contact with the membrane, the latter may be damaged. The improvement permits such batteries to be prefilled with catholyte and shipped, at ordinary temperatures.

  17. Superconductivity in alkali metal fullerides

    NASA Astrophysics Data System (ADS)

    Murphy, D. W.; Rosseinsky, M. J.; Haddon, R. C.; Ramirez, A. P.; Hebard, A. F.; Tycko, R.; Fleming, R. M.; Dabbagh, G.

    1991-12-01

    The recent synthesis of macroscopic quantities of spherical molecular carbon compounds, commonly called fullerenes, has stimulated a wide variety of studies of the chemical and physical properties of this novel class of compounds. We discovered that the smallest of the known fullerenes, C 60, could be made conducting and superconducting by reaction with alkali metals. In this paper, an overview of the motivation for these discoveries and some recent results are presented.

  18. Aqueous dissolution of sodium aluminosilicate geopolymers derived from metakaolin

    NASA Astrophysics Data System (ADS)

    Aly, Z.; Vance, E. R.; Perera, D. S.

    2012-05-01

    In dilute aqueous solutions, the elemental releases of Na, Al and Si from a metakaolin-based sodium aluminosilicate geopolymer were not very sensitive to pH in the range of 4-10 but increased outside this range, particularly on the acidic side. To minimise pH drifts, experiments were carried out using small amounts of graded powders in relatively large volumes of water. In deionised water, the Na dissolution rate in 7 days was dominant and increased by at least a factor of ˜4 on heating from 18 to 90 °C, with greater increases in the extractions of Al and Si. At 18 °C the elemental extractions in deionised water increased approximately linearly with time over the 1-7 days period. Further exposure led to a slower extraction into solution for Na and Si, with a decrease in extraction of Al. It was deduced that framework dissolution was important in significantly acidic or alkaline solutions, but that contributions from water transfer from pores to elemental extractions were present, even at low temperatures in neutral solutions. It was also deduced from the Na release data that the Na leaching kinetics of geopolymer in deionised water (dilute solutions) followed the pseudo-second-order kinetic model and the pseudo-second-order rate constant evaluated. Contact with KCl, KHCO3, and pH ˜6 and 10 potassium phthalate buffer solutions gave rise to a high degree of Na+ ↔ K+ exchange and rendered the framework ions less leachable in water.

  19. Alkali metal sources for OLED devices

    NASA Astrophysics Data System (ADS)

    Cattaneo, Lorena; Longoni, Giorgio; Bonucci, Antonio; Tominetti, Stefano

    2005-07-01

    In OLED organic layers electron injection is improved by using alkali metals as cathodes, to lower work function or, as dopants of organic layer at cathode interface. The creation of an alkali metal layer can be accomplished through conventional physical vapor deposition from a heated dispenser. However alkali metals are very reactive and must be handled in inert atmosphere all through the entire process. If a contamination takes place, it reduces the lithium deposition rate and also the lithium total yield in a not controlled way. An innovative alkali metal dispensing technology has been developed to overcome these problems and ensure OLED alkali metal cathode reliability. The alkali Metal dispenser, called Alkamax, will be able to release up to a few grams of alkali metals (in particular Li and Cs) throughout the adoption of a very stable form of the alkali metal. Lithium, for example, can be evaporated "on demand": the evaporation could be stopped and re-activated without losing alkali metal yield because the metal not yet consumed remains in its stable form. A full characterization of dispensing material, dispenser configuration and dispensing process has been carried out in order to optimize the evaporation and deposition dynamics of alkali metals layers. The study has been performed applying also inside developed simulations tools.

  20. Relationship between microstructure and efficiency of scintillating glasses

    SciTech Connect

    Bliss, M.; Craig, R.A.; Reeder, P.L.; Sunberg, D.S.; Weber, M.J.

    1994-04-01

    Prior work has shown that there is a correlation between trap densities and scintillation efficiency of cerium-activated, lithium-aluminosilicate glasses. Raman spectroscopy has strongly suggested that phase separation may be playing an important role in governing the scintillation efficiency. This study, relates the thermoluminescence glow-curve data and microstructural analysis for a compositional series. The thermoluminescence data provide information about the traps in the neighborhood of the activator (Ce{sup 3+}). The microscopy and crystallization of the glasses provide direct evidence of activator partitioning.

  1. Characterization of Glass-Like Fragments from the 3714 Building

    SciTech Connect

    Buck, Edgar C.

    2010-02-23

    This report describes characterization of a sample obtained from the 3714 building in the 300 Area. Characterization of this unknown material was required for the demonolition activities in the 300 Area. The object of the study was to dertermine the nature of the material, composition, possible structure, evidence for hazards components. The green material is a sodium alumino-silicate glass. This conclusion is based on the composition provided by SEM-EDS, and the images that suggest a glass-like morphology. Further analysis with Ramin and/or infrared could be used to determine the presence of any organics.

  2. Formation and durability of hydrated layers for several oxide glasses

    SciTech Connect

    Nishii, Junji; Akai, Tomoko; Yamashita, Masaru; Yamanaka, Hiroshi; Wakabayashi, Hajimu

    1995-12-31

    Formations and durabilities of hydrated layers were compared between a soda-aluminosilicate (NAS), a soda-lime-aluminosilicate (NCAS) and a soda-lime-alumino-borosilicate (NCABS) glasses. The first step of the study was to prepare the optically transparent hydrated layers on the surface of specimens by an autoclave (400 C, 20 kgf/cm{sup 2}) treatment. Distributions of OH groups in hydrated layers were analyzed by an etch sectioning and FTIR measurement. The rates of hydration of the glasses were in the order NAS {much_gt} NCAS > NCABS. The hydration of the NCABS glass, which is a modified nuclear waste glass, required the treatment longer than those of the NAS and NCAS glasses. In the second step, the authors investigated the durabilities of hydrated layers by immersing the specimens into a distilled water at 100 C. The dissolutions of hydrated layers were confirmed for each glass. The dissolution rates of hydrated layers were in the order NCAS > NCABS {much_gt} NAS. It has become apparent by an XPS analysis that the highest durability of the hydrated NAS glass was due to the formation of a sodium free Al{sub 2}O{sub 3}-SiO{sub 2} layer on the surface. The hydrated layer of the NCAS glass, while the sodium ions were almost leached out during immersion, dissolved to water most quickly than those of other glasses. In the hydrated layer of the NCABS glass, a half amount of sodium and boron ions remained and inhibited the dissolution of hydrated layer.

  3. Simultaneous high-temperature removal of alkali and particulates in a pressurized gasification system. First quarterly project report, April-June 1981

    SciTech Connect

    Mulik, P.R.; Alvin, M.A.; Bachovchin, D.M.; Lippert, T.E.

    1981-07-01

    This program is directed at performing experimental and analytical investigations, system designs, and cost estimates to ascertain the feasibility of using aluminosilicate-based getters for controlling alkali in pressurized gasification systems. Its overall objective is to develop a comprehensive plan for evaluating a scaled-up version of the gettering process as a unit operation or as an integral part of a particulate removal device. This report describes work completed on thermodynamic projections, getter selection and qualification, and system performance projections during the first three months of the project, as well as work applicable to this program under two companion DOE projects at Westinghouse. These latter efforts occurred in the interim between the current and a previous contract on alkali gettering.

  4. Synthesis and immobilization of silver nanoparticles on aluminosilicate nanotubes and their antibacterial properties

    NASA Astrophysics Data System (ADS)

    Ipek Yucelen, G.; Connell, Rachel E.; Terbush, Jessica R.; Westenberg, David J.; Dogan, Fatih

    2016-04-01

    A novel colloidal method is presented to synthesize silver nanoparticles on aluminosilicate nanotubes. The technique involves decomposition of AgNO3 solution to Ag nanoparticles in the presence of aluminosilicate nanotubes at room temperature without utilizing of reducing agents or any organic additives. Aluminosilicate nanotubes are shown to be capable of providing a unique chemical environment, not only for in situ conversion of Ag+ into Ag0, but also for stabilization and immobilization of Ag nanoparticles. The synthesis strategy described here could be implemented to obtain self-assembled nanoparticles on other single-walled metal oxide nanotubes for unique applications. Finally, we demonstrated that nanotube/nanoparticle hybrid show strong antibacterial activity toward Gram-positive Staphylococcus epidermidis and Gram-negative Escherichia coli.

  5. Evidence for lithium-aluminosilicate supersaturation of pegmatite-forming melts

    NASA Astrophysics Data System (ADS)

    Maneta, Victoria; Baker, Don R.; Minarik, William

    2015-07-01

    New experimental data on the solubility of lithium (Li) at spodumene (LiAlSi2O6) and petalite (LiAlSi4O10) saturation at 500 MPa and 550-750 °C reveal evidence for lithium supersaturation of pegmatite-forming melts before the formation of Li-aluminosilicates. The degree of Li enrichment in granitic melts can reach ~11,000 ppm above the saturation value before the crystallization of Li-aluminosilicate minerals at lower temperatures. Comparison of the experimental results with the spodumene-rich Moblan pegmatite (Quebec) is consistent with extreme Li enrichment of the pegmatite-forming melt prior to emplacement, which cannot be explained with equilibrium crystallization of Li-aluminosilicates from a common granitic melt. The results of this study support the model of disequilibrium fractional crystallization through liquidus undercooling as the most plausible mechanism for the generation of such Li-rich ore resources.

  6. Li{sup +} alumino-silicate ion source development for the neutralized drift compression experiment

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.; Seidl, Peter A.; Waldron, William L.; Wu, James K.

    2011-01-15

    We report results on lithium alumino-silicate ion source development in preparation for warm dense matter heating experiments on the new neutralized drift compression experiment II. The practical limit to the current density for a lithium alumino-silicate source is determined by the maximum operating temperature that the ion source can withstand before running into problems of heat transfer, melting of the alumino-silicate material, and emission lifetime. Using small prototype emitters, at a temperature of {approx_equal}1275 deg. C, a space-charge limited Li{sup +} beam current density of J {approx_equal}1 mA/cm{sup 2} was obtained. The lifetime of the ion source was {approx_equal}50 h while pulsing at a rate of 0.033 Hz with a pulse duration of 5-6 {mu}s.

  7. Li+ alumino-silicate ion source development for the Neutralized Drift Compression Experiment (NDCX)

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.; Seidl, Peter A.; Waldron, William L.; Wu, James K.

    2010-10-01

    We report results on lithium alumino-silicate ion source development in preparation for warmdense-matter heating experiments on the new Neutralized Drift Compression Experiment (NDCXII). The practical limit to the current density for a lithium alumino-silicate source is determined by the maximum operating temperature that the ion source can withstand before running into problems of heat transfer, melting of the alumino-silicate material, and emission lifetime. Using small prototype emitters, at a temperature of ~;;1275 oC, a space-charge-limited Li+ beam current density of J ~;;1 mA/cm2 was obtained. The lifetime of the ion source was ~;;50 hours while pulsing at a rate of 0.033 Hz with a pulse duration of 5-6 mu s.

  8. Interface Induced Growth and Transformation of Polymer-Conjugated Proto-Crystalline Phases in Aluminosilicate Hybrids: A Multiple-Quantum (23)Na-(23)Na MAS NMR Correlation Spectroscopy Study.

    PubMed

    Brus, Jiri; Kobera, Libor; Urbanova, Martina; Doušová, Barbora; Lhotka, Miloslav; Koloušek, David; Kotek, Jiří; Čuba, Pavel; Czernek, Jiri; Dědeček, Jiří

    2016-03-22

    Nanostructured materials typically offer enhanced physicochemical properties because of their large interfacial area. In this contribution, we present a comprehensive structural characterization of aluminosilicate hybrids with polymer-conjugated nanosized zeolites specifically grown at the organic-inorganic interface. The inorganic amorphous Al-O-Si framework is formed by alkali-activated low-temperature transformation of metakaoline, whereas simultaneous copolymerization of organic comonomers creates a secondary epoxide network covalently bound to the aluminosilicate matrix. This secondary epoxide phase not only enhances the mechanical integrity of the resulting hybrids but also introduces additional binding sites accessible for compensating negative charge on the aluminosilicate framework. This way, the polymer network initiates growth and subsequent transformation of protocrystalline short-range ordered zeolite domains that are located at the organic-inorganic interface. By applying an experimental approach based on 2D (23)Na-(23)Na double-quantum (DQ) MAS NMR spectroscopy, we discovered multiple sodium binding sites in these protocrystalline domains, in which immobilized Na(+) ions form pairs or small clusters. It is further demonstrated that these sites, the local geometry of which allows for the pairing of sodium ions, are preferentially occupied by Pb(2+) ions during the ion exchange. The proposed synthesis protocol thus allows for the preparation of a novel type of geopolymer hybrids with polymer-conjugated zeolite phases suitable for capturing and storage of metal cations. The demonstrated (23)Na-(23)Na DQ MAS NMR combined with DFT calculations represents a suitable approach for understanding the role of Na(+) ions in aluminositicate solids and related inorganic-organic hybrids, particularly their specific arrangement and clustering at interfacial areas. PMID:26931131

  9. Protein adsorption to multi-component glasses

    NASA Astrophysics Data System (ADS)

    Hall, Matthew Micah

    2003-07-01

    The adsorption of human serum albumin (HSA) to sodium silicate, soda lime silicate (SLS), and sodium aluminosilicate (SAS) glass microspheres was investigated using sodiumdodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) in conjunction with a colloidal silver stain for visualization. The 30 Na2O·70 SiO2 composition could not be evaluated due to an apparent chemical interference that occurred during silver staining. This inhibitory effect was attributed to the extensive corrosion that occurred during the protein elution and caused an elevation in the pH of the solution. The remaining glass compositions were sufficiently durable for further study. The HSA adsorption capacity of SLS glass microspheres containing 70 and 80 mol% SiO2 increased as CaO was substituted for Na2O. An abrupt decrease in the HSA adsorption capacity was observed for SLS glasses containing 60 mol% SiO2. A similar trend was observed for the SAS glass microspheres, although the SAS glasses adsorbed less HSA than the SLS glasses containing equivalent molar percentages of SiO2. The initial increase in HSA adsorption capacity for SLS and SAS glasses containing 70 and 80 MOM SiO2 was attributed to the introduction of positive charges into the glass surfaces via Ca2+ and Al3+ cations. The decrease in HSA adsorption capacity for SLS and SAS glasses containing 60 mol% SiO2 may be due to an enhanced affinity between the glasses and HSA, resulting in a "flattened" conformation that limits the total accessible area for adsorption.

  10. Aflatoxin adsorbent capacity of two Mexican aluminosilicates in experimentally contaminated chick diets.

    PubMed

    Márquez Márquez, R N; Tejada de Hernandez, I

    1995-01-01

    To study the aflatoxin-adsorbent capacity of two Mexican aluminosilicates (ALS) identified as Atapulgita (AT) and Füller earth (FE), these ALS were compared with a commercial aluminosilicate, Novasil (NV), at two concentrations (0.05 and 1.0%) added to chick diets with 55% of experimentally contaminated corn (200 micrograms/kg). Eight treatments were studied with two replicates for treatment and four chicks per cage. Results (weight gain, feed efficiency, gross and microscopic pathology) at 3 weeks showed that both Mexican ALS were as efficient as the commercial material in protecting chicks against the aflatoxin toxicity. PMID:7664939

  11. Calculation of the Aluminosilicate Half-Life Formation Time in the 2H Evaporator

    SciTech Connect

    Fondeur, F.F.

    2000-09-21

    The 2H Evaporator contains large quantities of aluminosilicate solids deposited on internal fixtures. The proposed cleaning operations will dissolve the solids in nitric acid. Operations will then neutralize the waste prior to transfer to a waste tank. Combining recent calculations of heat transfer for the 2H Evaporator cleaning operations and laboratory experiments for dissolution of solid samples from the pot, the authors estimated the re-formation rate for aluminosilicates during cooling. The results indicate a half-life formation of 17 hours when evaporator solution cools from 60 degrees C and 9 hours when cooled from 90 degrees C.

  12. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, Sheldon H. D.

    1992-01-01

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases.

  13. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, S.H.D.

    1992-12-22

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases. 6 figs.

  14. Technetium (VII) Co-precipitation with Framework Aluminosilicates

    SciTech Connect

    Harsh, James B.; Dickson, Johnbull Otah; Pierce, Eric M.; Bargar, John

    2015-07-13

    Technetium-99 (99Tc), a long-lived radionuclide, is one of the most widespread contaminants within the Hanford subsurface. At some depths, it is only extractable with strong acids, suggesting incorporation into a solid phase. We hypothesized that Tc may have coprecipitated with feldspathoid aluminosilicates under waste tanks that had leaked caustic solutions into the vadose zone. Our objectives were to determine if Tc could be incorporated into the feldspathoids cancrinite and sodalite and under what conditions coprecipitation could occur. Our hypothesis was that sodalite was more likely to incorporate and retain Tc. Our approach was to use known methods of feldspathoid formation in solutions resembling those in Hanford waste tanks contacting sediments in terms of major ion (Na, NO3, OH, Al(OH)4, and Si(OH)4 concentrations. In some cases, Al and Si were supplied from zeolite. We used perrhenate (ReO4) as a surrogate for pertechnetate (TcO4) to avoid the radioactivity. The major findings of this study were 1) ReO4 could be incorporated into either sodalite or cancrinite but the concentration in the solid was < 1% of the competing ion Cl, NO3, or NO2. 2) The small amount of ReO4 incorporated was not exchangeable with NO3 or NO2. 3) In sodalite, NO3 was highly preferred over ReO4 but significant Re-sodalite was formed when the mole fraction in solution (Re/Re+N) exceeded 0.8. 4) A nonlinear relation between the unit cell parameter and amount of Re incorporated suggested that a separate Re-sodalite phase was formed rather than a solid solution. 5) We determined that sodalite preference for sodalite in the presence of different anions increased with the ionic size of the competing anion: Cl < CO3 < NO3 < SO4 < MnO4 < WO4 and significant incorporation did not occur unless the difference in anion radii was less than 12%. 6) Re(VII) was not significantly reduced to Re(IV) under the conditions of this experiment and Re appeared to be a good surrogate for Tc under oxidizing

  15. Alkali Activated Systems: Understanding the Influence of Curing Conditions and Activator Type/Chemistry on the Mechanical Strength and Chemical Structure of Fly Ash/Slag Systems

    NASA Astrophysics Data System (ADS)

    Chowdhury, Ussala

    The alkali activation of aluminosilicate materials as binder systems derived from industrial byproducts have been extensively studied due to the advantages they offer in terms enhanced material properties, while increasing sustainability by the reuse of industrial waste and byproducts and reducing the adverse impacts of OPC production. Fly ash and ground granulated blast furnace slag are commonly used for their content of soluble silica and aluminate species that can undergo dissolution, polymerization with the alkali, condensation on particle surfaces and solidification. The following topics are the focus of this thesis: (i) the use of microwave assisted thermal processing, in addition to heat-curing as a means of alkali activation and (ii) the relative effects of alkali cations (K or Na) in the activator (powder activators) on the mechanical properties and chemical structure of these systems. Unsuitable curing conditions instigate carbonation, which in turn lowers the pH of the system causing significant reductions in the rate of fly ash activation and mechanical strength development. This study explores the effects of sealing the samples during the curing process, which effectively traps the free water in the system, and allows for increased aluminosilicate activation. The use of microwave-curing in lieu of thermal-curing is also studied in order to reduce energy consumption and for its ability to provide fast volumetric heating. Potassium-based powder activators dry blended into the slag binder system is shown to be effective in obtaining very high compressive strengths under moist curing conditions (greater than 70 MPa), whereas sodium-based powder activation is much weaker (around 25 MPa). Compressive strength decreases when fly ash is introduced into the system. Isothermal calorimetry is used to evaluate the early hydration process, and to understand the reaction kinetics of the alkali powder activated systems. A qualitative evidence of the alkali

  16. Glass transition temperature and conductivity in Li2O and Na2O doped borophosphate glasses

    NASA Astrophysics Data System (ADS)

    Ashwajeet, J. S.; Sankarappa, T.; Ramanna, R.; Sujatha, T.; Awasthi, A. M.

    2015-08-01

    Two alkali doped Borophosphate glasses in the composition, (B2O3)0.2. (P2O5)0.3. (Na2O)(0.5-x). (Li2O)x, where x = 0.05 to 0.50 were prepared by standard melt quenching method at 1200K. Non-crystalline nature was confirmed by XRD studies. Room temperature density was measured by Archimedes principle. DC conductivity in the temperature range from 300K to 575K has been measured. Samples were DSC studied in the temperature range from 423K to 673K and glass transition temperature was determined. Glass transition temperature passed through minima for Li2O con.2centration between 0.25 and 0.30 mole fractions. Activation energy of conduction has been determined by analyzing temperature variation of conductivity determining Arrhenius law. Conductivity passed through minimum and activation passed through maximum for Li2O content from 0.25 to 0.30 mole fractions. Glass transition temperature passed through minimum for the same range of Li2O content. These results revealed mixed alkali effect taking place in these glasses. It is for the first time borophosphate glasses doped with Li2O and Na2O have been studied for density and dc conductivity and, the mixed alkali effect (MAE) has been observed.

  17. Symplectites in garnet megacrysts captured by alkali mafic magma

    NASA Astrophysics Data System (ADS)

    Aseeva, Anna; Vysotskiy, Sergey; Karabtsov, Alexander; Alexandrov, Igor; Chashchin, Alexander

    2014-05-01

    Megacrysts are widespread in Cenozoic alkali-basalts of many volcanic provinces of the world. Garnet megacrysts containing symplectites are the most interesting, as can be used for reconstruction of physical and chemical conditions in liquid basalt at the moment of garnet crystal capture. The collection of garnet megacrysts and garnet-pyroxene aggregates from Shavaryn-Tsaram (Hangaj plateau, Mongolia) and Bartoj (Dzhida basaltic field, Russia) paleovolcanoes has studied. Cenozoic alkali basaltic volcanism of these two spatially separated areas is considered to be related to a uniform process of lithosphere spreading in Baikal and related Central Asian rift systems. The studying of garnet-pyroxene aggregate and fragments of garnet megacrysts from these two paleovolcanoes revealed two mineral associations: primary and secondary. The former includes garnet and clinopyroxene, the letter (symplectite) is presented by products of garnet disintegration (clinopyroxene remain unaltered). At least two paragenesis can be allocated: 1) shpinel - plagioclase-olivine sometimes with gedrite and orthopyroxene; 2) olivine (with glass). Experimental modeling of decomposition process in garnet megacryst has been carried out with the help of 'Selector' softwear at various P-T parameters. Physical and chemical conditions of this paragenesis occurrence have also been estimated by up-to-date geothermometers and geobarometers (T 950-1000 C, P 4-4.5 kbar. Conclusions: 1. Garnet megacrysts are apparently in non-equilibrium with alkali-basalts. They were formed in conditions corresponding to zones of mantle plums at the bottom of crust, in magmatic chambers at constant infiltration of fluid. Subsequently megacrysts were captured by alkali-basalt magma and taken out to the surface. 2. Kelyphitic rims on garnet megacrysts is a result of partial melting of megacrysts on interaction with the hosting alkali basaltic rock. During melting garnet transforms with the formation of Na-K glass and Mg

  18. Durabiliy of two simulated nuclear waste glasses, a frit glass, and tektite in aqueous solutions: Final report, Volume I

    SciTech Connect

    Hagen, D.A.; Altstetter, C.J.; Brown, S.D.

    1988-05-01

    High level nuclear waste is commonly incorporated into glass for disposal. Therefore the long term aqueous durability of the waste glass is important. The leaching behavior of three simulated nuclear waste glasses (AH10, AH165, and Frit 165) and a natural glass (tektite) were examined using nuclear reaction analysis, leachate solution analysis, and microscopy. The three simulated waste glasses developed hydrated layers which increased in thickness by t/sup /1/2//. The hydrated layer in Frit 165 reached a constant thickness of about one micron. Alkali were preferentially removed from the Frit 165 and AH10. The tektite corroded by slow uniform dissolution. 94 refs., 68 figs., 13 tabs.

  19. Alkali-Metal Spin Maser.

    PubMed

    Chalupczak, W; Josephs-Franks, P

    2015-07-17

    Quantum measurement is a combination of a read-out and a perturbation of the quantum system. We explore the nonlinear spin dynamics generated by a linearly polarized probe beam in a continuous measurement of the collective spin state in a thermal alkali-metal atomic sample. We demonstrate that the probe-beam-driven perturbation leads, in the presence of indirect pumping, to complete polarization of the sample and macroscopic coherent spin oscillations. As a consequence of the former we report observation of spectral profiles free from collisional broadening. Nonlinear dynamics is studied through exploring its effect on radio frequency as well as spin noise spectra. PMID:26230788

  20. The BRAG and GM2003 Models for Glass Dissolution

    SciTech Connect

    Aertsens, Marc

    2007-07-01

    The GM2003 model extends the r(t) glass dissolution model with water diffusion through the diffusion layer. Boron and alkali diffusion through the diffusion layer is described by introducing a retention factor K{sub d,i} between boron/alkali and water in the diffusion layer. Introducing a boron/alkali diffusion coefficient, the BRAG model describes boron/alkali diffusion in the diffusion layer as well. It is shown that both models are consistent with each other and an expression is derived for the boron/alkali diffusion coefficient (BRAG) as a function of both parameters of GM2003: the retention factor K{sub d,i} and the water diffusion coefficient D{sub H{sub 2}}{sub O} in the diffusion layer. From dissolution data only, it is possible to fit the value for the boron/alkali diffusion coefficient in the diffusion layer but due to correlations the individual values of both parameters K{sub d,i} and DH{sub 2}O of GM2003 cannot be determined. From theoretical considerations follows that the K{sub d,i} value for boron/alkali should be slightly larger than 0.1 kg/liter. A user friendly code for the BRAG model allows automatic fits of glass dissolution data in water. (authors)

  1. Synthesis and Luminescence Properties of Transparent Nanocrystalline GdF3:Tb Glass-Ceramic Scintillator.

    PubMed

    Lee, Gyuhyon; Savage, Nicholas; Wagner, Brent; Zhang, Yuelan; Jacobs, Benjamin; Menkara, Hisham; Summers, Christopher; Kang, Zhitao

    2014-03-01

    Transparent glass-ceramic containing rare-earth doped halide nanocrystals exhibits enhanced luminescence performance. In this study, a glass-ceramic with Tb doped gadolinium fluoride nanocrystals embedded in an aluminosilicate glass matrix is investigated for X-ray imaging applications. The nanocrystalline glass-ceramic scintillator was prepared by a melt-quench method followed by an anneal. The GdF3:Tb nanocrystals precipitated within the oxide glass matrix during the processing and their luminescence and scintillation properties were investigated. In this nanocomposite scintillator system, the incorporation of high atomic number Gd compound into the glass matrix increases the X-ray stopping power of the glass scintillator, and effective energy transfer between Gd(3+) and Tb(3+) ions in the nanocrystals enhances the scintillation efficiency. PMID:24610960

  2. Synthesis and Luminescence Properties of Transparent Nanocrystalline GdF3:Tb Glass-Ceramic Scintillator

    PubMed Central

    Lee, Gyuhyon; Savage, Nicholas; Wagner, Brent; Zhang, Yuelan; Jacobs, Benjamin; Menkara, Hisham; Summers, Christopher; Kang, Zhitao

    2014-01-01

    Transparent glass-ceramic containing rare-earth doped halide nanocrystals exhibits enhanced luminescence performance. In this study, a glass-ceramic with Tb doped gadolinium fluoride nanocrystals embedded in an aluminosilicate glass matrix is investigated for X-ray imaging applications. The nanocrystalline glass-ceramic scintillator was prepared by a melt-quench method followed by an anneal. The GdF3:Tb nanocrystals precipitated within the oxide glass matrix during the processing and their luminescence and scintillation properties were investigated. In this nanocomposite scintillator system, the incorporation of high atomic number Gd compound into the glass matrix increases the X-ray stopping power of the glass scintillator, and effective energy transfer between Gd3+ and Tb3+ ions in the nanocrystals enhances the scintillation efficiency. PMID:24610960

  3. Glass sealing

    SciTech Connect

    Brow, R.K.; Kovacic, L.; Chambers, R.S.

    1996-04-01

    Hernetic glass sealing technologies developed for weapons component applications can be utilized for the design and manufacture of fuel cells. Design and processing of of a seal are optimized through an integrated approach based on glass composition research, finite element analysis, and sealing process definition. Glass sealing procedures are selected to accommodate the limits imposed by glass composition and predicted calculations.

  4. Space processing of chalcogenide glasses

    NASA Technical Reports Server (NTRS)

    Larsen, D. C.; Ali, M. A.

    1975-01-01

    Chalcogenide glasses are discussed as good infrared transmitters, possessing the strength, corrosion resistance, and scale-up potential necessary for large 10.6-micron windows. The disadvantage of earth-produced chalcogenide glasses is shown to be an infrared absorption coefficient which is unacceptably high relative to alkali halides. This coefficient is traced to optical nonhomogeneities resulting from environmental and container contamination. Space processing is considered as a means of improving the infrared transmission quality of chalcogenides and of eliminating the following problems: optical inhomogeneities caused by thermal currents and density fluctuation in the l-g earth environment; contamination from the earth-melting crucible by oxygen and other elements deleterious to infrared transmission; and, heterogeneous nucleation at the earth-melting crucible-glass interface.

  5. One-pot surfactant assisted synthesis of aluminosilicate macrochannels with tunable micro- or mesoporous wall structure.

    PubMed

    Léonard, Alexandre; Blin, Jean-Luc; Su, Bao-Lian

    2003-10-21

    A one-step surfactant assisted synthesis pathway was developed leading to novel hierarchical macro-meso- (or micro-)porous aluminosilicates made of an assembly of macrochannels with openings between 0.5 and 2.0 microm and wormhole-like amorphous walls with tunable pore sizes. PMID:14594284

  6. EFFECT OF IMPURITIES ASSOCIATED WITH ALUMINOSILICATES ON ARSENIC SORPTION AND OXIDATION

    EPA Science Inventory

    Arsenite, As(III), and arsenate, As(V), are of increasing environmental concern. Risk assessment and risk management of arsenic contaminated sites requires a better understanding of arsenic-mineral interactions. Aluminosilicate minerals, such as feldspars and clays, are the mos...

  7. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, S.; Boehm, L.; Volin, K.J.; Delbecq, C.J.

    1982-05-06

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS/sub 2/, B/sub 2/S/sub 2/ and SiS/sub 2/ in mixture with a glass modifier such as Na/sub 2/S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1 - X) Na/sub 2/O:XB/sub 2/S/sub 3/ is disclosed.

  8. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, S.; Delbecq, C.J.; Volin, K.J.; Boehm, L.

    1984-02-21

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS[sub 2], B[sub 2]S[sub 3] and SiS[sub 2] in mixture with a glass modifier such as Na[sub 2]S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na[sub 2]O:XB[sub 2]S[sub 3] is disclosed. 4 figs.

  9. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, Sherman; Boehm, Leah; Volin, Kenneth J.; Delbacq, Charles J.

    1985-01-01

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS.sub.2, B.sub.2 S.sub.3 and SiS.sub.2 in mixture with a glass modifier such as Na.sub.2 S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na.sub.2 O:XB.sub.2 S.sub.3 is disclosed.

  10. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, Sherman; Delbecq, Charles J.; Volin, Kenneth J.; Boehm, Leah

    1984-01-01

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS.sub.2, B.sub.2 S.sub.3 and SiS.sub.2 in mixture with a glass modifier such as Na.sub.2 S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na.sub.2 O:XB.sub.2 S.sub.3 is disclosed.

  11. Water Content of Lunar Alkali Fedlspar

    NASA Technical Reports Server (NTRS)

    Mills, R. D.; Simon, J. I.; Wang, J.; Alexander, C. M. O'D.; Hauri, E. H.

    2016-01-01

    Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of < 1 ppm in urKREEP. Using these data, predict that the bulk water content of the magma ocean would have <10 ppm. In contrast, estimate water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was

  12. Glass Ceramic Formulation Data Package

    SciTech Connect

    Crum, Jarrod V.; Rodriguez, Carmen P.; McCloy, John S.; Vienna, John D.; Chung, Chul-Woo

    2012-06-17

    A glass ceramic waste form is being developed for treatment of secondary waste streams generated by aqueous reprocessing of commercial used nuclear fuel (Crum et al. 2012b). The waste stream contains a mixture of transition metals, alkali, alkaline earths, and lanthanides, several of which exceed the solubility limits of a single phase borosilicate glass (Crum et al. 2009; Caurant et al. 2007). A multi-phase glass ceramic waste form allows incorporation of insoluble components of the waste by designed crystallization into durable heat tolerant phases. The glass ceramic formulation and processing targets the formation of the following three stable crystalline phases: (1) powellite (XMoO4) where X can be (Ca, Sr, Ba, and/or Ln), (2) oxyapatite Yx,Z(10-x)Si6O26 where Y is alkaline earth, Z is Ln, and (3) lanthanide borosilicate (Ln5BSi2O13). These three phases incorporate the waste components that are above the solubility limit of a single-phase borosilicate glass. The glass ceramic is designed to be a single phase melt, just like a borosilicate glass, and then crystallize upon slow cooling to form the targeted phases. The slow cooling schedule is based on the centerline cooling profile of a 2 foot diameter canister such as the Hanford High-Level Waste canister. Up to this point, crucible testing has been used for glass ceramic development, with cold crucible induction melter (CCIM) targeted as the ultimate processing technology for the waste form. Idaho National Laboratory (INL) will conduct a scaled CCIM test in FY2012 with a glass ceramic to demonstrate the processing behavior. This Data Package documents the laboratory studies of the glass ceramic composition to support the CCIM test. Pacific Northwest National Laboratory (PNNL) measured melt viscosity, electrical conductivity, and crystallization behavior upon cooling to identify a processing window (temperature range) for melter operation and cooling profiles necessary to crystallize the targeted phases in the

  13. Effect of host glass matrix on structural and optical behavior of glass-ceramic nanocomposite scintillators

    NASA Astrophysics Data System (ADS)

    Brooke Barta, M.; Nadler, Jason H.; Kang, Zhitao; Wagner, Brent K.; Rosson, Robert; Kahn, Bernd

    2013-12-01

    Composite scintillator systems have received increased attention in recent years due to their promise for merging the radioisotope discrimination capabilities of single crystal scintillators with the high throughput scanning capabilities of portal monitors. However, producing the high light yield required for good energy resolution has proven challenging as scintillation photons are often scattered by variations in refractive index and agglomerated scintillator crystals within the composite. This investigation sought to mitigate these common problems by using glass-ceramic nanocomposite materials systems in which nanoscale scintillating crystallites are precipitated in a controlled manner from a transparent glass matrix. Precipitating crystallites in situ precludes nanoparticle agglomeration, and limiting crystallite size to 50 nm or less mitigates the effect of refractive index mismatch between the crystals and host glass. Cerium-doped gadolinium bromide (GdBr3(Ce)) scintillating crystals were incorporated into sodium-aluminosilicate (NAS) and alumino-borosilicate (ABS) host glass matrices, and the resulting glass-ceramic structures and luminescence behavior were characterized. The as-cast glass from the ABS system displayed a highly ordered microstructure that produced the highest luminescence intensity (light yield) of the samples studied. However, heat treating to form the glass-ceramic precipitated rare-earth oxide crystallites rather than rare-earth halides. This degraded light yield relative to the unaged sample.

  14. Process for the disposal of alkali metals

    DOEpatents

    Lewis, Leroy C.

    1977-01-01

    Large quantities of alkali metals may be safely reacted for ultimate disposal by contact with a hot concentrated caustic solution. The alkali metals react with water in the caustic solution in a controlled reaction while steam dilutes the hydrogen formed by the reaction to a safe level.

  15. The alkali metals: 200 years of surprises.

    PubMed

    Dye, James L

    2015-03-13

    Alkali metal compounds have been known since antiquity. In 1807, Sir Humphry Davy surprised everyone by electrolytically preparing (and naming) potassium and sodium metals. In 1808, he noted their interaction with ammonia, which, 100 years later, was attributed to solvated electrons. After 1960, pulse radiolysis of nearly any solvent produced solvated electrons, which became one of the most studied species in chemistry. In 1968, alkali metal solutions in amines and ethers were shown to contain alkali metal anions in addition to solvated electrons. The advent of crown ethers and cryptands as complexants for alkali cations greatly enhanced alkali metal solubilities. This permitted us to prepare a crystalline salt of Na(-) in 1974, followed by 30 other alkalides with Na(-), K(-), Rb(-) and Cs(-) anions. This firmly established the -1 oxidation state of alkali metals. The synthesis of alkalides led to the crystallization of electrides, with trapped electrons as the anions. Electrides have a variety of electronic and magnetic properties, depending on the geometries and connectivities of the trapping sites. In 2009, the final surprise was the experimental demonstration that alkali metals under high pressure lose their metallic character as the electrons are localized in voids between the alkali cations to become high-pressure electrides! PMID:25666067

  16. Borosilicate glass alteration driven by magnesium carbonates

    NASA Astrophysics Data System (ADS)

    Debure, M.; Frugier, P.; De Windt, L.; Gin, S.

    2012-01-01

    The alteration of simplified synthetic glass, representative of the French reference nuclear glass R7T7, in presence of hydromagnesite has been experimentally investigated and modeled. Magnesium in solution is known to potentially enhance glass alteration; nuclear glass clayed host rocks contain magnesium and can dissolve to maintain the concentration of magnesium in solution. For modeling purposes, it was suitable to study a simple system. Hydromagnesite was therefore chosen as a simple model mineral in order to check the influence of an Mg-rich mineral on glass alteration. Since the models use thermodynamic and kinetic parameters measured in pure water and pH-buffered solutions, changing the solution composition or adding minerals is a key step towards the validation of the modeling assumptions before using the model for predictive purposes. Experiments revealed that glass alteration is enhanced in presence of hydromagnesite. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC reactive transport code. Modeling proved useful both for explaining the mechanisms involved and quantifying the impact on glass alteration: Mg coming from hydromagnesite dissolution reacts with Si provided by the glass in order to form magnesium silicates. This reaction decreases the pH down to neutral conditions where magnesium silicates are more soluble than at the natural alkali pH imposed by glass or hydromagnesite dissolution. The driving force of the magnesium silicate precipitation is eventually the interdiffusion of alkali within the altered amorphous glass layer as this mechanism consumes protons. The model's ability to describe the concentrations of elements in solution and formed solids whatever the glass/hydromagnesite ratio strongly supports the basic modeling hypothesis.

  17. Determination of the Structure of Vitrified Hydroceramic/CBC Waste Form Glasses Manufactured from DOE Reprocessing Waste

    SciTech Connect

    Scheetz, B.E.; White, W. B.; Chesleigh, M.; Portanova, A.; Olanrewaju, J.

    2005-05-31

    The selection of a glass-making option for the solidification of nuclear waste has dominated DOE waste form programs since the early 1980's. Both West Valley and Savannah River are routinely manufacturing glass logs from the high level waste inventory in tank sludges. However, for some wastes, direct conversion to glass is clearly not the optimum strategy for immobilization. INEEL, for example, has approximately 4400 m{sup 3} of calcined high level waste with an activity that produces approximately 45 watts/m{sup 3}, a rather low concentration of radioactive constituents. For these wastes, there is value in seeking alternatives to glass. An alternative approach has been developed and the efficacy of the process demonstrated that offers a significant savings in both human health and safety exposures and also a lower cost relative to the vitrification option. The alternative approach utilizes the intrinsic chemical reactivity of the highly alkaline waste with the addition of aluminosilicate admixtures in the appropriate proportions to form zeolites. The process is one in which a chemically bonded ceramic is produced. The driving force for reaction is derived from the chemical system itself at very modest temperatures and yet forms predominantly crystalline phases. Because the chemically bonded ceramic requires an aqueous medium to serve as a vehicle for the chemical reaction, the proposed zeolite-containing waste form can more adequately be described as a hydroceramic. The hydrated crystalline materials are then subject to hot isostatic pressing (HIP) which partially melts the material to form a glass ceramic. The scientific advantages of the hydroceramic/CBC approach are: (1) Low temperature processing; (2) High waste loading and thus only modest volumetric bulking from the addition of admixtures; (3) Ability to immobilize sodium; (4) Ability to handle low levels of nitrate (2-3% NO{sub 3}{sup -}); (5) The flexibility of a vitrifiable waste; and (6) A process that

  18. Purification of sulfide-alkali effluent with the aid of ionizing radiation. [Gamma radiation

    SciTech Connect

    Petryaev, E.P.; Gerasimovich, O.A.; Kovalevskaya, A.M.; Plyuto, I.Ch.; Shlyk, V.G.

    1984-03-01

    The treatment of sulfide-alkali effluent under the effect of ionizing radiation was investigated. The source was an LMB-..gamma..-1M ..gamma..-apparatus with /sup 137/Cs source. The dose rate was 52 rad/s. Irradiation was done in glass ampules and in vessels allowing bubbling with air and irradiation to be carried out at the same time. 7 references, 1 figure, 1 table.

  19. Chemical durability of simulated nuclear glasses containing water

    SciTech Connect

    Li, H.; Tomozawa, M.

    1995-04-01

    The chemical durability of simulated nuclear waste glasses having different water contents was studied. Results from the product consistency test (PCT) showed that glass dissolution increased with water content in the glass. This trend was not observed during MCC-1 testing. This difference was attributed to the differences in reactions between glass and water. In the PCT, the glass network dissolution controlled the elemental releases, and water in the glass accelerated the reaction rate. On the other hand, alkali ion exchange with hydronium played an important role in the MCC-1. For the latter, the amount of water introduced into a leached layer from ion-exchange was found to be much greater than that of initially incorporated water in the glass. Hence, the initial water content has no effect on glass dissolution as measured by the MCC-1 test.

  20. Alkali burns from wet cement.

    PubMed Central

    Peters, W. J.

    1984-01-01

    When water is added to the dry materials of Portland cement calcium hydroxide is formed; the wet cement is caustic (with a pH as high as 12.9) and can produce third-degree alkali burns after 2 hours of contact. Unlike professional cement workers, amateurs are usually not aware of any danger and may stand or kneel in the cement for long periods. As illustrated in a case report, general physicians may recognize neither the seriousness of the injury in its early stages nor the significance of a history of prolonged contact with wet cement. All people working with cement should be warned about its dangers and advised to immediately wash and dry the skin if contact does occur. Images Fig. 1 PMID:6561052

  1. Crystallization kinetics of BaO-Al2O3-SiO2 glasses

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Hyatt, Mark J.

    1988-01-01

    Barium aluminosilicate glasses are being investigated as matrix materials in high-temperature ceramic composites for structural applications. Kinetics of crystallization of two refractory glass compositions in the barium aluminosilicate system were studied by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). From variable heating rate DTA, the crystallization activation energies for glass compositions (wt percent) 10BaO-38Al2O3-51SiO2-1MoO3 (glass A) and 39BaO-25Al2O3-35SiO2-1MoO3 (glass B) were determined to be 553 and 558 kJ/mol, respectively. On thermal treatment, the crystalline phases in glasses A and B were identified as mullite (3Al2O3-2SiO2) and hexacelsian (BaO-Al2O3-2SiO2), respectively. Hexacelsian is a high-temperature polymorph which is metastable below 1590 C. It undergoes structural transformation into the orthorhombic form at approximately 300 C accompanied by a large volume change which is undesirable for structural applications. A process needs to be developed where stable monoclinic celsian, rather than hexacelsian, precipitates out as the crystal phase in glass B.

  2. Crystallization kinetics of BaO-Al2O3-SiO2 glasses

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Hyatt, Mark J.

    1989-01-01

    Barium aluminosilicate glasses are being investigated as matrix materials in high-temperature ceramic composites for structural applications. Kinetics of crystallization of two refractory glass compositions in the barium aluminosilicate system were studied by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). From variable heating rate DTA, the crystallization activation energies for glass compositions (wt percent) 10BaO-38Al2O3-51SiO2-1MoO3 (glass A) and 39BaO-25Al2O3-35SiO2-1MoO3 (glass B) were determined to be 553 and 558 kJ/mol, respectively. On thermal treatment, the crystalline phases in glasses A and B were identified as mullite (3Al2O3-2SiO2) and hexacelsian (BaO-Al2O3-2SiO2), respectively. Hexacelsian is a high-temperature polymorph which is metastable below 1590 C. It undergoes structural transformation into the orthorhombic form at approximately 300 C accompanied by a large volume change which is undesirable for structural applications. A process needs to be developed where stable monoclinic celsian, rather than hexacelsian, precipitates out as the crystal phase in glass B.

  3. Alkali Silicate Vehicle Forms Durable, Fireproof Paint

    NASA Technical Reports Server (NTRS)

    Schutt, John B.; Seindenberg, Benjamin

    1964-01-01

    The problem: To develop a paint for use on satellites or space vehicles that exhibits high resistance to cracking, peeling, or flaking when subjected to a wide range of temperatures. Organic coatings will partially meet the required specifications but have the inherent disadvantage of combustibility. Alkali-silicate binders, used in some industrial coatings and adhesives, show evidence of forming a fireproof paint, but the problem of high surface-tension, a characteristic of alkali silicates, has not been resolved. The solution: Use of a suitable non-ionic wetting agent combined with a paint incorporating alkali silicate as the binder.

  4. Diode pumped alkali vapor fiber laser

    DOEpatents

    Payne, Stephen A.; Beach, Raymond J.; Dawson, Jay W.; Krupke, William F.

    2007-10-23

    A method and apparatus is provided for producing near-diffraction-limited laser light, or amplifying near-diffraction-limited light, in diode pumped alkali vapor photonic-band-gap fiber lasers or amplifiers. Laser light is both substantially generated and propagated in an alkali gas instead of a solid, allowing the nonlinear and damage limitations of conventional solid core fibers to be circumvented. Alkali vapor is introduced into the center hole of a photonic-band-gap fiber, which can then be pumped with light from a pump laser and operated as an oscillator with a seed beam, or can be configured as an amplifier.

  5. Diode pumped alkali vapor fiber laser

    DOEpatents

    Payne, Stephen A.; Beach, Raymond J.; Dawson, Jay W.; Krupke, William F.

    2006-07-26

    A method and apparatus is provided for producing near-diffraction-limited laser light, or amplifying near-diffraction-limited light, in diode pumped alkali vapor photonic-band-gap fiber lasers or amplifiers. Laser light is both substantially generated and propagated in an alkali gas instead of a solid, allowing the nonlinear and damage limitations of conventional solid core fibers to be circumvented. Alkali vapor is introduced into the center hole of a photonic-band-gap fiber, which can then be pumped with light from a pump laser and operated as an oscillator with a seed beam, or can be configured as an amplifier.

  6. Advancements in flowing diode pumped alkali lasers

    NASA Astrophysics Data System (ADS)

    Pitz, Greg A.; Stalnaker, Donald M.; Guild, Eric M.; Oliker, Benjamin Q.; Moran, Paul J.; Townsend, Steven W.; Hostutler, David A.

    2016-03-01

    Multiple variants of the Diode Pumped Alkali Laser (DPAL) have recently been demonstrated at the Air Force Research Laboratory (AFRL). Highlights of this ongoing research effort include: a) a 571W rubidium (Rb) based Master Oscillator Power Amplifier (MOPA) with a gain (2α) of 0.48 cm-1, b) a rubidium-cesium (Cs) Multi-Alkali Multi-Line (MAML) laser that simultaneously lases at both 795 nm and 895 nm, and c) a 1.5 kW resonantly pumped potassium (K) DPAL with a slope efficiency of 50%. The common factor among these experiments is the use of a flowing alkali test bed.

  7. The Impact of the Source of Alkali on Sludge Batch 3 Melt Rate (U)

    SciTech Connect

    Smith, M

    2005-04-01

    Previous Savannah River National Laboratory (SRNL) melt rate tests in support of the Defense Waste Processing Facility (DWPF) have indicated that improvements in melt rate can be achieved through an increase in the total alkali of the melter feed. Higher alkali can be attained by the use of an ''underwashed'' sludge, a high alkali frit, or a combination of the two. Although the general trend between melt rate and total alkali (in particular Na{sub 2}O content) has been demonstrated, the question of ''does the source of alkali (SOA) matter?'' still exists. Therefore the purpose of this set of tests was to determine if the source of alkali (frit versus sludge) can impact melt rate. The general test concept was to transition from a Na{sub 2}O-rich frit to a Na{sub 2}O-deficient frit while compensating the Na{sub 2}O content in the sludge to maintain the same overall Na{sub 2}O content in the melter feed. Specifically, the strategy was to vary the amount of alkali in frits and in the sludge batch 3 (SB3) sludge simulant (midpoint or baseline feed was SB3/Frit 418 at 35% waste loading) so that the resultant feeds had the same final glass composition when vitrified. A set of SOA feeds using frits ranging from 0 to 16 weight % Na{sub 2}O (in 4% increments) was first tested in the Melt Rate Furnace (MRF) to determine if indeed there was an impact. The dry-fed MRF tests indicated that if the alkali is too depleted from either the sludge (16% Na{sub 2}O feed) or the frit (the 0% Na{sub 2}O feed), then melt rate was negatively impacted when compared to the baseline SB3/Frit 418 feed currently being processed at DWPF. The MRF melt rates for the 4 and 12% SOA feeds were similar to the baseline SB3/Frit 418 (8% SOA) feed. Due to this finding, a smaller subset of SOA feeds that could be processed in the DWPF (4 and 12% SOA feeds) was then tested in the Slurry-fed Melt Rate Furnace (SMRF). The results from a previous SMRF test with SB3/Frit 418 (Smith et al. 2004) were used as the

  8. Chalcogenide glasses

    SciTech Connect

    Taylor, P.C.

    1987-08-15

    Although there are some significant exceptions, most important glass-forming systems contain elements from the sixth, or chalcogenide, column of the periodic table (oxygen, sulfur, selenium, or tellurium). The glasses that contain oxygen are typically insulators, while those that contain the heavier chalcogen elements are usually semiconductors. Even though oxygen is technically a chalcogen element, the term chalcogenide glass is commonly used to denote those largely covalent, semiconducting glasses contain sulfur, selenium, or tellurium as one of the constituents.

  9. Influence of Boehmite Precursor on Aluminosilicate Aerogel Pore Structure, Phase Stability and Resistance to Densification at High Temperatures

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Guo, Haiquan; Newlin, Katy N.

    2011-01-01

    Aluminosilicate aerogels are of interest as constituents of thermal insulation systems for use at temperatures higher than those attainable with silica aerogels. It is anticipated that their effectiveness as thermal insulators will be influenced by their morphology, pore size distribution, physical and skeletal densities. The present study focuses on the synthesis of aluminosilicate aerogel from a variety of Boehmite (precursors as the Al source, and tetraethylorthosilicate (TEOS) as the Si source, and the influence of starting powder on pore structure and thermal stability.

  10. Nuclear Magnetic Resonance Studies of Aluminosilicate Gels Prepared in High-Alkaline and Salt-Concentrated Solutions

    SciTech Connect

    Wang, Li Q.; Mattigod, Shas V.; Parker, Kent E.; Hobbs, David T.; McCready, David E.

    2005-01-11

    We have examined the formation of aluminosilicate in high alkaline and salt concentrated solutions characteristic of nuclear tank wastes. Information on the mechanism and kinetics of the phase formation under hydrothermal conditions was obtained by characterization the structures of gel phases as a function of time and composition using multinuclear NMR techniques in combination with x-ray diffraction. This work offers a new insight into the aluminum and aluminosilicate chemistry in simulated nuclear tank wastes.

  11. Alkali metal for ultraviolet band-pass filter

    NASA Technical Reports Server (NTRS)

    Mardesich, Nick (Inventor); Fraschetti, George A. (Inventor); Mccann, Timothy A. (Inventor); Mayall, Sherwood D. (Inventor); Dunn, Donald E. (Inventor); Trauger, John T. (Inventor)

    1993-01-01

    An alkali metal filter having a layer of metallic bismuth deposited onto the alkali metal is provided. The metallic bismuth acts to stabilize the surface of the alkali metal to prevent substantial surface migration from occurring on the alkali metal, which may degrade optical characteristics of the filter. To this end, a layer of metallic bismuth is deposited by vapor deposition over the alkali metal to a depth of approximately 5 to 10 A. A complete alkali metal filter is described along with a method for fabricating the alkali metal filter.

  12. Alkali Metal Handling Practices at NASA MSFC

    NASA Technical Reports Server (NTRS)

    Salvail, Patrick G.; Carter, Robert R.

    2002-01-01

    NASA Marshall Space Flight Center (MSFC) is NASA s principle propulsion development center. Research and development is coordinated and carried out on not only the existing transportation systems, but also those that may be flown in the near future. Heat pipe cooled fast fission cores are among several concepts being considered for the Nuclear Systems Initiative. Marshall Space Flight Center has developed a capability to handle high-purity alkali metals for use in heat pipes or liquid metal heat transfer loops. This capability is a low budget prototype of an alkali metal handling system that would allow the production of flight qualified heat pipe modules or alkali metal loops. The processing approach used to introduce pure alkali metal into heat pipe modules and other test articles are described in this paper.

  13. Alkali-metal intercalation in carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Béguin, F.; Duclaux, L.; Méténier, K.; Frackowiak, E.; Salvetat, J. P.; Conard, J.; Bonnamy, S.; Lauginie, P.

    1999-09-01

    We report on successful intercalation of multiwall (MWNT) and single wall (SWNT) carbon nanotubes with alkali metals by electrochemical and vapor phase reactions. A LiC10 compound was produced by full electrochemical reduction of MWNT. KC8 and CsC8-MWNT first stage derivatives were synthesized in conditions of alkali vapor saturation. Their identity periods and the 2×2 R 0° alkali superlattice are comparable to their parent graphite compounds. The dysonian shape of KC8 EPR line and the temperature-independent Pauli susceptibility are both characteristic of a metallic behavior, which was confirmed by 13C NMR anisotropic shifts. Exposure of SWNT bundles to alkali vapor led to an increase of the pristine triangular lattice from 1.67 nm to 1.85 nm and 1.87 nm for potassium and rubidium, respectively.

  14. Formation processes and main properties of hollow aluminosilicate microspheres in fly ash from thermal power stations

    SciTech Connect

    V.S. Drozhzhin; M.Ya. Shpirt; L.D. Danilin; M.D. Kuvaev; I.V. Pikulin; G.A. Potemkin; S.A. Redyushev

    2008-04-15

    The main parameters of aluminosilicate microspheres formed at thermal power stations in Russia were studied. These parameters are responsible for the prospective industrial application of these microspheres. A comparative analysis of the properties of mineral coal components, the conditions of coal combustion, and the effects of chemical and phase-mineralogical compositions of mineral impurities in coals from almost all of the main coal deposits on the formation of microspheres was performed. The effects of thermal treatment conditions on gas evolution processes in mineral particles and on the fraction of aluminosilicate microspheres in fly ash were considered. It was found that the yield of microspheres was higher in pulverized coal combustion in furnaces with liquid slag removal, all other factors being equal. The regularities of microsphere formation were analyzed, and the mechanism of microsphere formation in fly ash during the combustion of solid fuels was considered.

  15. Structural Aspects of Several Oxide Glasses as Elucidated by Multinuclear NMR.

    NASA Astrophysics Data System (ADS)

    Zhong, Jianhui

    1988-03-01

    NMR is sensitive to many interactions that the nucleus experiences with its environment. Included among these interactions are two that were heavily exploited in this thesis. They are the electric quadrupole interaction and the chemical shift interaction. These interactions yield structural information on short-range order and atom coordinations, which are very valuable and important to the understanding of properties and microstructures of glasses. Both the static or MASS NMR at high field and low field CW NMR were utilized to obtain information concerning the coordinations and local environments of several oxide glasses. For some systems, other spectroscopic methods (thermal analysis, X-ray and IR spectroscopies) were also used to assist NMR studies. In Chapter I relevant NMR theory and detection techniques used for this work are introduced. In Chapters 2-4, some structural aspects of alkali borate, borosilicate or alkali boroaluminate glasses are studied. In particular, boron coordinations in these glasses are carefully reinvestigated. The relationship between the change in boron coordinations and the changes in macroscopic characteristics of the glasses (such as electric conductivity and the mixed alkali effects) are studied. In mixed alkali glasses, the postulated alkali -pairing model provides a reasonable explanation for the structural changes. Chapter 5 is dedicated to the ^{71}Ga and ^{69 }Ga NMR studies of alkali gallate glasses. The glassforming range is explored and the gallium atom coordinations are studied. A structural model for the glass systems is suggested based on the distribution of galliums of different coordinations and structural parameters (quadrupole coupling constants, asymmetry parameters, and isotropic chemical shifts, etc.). A study of ^{31} P spectra in lead-iron-phosphate nuclear waste glasses is presented in Chapter 6. By subjecting the samples to various magnetic field strengths and different temperatures, information on the local

  16. Alkali basalts and enclosed ultramafic xenoliths near Ushuaia, Tierra Del Fuego, Argentina.

    PubMed

    Acevedo, Rogelio Daniel

    2016-01-01

    At the southernmost part of Tierra del Fuego a few outcrops and erratic boulders of alkali basaltic rocks with ultramafic enclaves have been studied. Alkali basalt plugs or pipes hitherto identified are scarce, and host rocks are constituted by slates that belong to Mesozoic deposition. The petrography, texture and composition of the basalt and xenoliths were investigated by petrographic microscope and electron microprobe analysis. Xenocrysts of amphibole and alkali feldspar, phenocrysts of nepheline, olivine, spinel, phlogopite and Fe-Ti minerals (10 %) and a diversity of xenoliths, mainly lherzolitic, pyroxenite and wehrlitic nodules (15 %), but also from metamorphic rocks provenance, are contained in the basalt groundmass (75 %). This finer-grained material is made up of laths or needles of plagioclase, pyroxene, opaque minerals, apatite and glass, with intersertal, hyalopilitic and pilotaxitic. Locally, rock has an even granoblastic texture. Former amygdules are filled by analcite, zeolites, sodalite and calcite. The normative classification, based on nepheline content, conclude that this rock is an alkali basalt. The chemical classification, considering immobile elements as Zr/TiO2 versus Nb/Y indicate an alkali basalt too and plots over the TAS diagram fall in the foidite (Na-rich or nephelinite) and basanite fields. The REE patterns are fractionated (La/Yb primitive mantle normalized is approximately 30). The K-Ar isotopic technique on individual macrocrysts gave ages of 146 ± 5 Ma (amphibole) and 127 ± 4 Ma (alkali feldspar); and K-Ar whole rock datum reported 8.3 ± 0.3 Ma. Nevertheless, fertile samples show geochemical features typical of deep derived material thus, based on the position in the actual tectonic setting, indicate that the basalt is older than its isotopic age. PMID:27610313

  17. Alkali metal intercalates of molybdenum disulfide.

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.

    1973-01-01

    Study of some of the physicochemical properties of compounds obtained by subjecting natural molybdenite and single crystals of molybdenum disulfide grown by chemical vapor transport to intercalation with the alkali group of metals (Li, Na, K, Rb, and Cs) by means of the liquid ammonia technique. Reported data and results include: (1) the intercalation of the entire alkali metal group, (2) stoichiometries and X-ray data on all of the compounds, and (3) superconductivity data for all the intercalation compounds.

  18. Superconductivity in alkali-doped C60

    NASA Astrophysics Data System (ADS)

    Ramirez, Arthur P.

    2015-07-01

    Superconductivity in alkali-doped C60 (A3C60, A = an alkali atom) is well described by an s-wave state produced by phonon mediated pairing. Moderate coupling of electrons to high-frequency shape-changing intra-molecular vibrational modes produces transition temperatures (Tc) up to 33 K in single-phase material. The good understanding of pairing in A3C60 offers a paradigm for the development of new superconducting materials.

  19. Desulfurizing Coal With an Alkali Treatment

    NASA Technical Reports Server (NTRS)

    Ravindram, M.; Kalvinskas, J. J.

    1987-01-01

    Experimental coal-desulfurization process uses alkalies and steam in fluidized-bed reactor. With highly volatile, high-sulfur bituminous coal, process removed 98 percent of pyritic sulfur and 47 percent of organic sulfur. Used in coal liquefaction and in production of clean solid fuels and synthetic liquid fuels. Nitrogen or steam flows through bed of coal in reactor. Alkalies react with sulfur, removing it from coal. Nitrogen flow fluidizes bed while heating or cooling; steam is fluidizing medium during reaction.

  20. Rb-Sr Isotopic Systematics of Alkali-Rich Fragments in the Yamato-74442 LL-Chondritic Breccia

    NASA Technical Reports Server (NTRS)

    Yokoyama, T.; Misawa, K.; Okano, O.; Shih, C.-Y.; Nyquist, L. E.; Simo, J. I.; Tappa, M. J.; Yoneda, S.

    2012-01-01

    Alkali-rich igneous fragments were identified in the brecciated LL-chondrites, Kr henberg (LL5)], Bhola (LL3-6) and Yamato (Y)-74442 (LL4), and show characteristic fractionation patterns of alkaline elements. The K-Rb-Cs-rich fragments in Kr henberg, Bhola, and Y-74442 are very similar in mineralogy and petrography (olivine + pyroxene + glass), suggesting that they could have come from related precursor materials. We have undertaken Rb-Sr isotopic studies on alkali-rich fragments in Y-74442 to precisely determine their crystallization ages and the isotopic signatures of their precursor material(s).

  1. High-Aluminum-Affinity Silica Is a Nanoparticle That Seeds Secondary Aluminosilicate Formation

    PubMed Central

    Jugdaohsingh, Ravin; Brown, Andy; Dietzel, Martin; Powell, Jonathan J.

    2013-01-01

    Despite the importance and abundance of aluminosilicates throughout our natural surroundings, their formation at neutral pH is, surprisingly, a matter of considerable debate. From our experiments in dilute aluminum and silica containing solutions (pH ~ 7) we previously identified a silica polymer with an extraordinarily high affinity for aluminium ions (high-aluminum-affinity silica polymer, HSP). Here, further characterization shows that HSP is a colloid of approximately 2.4 nm in diameter with a mean specific surface area of about 1,000 m2 g-1 and it competes effectively with transferrin for Al(III) binding. Aluminum binding to HSP strongly inhibited its decomposition whilst the reaction rate constant for the formation of the β-silicomolybdic acid complex indicated a diameter between 3.6 and 4.1 nm for these aluminum-containing nanoparticles. Similarly, high resolution microscopic analysis of the air dried aluminum-containing silica colloid solution revealed 3.9 ± 1.3 nm sized crystalline Al-rich silica nanoparticles (ASP) with an estimated Al:Si ratio of between 2 and 3 which is close to the range of secondary aluminosilicates such as imogolite. Thus the high-aluminum-affinity silica polymer is a nanoparticle that seeds early aluminosilicate formation through highly competitive binding of Al(III) ions. In niche environments, especially in vivo, this may serve as an alternative mechanism to polyhydroxy Al(III) species binding monomeric silica to form early phase, non-toxic aluminosilicates. PMID:24349573

  2. Alkali metal crystalline polymer electrolytes.

    PubMed

    Zhang, Chuhong; Gamble, Stephen; Ainsworth, David; Slawin, Alexandra M Z; Andreev, Yuri G; Bruce, Peter G

    2009-07-01

    Polymer electrolytes have been studied extensively because uniquely they combine ionic conductivity with solid yet flexible mechanical properties, rendering them important for all-solid-state devices including batteries, electrochromic displays and smart windows. For some 30 years, ionic conductivity in polymers was considered to occur only in the amorphous state above Tg. Crystalline polymers were believed to be insulators. This changed with the discovery of Li(+) conductivity in crystalline poly(ethylene oxide)(6):LiAsF(6). However, new crystalline polymer electrolytes have proved elusive, questioning whether the 6:1 complex has particular structural features making it a unique exception to the rule that only amorphous polymers conduct. Here, we demonstrate that ionic conductivity in crystalline polymers is not unique to the 6:1 complex by reporting several new crystalline polymer electrolytes containing different alkali metal salts (Na(+), K(+) and Rb(+)), including the best conductor poly(ethylene oxide)(8):NaAsF(6) discovered so far, with a conductivity 1.5 orders of magnitude higher than poly(ethylene oxide)(6):LiAsF(6). These are the first crystalline polymer electrolytes with a different composition and structures to that of the 6:1 Li(+) complex. PMID:19543313

  3. The effects of intrapleural injections of alumina and aluminosilicate (ceramic) fibres.

    PubMed Central

    Pigott, G. H.; Ishmael, J.

    1992-01-01

    Groups of rats, 24 male and 24 female, approximately 8 weeks old, were dosed by a single intrapleural injection with a saline suspension of refractory alumina fibres (Saffil fibres ICI plc) either as manufactured or after extensive thermal ageing; or one of two aluminosilicate ('ceramic') fibres with different diameter distributions. Similar groups were dosed with a suspension of UICC chrysotile A asbestos or saline solution to serve as positive and negative controls respectively. Rats were maintained to 85% mortality and all decedents and terminal sacrifices were closely examined for the presence of mesothelioma. Malignant mesothelioma was diagnosed in ten rats, seven dosed with asbestos and three dosed with aluminosilicate fibre B. No mesothelioma was detected in any rat dosed with Saffil fibres or aluminosilicate fibre A or in negative controls. The results support the predicted inert nature of Saffil alumina fibres and provide further evidence for the importance of fibre dimension in the induction of mesothelioma. The implication of the results for inhalation exposures is discussed. PMID:1571274

  4. STUDIES OF POTENTIAL INHIBITORS OF SODIUM ALUMINOSILICATE SCALES IN HIGH-LEVEL WASTE EVAPORATION

    SciTech Connect

    Wilmarth, B; Lawrence Oji, L; Terri Fellinger, T; David Hobbs, D; Nilesh Badheka, N

    2008-02-27

    The Savannah River Site (SRS) has 49 underground storage tanks used to store High Level Waste (HLW). The tank space in these tanks must be managed to support the continued operation of key facilities. The reduction of the tank volumes in these tanks are accomplished through the use of three atmospheric pressure HLW evaporators. For a decade, evaporation of highly alkaline HLW containing aluminum and silicates has produced sodium aluminosilicate scales causing both operation and criticality hazards in the 2H Evaporator System. Segregation of aluminum-rich wastes from silicate-rich wastes minimizes the amount of scale produced and reduces cleaning expenses, but does not eliminate the scaling nor increases operation flexibility in waste process. Similar issues have affected the aluminum refining industry for many decades. Over the past several years, successful commercial products have been identified to eliminate aluminosilicate fouling in the aluminum industry, but have not been utilized in a nuclear environment. Laboratory quantities of three proprietary aluminosilicate scale inhibitors have been produced and been shown to prevent formation of scales. SRNL has been actively testing these potential inhibitors to examine their radiation stability, radiolytic degradation behaviors, and downstream impacts to determine their viability within the HLW system. One of the tested polymers successfully meets the established criteria for application in the nuclear environment. This paper will describe a summary of the methodology used to prioritize laboratory testing protocols based on potential impacts/risks identified for inhibitor deployment at SRS.

  5. Source fabrication and lifetime for Li{sup +} ion beams extracted from alumino-silicate sources

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.

    2012-04-15

    A space-charge-limited beam with current densities (J) exceeding 1 mA/cm{sup 2} have been measured from lithium alumino-silicate ion sources at a temperature of {approx}1275 deg. C. At higher extraction voltages, the source appears to become emission limited with J{>=} 1.5 mA/cm{sup 2}, and J increases weakly with the applied voltage. A 6.35 mm diameter source with an alumino-silicate coating, {<=}0.25 mm thick, has a measured lifetime of {approx}40 h at {approx}1275 deg. C, when pulsed at 0.05 Hz and with pulse length of {approx}6 {mu}s each. At this rate, the source lifetime was independent of the actual beam charge extracted due to the loss of neutral atoms at high temperature. The source lifetime increases with the amount of alumino-silicate coated on the emitting surface, and may also be further extended if the temperature is reduced between pulses.

  6. Adsorption into mineral mesopores as a stabilization mechanism for organic matter on aluminosilicates

    SciTech Connect

    Mayer, L.M. . Dept. of Oceanography)

    1992-01-01

    Measurements of mineral specific surface area and total organic carbon (TOC) indicate that many marine shelf and estuarine sediments, and aluminosilicate soils, have a TOC content equivalent to a monolayer of organic matter covering all mineral surfaces. Density separations of discrete organic particulates from mineral-associated OC are consistent with a primarily adsorbed nature foremost of TOC. Nitrogen gas adsorption data also suggest extensive organic coatings on the mineral grains. Downcore analyses indicate that sediments with TOC starting in excess of monolayer-equivalent (ME) levels decay with core depth to the ME level and then markedly slow their OC loss rate--i.e., the ME level determines the refractory background concentration of TOC. Pore size distributions of marine sediments, determined by nitrogen adsorption or mercury porosimetry, indicate that most surface area of minerals is to be found in pores of < 10 nm diameter. These observations lead to the hypothesis that organic matter is stabilized on aluminosilicate minerals by adsorption into pores too small to allow entry or functioning of the hydrolytic enzymes responsible for OC degradation. This hypothesis is consistent with, but does not require, humification reactions as necessary for OC stabilization. The ME levels of TOC found in continental platform aluminosilicates hence represent a cap on the amount of organic matter that can be protected in this manner and thus attain a residence time of > 1,000 y. Stabilization of higher levels of TOC, as in acid soils or anoxic sediments, presumably results from protection by different mechanisms.

  7. Anti wetting additives for aluminosilicate refractories in molten aluminum contact applications

    NASA Astrophysics Data System (ADS)

    Shukla, Devdutt Pramod

    Aluminosilicate based refractories are widely used in furnace installations for melting aluminum because they are inexpensive, readily available and generally exhibit the properties desired from a refractory material. However, they face severe corrosion and degradation issues due to the extremely reducing nature of molten aluminum alloys. Isothermal static cup testing is widely used as a tool to evaluate the performance of refractories against penetration by molten aluminum alloys. Various testing methods were reviewed and an upgraded static cup test was recommended. Commercially available aluminosilicate refractories were tested using this method and their results were studied in order to understand the corrosion process. Barium sulfate, which is widely used as an anti-wetting additive to improve refractory performance by limiting physical contact between molten metal and the refractory, has proved ineffective at temperatures above 1000°C. A literature review suggested that barium sulfate formed barium celsian at high temperatures and that the celsian was responsible for the non-wetting effect. Wetting angle measurements of molten AL 5083 on synthetic celsian discs revealed that barium celsian and strontium celsian were both not wetted by molten aluminum. Static cup tests were performed on aluminosilicate refractories containing barium carbonate and strontium carbonate. These additives led to the in-situ formation of celsian phases within the refractory matrix that led to improved corrosion resistance at 1300°C. Phase analysis revealed that celsian formation suppressed the formation of mullite within refractories, thereby reducing penetration.

  8. Studies of Potential Inhibitors of Sodium Aluminosilicate Scales in High-Level Waste Evaporation

    SciTech Connect

    Oji, L.N.; Fellinger, T.L.; Hobbs, D.T.; Badheka, N.P.; Wilmarth, W.R.

    2008-07-01

    The Savannah River Site (SRS) has 49 underground storage tanks used to store High Level Waste (HLW). The tank space in these tanks must be managed to support the continued operation of key facilities. The reduction of the tank volumes in these tanks are accomplished through the use of three atmospheric pressure HLW evaporators. For a decade, evaporation of highly alkaline HLW containing dissolved aluminate and silicate has produced sodium aluminosilicate scales causing both operation and criticality hazards in the 2H Evaporator System. Segregation of aluminum-rich wastes from silicate-rich wastes minimizes the amount of scale produced and reduces cleaning expenses, but does not eliminate the scaling nor increases operation flexibility in waste process. Similar issues have affected the aluminum refining industry for many decades. Over the past several years, successful commercial products have been identified to eliminate aluminosilicate fouling in the aluminum industry, but have not been utilized in a nuclear environment. Laboratory quantities of three proprietary aluminosilicate scale inhibitors have been produced and been shown to prevent formation of scales. SRNL has been actively testing these potential inhibitors to examine their radiation stability, radiolytic degradation behaviors, and downstream impacts to determine their viability within the HLW system. One of the tested polymers successfully meets the established criteria for application in the nuclear environment. This paper will describe a summary of the methodology used to prioritize laboratory testing protocols based on potential impacts/risks identified for inhibitor deployment at SRS. (authors)

  9. Mesoporous aluminosilicates with ordered hexagonal structure, strong acidity, and extraordinary hydrothermal stability at high temperatures.

    PubMed

    Zhang, Z; Han, Y; Xiao, F S; Qiu, S; Zhu, L; Wang, R; Yu, Y; Zhang, Z; Zou, B; Wang, Y; Sun, H; Zhao, D; Wei, Y

    2001-05-30

    Highly ordered hexagonal mesoporous aluminosilicates (MAS-5) with uniform pore sizes have been successfully synthesized from assembly of preformed aluminosilcate precursors with cetyltrimethylammonium bromide (CTAB) surfactant. The aluminosilicate precursors were obtained by heating, at 100--140 degrees C for 2--10 h, aluminasilica gels at the Al(2)O(3)/SiO(2)/TEAOH/H(2)O molar ratios of 1.0/7.0--350/10.0--33.0/500--2000. Mesoporous MAS-5 shows extraordinary stability both in boiling water (over 300 h) and in steam (800 degrees C for 2 h). Temperature-programmed desorption of ammonia shows that the acidic strength of MAS-5 is much higher than that of MCM-41 and is comparable to that of microporous Beta zeolite. In catalytic cracking of 1,3,5-triisopropylbenzene and alkylation of isobutane with butene, MAS-5 exhibits greater catalytic activity and selectivity, as compared with MCM-41 and HZSM-5. The MAS-5 samples were characterized with infrared, UV--Raman, and NMR spectroscopy and numerous other techniques. The results suggest that MAS-5 consists of both mesopores and micropores and that the pore walls of MAS-5 contain primary and secondary structural building units, similar to those of microporous zeolites. Such unique structural features might be responsible for the observed strong acidity and high thermal stability of the mesoporous aluminosilicates with well-ordered hexagonal symmetry. PMID:11457329

  10. Source fabrication and lifetime for Li+ ion beams extracted from alumino-silicate sources.

    PubMed

    Roy, Prabir K; Greenway, Wayne G; Kwan, Joe W

    2012-04-01

    A space-charge-limited beam with current densities (J) exceeding 1 mA/cm(2) have been measured from lithium alumino-silicate ion sources at a temperature of ∼1275 °C. At higher extraction voltages, the source appears to become emission limited with J ≥ 1.5 mA/cm(2), and J increases weakly with the applied voltage. A 6.35 mm diameter source with an alumino-silicate coating, ≤0.25 mm thick, has a measured lifetime of ∼40 h at ∼1275 °C, when pulsed at 0.05 Hz and with pulse length of ∼6 μs each. At this rate, the source lifetime was independent of the actual beam charge extracted due to the loss of neutral atoms at high temperature. The source lifetime increases with the amount of alumino-silicate coated on the emitting surface, and may also be further extended if the temperature is reduced between pulses. PMID:22559528

  11. Impact Of Sodium Oxalate, Sodium Aluminosilicate, and Gibbsite/Boehmite on ARP Filter Performance

    SciTech Connect

    Poirier, M.; Burket, P.

    2015-11-01

    The Savannah River Site (SRS) is currently treating radioactive liquid waste with the Actinide Removal Process (ARP) and the Modular Caustic Side Solvent Extraction Unit (MCU). Recently, the low filter flux through the ARP of approximately 5 gallons per minute has limited the rate at which radioactive liquid waste can be treated. Salt Batch 6 had a lower processing rate and required frequent filter cleaning. Savannah River Remediation (SRR) has a desire to understand the causes of the low filter flux and to increase ARP/MCU throughput. SRR requested SRNL to conduct bench-scale filter tests to evaluate whether sodium oxalate, sodium aluminosilicate, or aluminum solids (i.e., gibbsite and boehmite) could be the cause of excessive fouling of the crossflow or secondary filter at ARP. The authors conducted the tests by preparing slurries containing 6.6 M sodium Salt Batch 6 supernate, 2.5 g MST/L slurry, and varying concentrations of sodium oxalate, sodium aluminosilicate, and aluminum solids, processing the slurry through a bench-scale filter unit that contains a crossflow primary filter and a dead-end secondary filter, and measuring filter flux and transmembrane pressure as a function of time. Among the conclusions drwn from this work are the following: (1) All of the tests showed some evidence of fouling the secondary filter. This fouling could be from fine particles passing through the crossflow filter. (2) The sodium oxalate-containing feeds behaved differently from the sodium aluminosilicate- and gibbsite/boehmite-containing feeds.

  12. Preliminary report on a glass burial experiment in granite

    SciTech Connect

    Clark, D.E.; Zhu, B.F.; Robinson, R.S.; Wicks, G.G.

    1983-01-01

    Preliminary results of a two-year burial experiment in granite are discussed. Three compositions of simulated alkali borosilicate waste glasses were placed in boreholes approximately 350 meters deep. The glass sample configurations include mini-cans (stainless steel rings into which glass has been cast) and pineapple slices (thin sections from cylindrical blocks). Assemblies of these glass samples were prepared by stacking them together with granite, compacted bentonite and metal rings to provide several types of interfaces that are expected to occur in the repository. The assemblies were maintained at either ambient mine temperature (8 to 10/sup 0/C) or 90/sup 0/C. The glasses were analyzed before burial and after one month storage at 90/sup 0/C. The most extensive surface degradation occurred on the glasses interfaced with bentonite. In general, very little attack was observed on glass surfaces in contact with the other materials. The limited field and laboratory data are compared.

  13. Scintillating glass fiber-optic neutron sensors

    NASA Astrophysics Data System (ADS)

    Abel, K. H.; Arthur, R. J.; Bliss, M.

    1994-04-01

    Pacific Northwest Laboratory (PNL) has fabricated cerium-activated lithium silicate scintillating fibers via a hot-downdraw process. These fibers, which, as produced, typically have a transmission length (e(sup -1) length) of greater than 2 meters, are found to undergo aging when subjected to room air. The aging, which is complete in a few weeks, reduces the transmission length to the order of 0.5 meter. Because of the high alkali content of the glass (on the order of 20-30 mole percent lithia), we have attributed this aging to aqueous corrosion at the polymer cladding/glass interface. Changes in transmission with chemical treatment of the surface support the corrosion model. Fiber transmission performance has been preserved by modifying the hot-downdraw to a double crucible to produce glass-on-glass waveguides.

  14. Computer Simulations of Supercooled Liquids and Glasses

    NASA Astrophysics Data System (ADS)

    Kob, Walter

    Glasses are materials that are ubiquitous in our daily life. We find them in such diverse items as window pans, optical fibers, computer chips, ceramics, all of which are oxide glasses, as well as in food, foams, polymers, gels, which are mainly of organic nature. Roughly speaking glasses are solid materials that have no translational or orientational order on the scale beyond O(10) diameters of the constituent particles (atoms, colloids, …) [1]. Note that these materials are not necessarily homogeneous since, e.g., alkali-glasses such as Na2O-SiO2 show (disordered!) structural features on the length scale of 6-10 Å (compare to the interatomic distance of 1-2 Å) and gels can have structural inhomogeneities that extend up to macroscopic length scales.

  15. Recovery of alumina and alkali in Bayer red mud by the formation of andradite-grossular hydrogarnet in hydrothermal process.

    PubMed

    Zhang, Ran; Zheng, Shili; Ma, Shuhua; Zhang, Yi

    2011-05-30

    Bayer red mud (RM) is an alumina refinery waste product rich in aluminum oxides and alkalis which are present primarily in the form of sodium hydro-aluminosilicate desilication product (DSP). A hydrothermal process was employed to recover alumina and alkali from "Fe-rich" and "Fe-lean" RM, the two representative species of RM produced in China. The hydrothermal process objective phase is andradite-grossular hydrogarnet characterized by the isomorphic substitution of Al and Fe. Batch experiments were used to evaluate the main factors influencing the recovery process, namely reaction temperature, caustic ratio (molar ratio of Na(2)O to Al(2)O(3) in sodium solution), sodium concentration and residence time. The results revealed that the Na(2)O content of 0.5 wt% and A/S of 0.3 (mass ratio of Al(2)O(3) to SiO(2)) in leached residue could be achieved with Fe-rich RM under optimal conditions. However, the hydrothermal treatment of Fe-lean RM proved less successful unless the reaction system was enriched with iron. Subsequent experiments examined the effects of the ferric compound's content and type on the substitution ratio. PMID:21444152

  16. Mechanical and microstructural properties of alkali-activated fly ash geopolymers.

    PubMed

    Komljenović, M; Bascarević, Z; Bradić, V

    2010-09-15

    This paper investigates the properties of geopolymer obtained by alkali-activation of fly ash (FA), i.e. the influence of characteristics of the representative group of FA (class F) from Serbia, as well as that of the nature and concentration of various activators on mechanical and microstructural properties of geopolymers. Aqueous solutions of Ca(OH)(2), NaOH, NaOH+Na(2)CO(3), KOH and sodium silicate (water glass) of various concentrations were used as alkali activators. It was established that the nature and concentration of the activator was the most dominant parameter in the alkali-activation process. In respect of physical characteristics of FA, the key parameter was fineness. The geopolymer based on FA with the highest content of fine particles (<43 microm), showed the highest compressive strength in all cases. Regardless of FA characteristics, nature and concentration of the activator, the alkali-activation products were mainly amorphous. The formation of crystalline phases (zeolites) occurred in some cases, depending on the reaction conditions. The highest compressive strength was obtained using sodium silicate. Together with the increase of sodium silicate SiO(2)/Na(2)O mass ratio, the atomic Si/Al ratio in the reaction products was also increased. Under the experimental conditions of this investigation, high strength was directly related to the high Si/Al ratio. PMID:20554110

  17. Interfacial alkali diffusion control in chalcopyrite thin-film solar cells.

    PubMed

    Ishizuka, Shogo; Yamada, Akimasa; Fons, Paul J; Shibata, Hajime; Niki, Shigeru

    2014-08-27

    Alkali elements, specifically sodium (Na), are key materials to enhance the energy conversion efficiencies of chalcopyrite and related thin-film photovoltaic solar cells. Recently, the effect of potassium (K) has also attracted attention because elemental K has unique effects different from Na as well as a similar beneficial effect in improving device performance. In this study, the control of selective alkali K and Na diffusion into chalcopyrite thin-films from soda-lime glass substrates, which serve as the monolithic alkali source material and contain both K and Na, is demonstrated using ternary CuGaSe2. Elemental K is found to be incorporated in the several ten nanometer thick Cu-deficient region, which is formed on the CuGaSe2 film surface, while Na is ejected, although both K and Na diffuse from the substrate to the CuGaSe2 film surface during growth. The alkali [K]/[Na] concentration ratio in the surface region of CuGaSe2 films strongly depends on the film structure and can be controlled by growth parameters under the same substrate temperature conditions. The results we present here offer new concepts necessary to explore and develop emerging new chalcopyrite and related materials and optimize their applications. PMID:25004458

  18. Alkali-Activated Aluminium-Silicate Composites as Insulation Materials for Industrial Application

    NASA Astrophysics Data System (ADS)

    Dembovska, L.; Bajare, D.; Pundiene, I.; Bumanis, G.

    2015-11-01

    The article reports on the study of thermal stability of alkali-activated aluminium- silicate composites (ASC) at temperature 800-1100°C. ASC were prepared by using calcined kaolinite clay, aluminium scrap recycling waste, lead-silicate glass waste and quartz sand. As alkali activator, commercial sodium silicate solution modified with an addition of sodium hydroxide was used. The obtained alkali activation solution had silica modulus Ms=1.67. Components of aluminium scrap recycling waste (aluminium nitride (AlN) and iron sulphite (FeSO3)) react in the alkali media and create gases - ammonia and sulphur dioxide, which provide the porous structure of the material [1]. Changes in the chemical composition of ASC during heating were identified and quantitatively analysed by using DTA/TG, dimension changes during the heating process were determined by using HTOM, pore microstructure was examined by SEM, and mineralogical composition of ASC was determined by XRD. The density of ASC was measured in accordance with EN 1097-7. ASC with density around 560 kg/m3 and heat resistance up to 1100°C with shrinkage less than 5% were obtained. The intended use of this material is the application as an insulation material for industrial purposes at elevated temperatures.

  19. Long-term product consistency test of simulated 90-19/Nd HLW glass

    NASA Astrophysics Data System (ADS)

    Gan, X. Y.; Zhang, Z. T.; Yuan, W. Y.; Wang, L.; Bai, Y.; Ma, H.

    2011-01-01

    Chemical durability of 90-19/Nd glass, a simulated high-level waste (HLW) glass in contact with the groundwater was investigated with a long-term product consistency test (PCT). Generally, it is difficult to observe the long term property of HLW glass due to the slow corrosion rate in a mild condition. In order to overcome this problem, increased contacting surface ( S/ V = 6000 m -1) and elevated temperature (150 °C) were employed to accelerate the glass corrosion evolution. The micro-morphological characteristics of the glass surface and the secondary minerals formed after the glass alteration were analyzed by SEM-EDS and XRD, and concentrations of elements in the leaching solution were determined by ICP-AES. In our experiments, two types of minerals, which have great impact on glass dissolution, were found to form on 90-19/Nd HLW glass surface when it was subjected to a long-term leaching in the groundwater. One is Mg-Fe-rich phyllosilicates with honeycomb structure; the other is aluminosilicates (zeolites). Mg and Fe in the leaching solution participated in the formation of phyllosilicates. The main components of phyllosilicates in alteration products of 90-19/Nd HLW glass are nontronite (Na 0.3Fe 2Si 4O 10(OH) 2·4H 2O) and montmorillonite (Ca 0.2(Al,Mg) 2Si 4O 10(OH) 2·4H 2O), and those of aluminosilicates are mordenite ((Na 2,K 2,Ca)Al 2Si 10O 24·7H 2O)) and clinoptilolite ((Na,K,Ca) 5Al 6Si 30O 72·18H 2O). Minerals like Ca(Mg)SO 4 and CaCO 3 with low solubility limits are prone to form precipitant on the glass surface. Appearance of the phyllosilicates and aluminosilicates result in the dissolution rate of 90-19/Nd HLW glass resumed, which is increased by several times over the stable rate. As further dissolution of the glass, both B and Na in the glass were found to leach out in borax form.

  20. Structure of rhenium-containing sodium borosilicate glass

    SciTech Connect

    Goel, Ashutosh; McCloy, John S.; Windisch, Charles F.; Riley, Brian J.; Schweiger, Michael J.; Rodriguez, Carmen P.; Ferreira, Jose M.

    2013-03-01

    A series of sodium borosilicate glasses were synthesized with increasing fractions of KReO4 or Re2O7, to 10000 ppm (1 mass%) target Re in glass, to assess the effects of large concentrations of rhenium on glass structure and to estimate the solubility of technetium, a radioactive component in typical low active waste nuclear waste glasses. Magic angle spinning nuclear magnetic resonance (MAS-NMR), Fourier transform infrared (FTIR) spectroscopy, and Raman spectroscopy were performed to characterize the glasses as a function of Re source additions. In general, silicon was found coordinated in a mixture of Q2 and Q3 structural units, while Al was 4-coordinated and B was largely 3-coordinate and partially 4-coordinated. The rhenium source did not appear to have significant effects on the glass structure. Thus, at the up to the concentrations that remain in dissolved in glass, ~3000 ppm Re by mass maximum. , the Re appeared to be neither a glass-former nor a strong glass modifier., Rhenium likely exists in isolated ReO4- anions in the interstices of the glass network, as evidenced by the polarized Raman spectrum of the Re glass in the absence of sulfate. Analogous to SO42-¬ in similar glasses, ReO4- is likely a network modifier and forms alkali salt phases on the surface and in the bulk glass above solubility.

  1. Simultaneous high-temperature removal of alkali and particulates in a pressurized gasification system. Third quarterly project report, October 1981-December 1981

    SciTech Connect

    Mulik, P.R.; Alvin, M.A.; Bachovchin, D.M.

    1982-02-01

    This program is directed at performing experimental and analytical investigations, deriving system designs, and eestimating costs to ascertain the feasibility of using aluminosilicate-based getters for controlling alkali in pressurized gasification systems. Its overall objective is to develop a comprehensive plan for evaluating a scaled-up version of the gettering process as a unit operation or as an integral part of a particulate removal device. This report describes work completed on thermodynamic projections, getter selection and qualification, and system performance projections. Work on the thermodynamic projections has been completed and includes an update of the data base, development of alkali phase diagrams, and projections for several gasification processes. Getter selection and qualification efforts involved eight tests with activated bauxite on the thermogravimetric analysis (TGA) system and a comprehensive getter screening test, along with an activated bauxite run with water vapor on the bench-scale unit. Finally, system performance projections entailed a study that attempted to define reaction stoichiometry for the complex gettering process. Data on the fates of alkali metals (Na and K) in 5 gasification processes are reported, including chemical species in the gas and chemical compounds stable at various temperatures in the ash.

  2. Canonical correlation of waste glass compositions and durability, including pH

    SciTech Connect

    Oeksoy, D.; Pye, L.D.; Bickford, D.F.; Ramsey, W.G.

    1993-05-01

    Control of waste glass durability is a major concern in the immobilization of radioactive and mixed wastes. Leaching rate in standardized laboratory tests is being used as a demonstration of consistency of the response of waste glasses in the final disposal environment. The leaching of silicate and borosilicate glasses containing alkali or alkaline earth elements is known to be autocatalytic, in that the initial ion exchange of alkali in the glass for hydrogen ions in water results in the formation of OH and increases the pH of the leachate. The increased pH then increases the rate of silicate network attack, accelerating the leaching effect. In well formulated glasses this effect reaches a thermodynamic equilibrium when leachate saturation of a critical species, such as silica, or a dynamic equilibrium is reached when the pH shift caused by incremental leaching has negligible effect on pH. This report analyzes results of a seven leach test on waste glasses.

  3. Canonical correlation of waste glass compositions and durability, including pH

    SciTech Connect

    Oeksoy, D.; Pye, L.D. ); Bickford, D.F.; Ramsey, W.G. )

    1993-01-01

    Control of waste glass durability is a major concern in the immobilization of radioactive and mixed wastes. Leaching rate in standardized laboratory tests is being used as a demonstration of consistency of the response of waste glasses in the final disposal environment. The leaching of silicate and borosilicate glasses containing alkali or alkaline earth elements is known to be autocatalytic, in that the initial ion exchange of alkali in the glass for hydrogen ions in water results in the formation of OH and increases the pH of the leachate. The increased pH then increases the rate of silicate network attack, accelerating the leaching effect. In well formulated glasses this effect reaches a thermodynamic equilibrium when leachate saturation of a critical species, such as silica, or a dynamic equilibrium is reached when the pH shift caused by incremental leaching has negligible effect on pH. This report analyzes results of a seven leach test on waste glasses.

  4. Strength Improvement of Glass Substrates by Using Surface Nanostructures

    NASA Astrophysics Data System (ADS)

    Kumar, Amarendra; Kashyap, Kunal; Hou, Max T.; Yeh, J. Andrew

    2016-05-01

    Defects and heterogeneities degrade the strength of glass with different surface and subsurface properties. This study uses surface nanostructures to improve the bending strength of glass and investigates the effect of defects on three glass types. Borosilicate and aluminosilicate glasses with a higher defect density than fused silica exhibited 118 and 48 % improvement, respectively, in bending strength after surface nanostructure fabrication. Fused silica, exhibited limited strength improvement. Therefore, a 4-μm-deep square notch was fabricated to study the effect of a dominant defect in low defect density glass. The reduced bending strength of fused silica caused by artificial defect increased 65 % in the presence of 2-μm-deep nanostructures, and the fused silica regained its original strength when the nanostructures were 4 μm deep. In fragmentation tests, the fused silica specimen broke into two major portions because of the creation of artificial defects. The number of fragments increased when nanostructures were fabricated on the fused silica surface. Bending strength improvement and fragmentation test confirm the usability of this method for glasses with low defect densities when a dominant defect is present on the surface. Our findings indicate that nanostructure-based strengthening is suitable for all types of glasses irrespective of defect density, and the observed Weibull modulus enhancement confirms the reliability of this method.

  5. Strength Improvement of Glass Substrates by Using Surface Nanostructures.

    PubMed

    Kumar, Amarendra; Kashyap, Kunal; Hou, Max T; Yeh, J Andrew

    2016-12-01

    Defects and heterogeneities degrade the strength of glass with different surface and subsurface properties. This study uses surface nanostructures to improve the bending strength of glass and investigates the effect of defects on three glass types. Borosilicate and aluminosilicate glasses with a higher defect density than fused silica exhibited 118 and 48 % improvement, respectively, in bending strength after surface nanostructure fabrication. Fused silica, exhibited limited strength improvement. Therefore, a 4-μm-deep square notch was fabricated to study the effect of a dominant defect in low defect density glass. The reduced bending strength of fused silica caused by artificial defect increased 65 % in the presence of 2-μm-deep nanostructures, and the fused silica regained its original strength when the nanostructures were 4 μm deep. In fragmentation tests, the fused silica specimen broke into two major portions because of the creation of artificial defects. The number of fragments increased when nanostructures were fabricated on the fused silica surface. Bending strength improvement and fragmentation test confirm the usability of this method for glasses with low defect densities when a dominant defect is present on the surface. Our findings indicate that nanostructure-based strengthening is suitable for all types of glasses irrespective of defect density, and the observed Weibull modulus enhancement confirms the reliability of this method. PMID:27194443

  6. Thermochemical study of rare earth and nitrogen incorporation in glasses

    NASA Astrophysics Data System (ADS)

    Zhang, Yahong

    Rare earth containing aluminosilicate, borosilicate, aluminate and nitrogen containing aluminosilicate glasses are technically important materials. They have extraordinary physical and chemical properties such as high glass transition temperature, very low electrical conductivity, and excellent chemical stability. These unique properties lead to applications as coatings on metals and ceramics, optical fibers, semiconductors, and nuclear waste containment materials. In addition, such systems contain the most widely used additives for sintering of Si3N4, SiAlON and SiC ceramics for high temperature applications. Thermodynamic properties and the relations among energetics, structure and bonding are essential to controlling processing parameters to synthesize, at lower cost, materials having better properties. Earlier investigations mainly pertained to specific physical properties of rare-earth doped oxide and oxynitride glasses. Work on the thermodynamic stability and materials compatibility has been very sparse. High temperature solution calorimetry in molten oxide solvents is a powerful tool for the thermodynamic study of refractory materials. With implementation and improvement, this technique has been applied to the first measurement of enthalpies of formation of RE-Si-Al-O glasses, REAlO3 glasses, RE-Si-Al-O-N glasses, and Si3N 4 and Ge3N4 with high pressure spinel structure. The first successful synthesis of REAlO3 glasses has been achieved by containerless melting. Their large enthalpies of crystallization confirm that they are reluctant glass formers. For glasses along the 2REAlO3 -3SiO2 join, the strongly negative heats of mixing support the absence of miscibility gaps except possibly at very high silica content. Energetic evidence has been presented for incipient phase-ordered regions in Gd- or Hf-containing sodium alumino-borosilicate glasses for plutonium immobilization. Linear relations between enthalpies of formation of RESiAlON glasses from elements and

  7. Alkali metal adsorption on Al(111)

    NASA Astrophysics Data System (ADS)

    Andersen, J. N.; Lundgren, E.; Nyholm, R.; Qvarford, M.

    1993-06-01

    The submonolayer adsorption of Na, K, Rb, and Cs on the Al(111) surface at 100 K and at room temperature is investigated by high resolution core level spectroscopy and low energy electron diffraction. It is found that the first alkali atoms on the surface adsorb at surface defects. At higher coverages, up to approximately one third of the maximum submonolayer coverage, alkali atoms adsorbed at defects coexist with a dispersed phase. At higher coverages island formation is found to occur for the majority of the systems. It is argued that all of the ordered structures formed at room temperature involve a disruption of the Al(111) surface in contrast to the situation at 100 K where the alkali atoms adsorb as adatoms.

  8. SAFE Alkali Metal Heat Pipe Reliability

    NASA Astrophysics Data System (ADS)

    Reid, Robert S.

    2003-01-01

    Alkali metal heat pipes are among the best understood and tested of components for first generation space fission reactors. A flight reactor will require production of a hundred or more heat pipes with assured reliability over a number of years. To date, alkali metal heat pipes have been built mostly in low budget development environments with little formal quality assurance. Despite this, heat pipe test samples suggest that high reliability can be achieved with the care justified for space flight qualification. Fabrication procedures have been established that, if consistently applied, ensure long-term trouble-free heat pipe operation. Alkali metal heat pipes have been successfully flight tested in micro gravity and also have been shown capable of multi-year operation with no evidence of sensitivity to fast neutron fluence up to 1023 n/cm2. This represents 50 times the fluence of the proposed Safe Affordable Fission Engine (SAFE-100) heat pipe reactor core.

  9. A-thermal elastic behavior of silicate glasses

    NASA Astrophysics Data System (ADS)

    Rabia, Mohammed Kamel; Degioanni, Simon; Martinet, Christine; Le Brusq, Jacques; Champagnon, Bernard; Vouagner, Dominique

    2016-02-01

    Depending on the composition of silicate glasses, their elastic moduli can increase or decrease as function of the temperature. Studying the Brillouin frequency shift of these glasses versus temperature allows the a-thermal composition corresponding to an intermediate glass to be determined. In an intermediate glass, the elastic moduli are independent of the temperature over a large temperature range. For sodium alumino-silicate glasses, the a-thermal composition is close to the albite glass (NaAlSi3O8). The structural origin of this property is studied by in situ high temperature Raman scattering. The structure of the intermediate albite glass and of silica are compared at different temperatures between room temperature and 600 °C. When the temperature increases, it is shown that the high frequency shift of the main band at 440 cm-1 in silica is a consequence of the cristobalite-like alpha-beta transformation of 6-membered rings. This effect is stronger in silica than bond elongation (anharmonic effects). As a consequence, the elastic moduli of silica increase as the temperature increases. In the albite glass, the substitution of 25% of Si4+ ions by Al3+ and Na+ ions decreases the proportion of SiO2 6-membered rings responsible for the silica anomaly. The effects of the silica anomaly balance the anharmonicity in albite glass and give rise to an intermediate a-thermal glass. Different networks, formers or modifiers, can be added to produce different a-thermal glasses with useful mechanical or chemical properties.

  10. A-thermal elastic behavior of silicate glasses.

    PubMed

    Rabia, Mohammed Kamel; Degioanni, Simon; Martinet, Christine; Le Brusq, Jacques; Champagnon, Bernard; Vouagner, Dominique

    2016-02-24

    Depending on the composition of silicate glasses, their elastic moduli can increase or decrease as function of the temperature. Studying the Brillouin frequency shift of these glasses versus temperature allows the a-thermal composition corresponding to an intermediate glass to be determined. In an intermediate glass, the elastic moduli are independent of the temperature over a large temperature range. For sodium alumino-silicate glasses, the a-thermal composition is close to the albite glass (NaAlSi3O8). The structural origin of this property is studied by in situ high temperature Raman scattering. The structure of the intermediate albite glass and of silica are compared at different temperatures between room temperature and 600 °C. When the temperature increases, it is shown that the high frequency shift of the main band at 440 cm(-1) in silica is a consequence of the cristobalite-like alpha-beta transformation of 6-membered rings. This effect is stronger in silica than bond elongation (anharmonic effects). As a consequence, the elastic moduli of silica increase as the temperature increases. In the albite glass, the substitution of 25% of Si(4+) ions by Al(3+) and Na(+) ions decreases the proportion of SiO2 6-membered rings responsible for the silica anomaly. The effects of the silica anomaly balance the anharmonicity in albite glass and give rise to an intermediate a-thermal glass. Different networks, formers or modifiers, can be added to produce different a-thermal glasses with useful mechanical or chemical properties. PMID:26815634

  11. Structure and the physicochemical properties of glasses and glass melts

    NASA Astrophysics Data System (ADS)

    Kucuk, Ahmet

    1999-11-01

    A user friendly experimental procedure (sessile and pendant drop arrangements) and calculation routine were developed to measure the physicochemical properties such as density, surface tension, and volatilization of glasses and glass melts at the temperature range of 500 to 1500°C. The influence of volatilization on the composition, density and surface tension of potassium, sodium silicate and soda lime silica melts at 1400°C was investigated using the sessile and pendant drop arrangements, diffuse reflectance Fourier transform spectrometry and electronic-balance. Volatilization of alkali from the melts was modeled as a combined mechanism that included diffusion of volatile species from bulk to surface and chemical decomposition reaction of alkali oxide on the surface. The surface tension of experimental and commercial glass melts, some containing iron, was measured under various atmospheres including 4%H 2/96%Ar, dry argon, dry air and wet air using the sessile drop and pendant drop arrangements. In general, the surface tension of the melts decreased in the given order: argon, dry air and wet air. OH groups from water vapor in the atmosphere behave as a surface active species according to the Gibbs adsorption equation and form a mono-layer on the surface with certain number of molecules according to the Langmuir adsorption theorem. The number of OH-like molecules in the monolayer is higher for the melts containing high ionic strength ions. Iron containing melts have higher surface tension and density for higher Fe2+/Fe3+ ratios. The presence of four-coordinated Fe3+ ions rather than six-coordinated Fe 2+ in the surface of iron bearing glass melts was found to be energetically more favorable. The structures of potassium and lithium silicate glasses and melts were modeled using the molecular dynamics simulation at 300 K and 1700 K, respectively. Despite of the excellent agreement between modeled and experimentally determined structure in the short range, modeled

  12. Diode pumped alkali lasers (DPALs): an overview

    NASA Astrophysics Data System (ADS)

    Krupke, William F.

    2008-05-01

    The concept of power-scalable, high beam-quality diode pumped alkali lasers was introduced in 2003 [Krupke, US Patent No. 6,643,311; Opt. Letters, 28, 2336 (2003)]. Since then several laboratory DPAL devices have been reported on, confirming many of the spectroscopic, kinetic, and laser characteristics projected from literature data. This talk will present an overview of the DPAL concept, summarize key relevant properties of the cesium, rubidium, and potassium alkali vapor gain media so-far examined, outline power scaling considerations, and highlight results of published DPAL laboratory experiments.

  13. Alkali metal vapors - Laser spectroscopy and applications

    NASA Technical Reports Server (NTRS)

    Stwalley, W. C.; Koch, M. E.

    1980-01-01

    The paper examines the rapidly expanding use of lasers for spectroscopic studies of alkali metal vapors. Since the alkali metals (lithium, sodium, potassium, rubidium and cesium) are theoretically simple ('visible hydrogen'), readily ionized, and strongly interacting with laser light, they represent ideal systems for quantitative understanding of microscopic interconversion mechanisms between photon (e.g., solar or laser), chemical, electrical and thermal energy. The possible implications of such understanding for a wide variety of practical applications (sodium lamps, thermionic converters, magnetohydrodynamic devices, new lasers, 'lithium waterfall' inertial confinement fusion reactors, etc.) are also discussed.

  14. Development of a Composite Non-Electrostatic Surface Complexation Model Describing Plutonium Sorption to Aluminosilicates

    SciTech Connect

    Powell, B A; Kersting, A; Zavarin, M; Zhao, P

    2008-10-28

    Due to their ubiquity in nature and chemical reactivity, aluminosilicate minerals play an important role in retarding actinide subsurface migration. However, very few studies have examined Pu interaction with clay minerals in sufficient detail to produce a credible mechanistic model of its behavior. In this work, Pu(IV) and Pu(V) interactions with silica, gibbsite (Aloxide), and Na-montmorillonite (smectite clay) were examined as a function of time and pH. Sorption of Pu(IV) and Pu(V) to gibbsite and silica increased with pH (4 to 10). The Pu(V) sorption edge shifted to lower pH values over time and approached that of Pu(IV). This behavior is apparently due to surface mediated reduction of Pu(V) to Pu(IV). Surface complexation constants describing Pu(IV)/Pu(V) sorption to aluminol and silanol groups were developed from the silica and gibbsite sorption experiments and applied to the montmorillonite dataset. The model provided an acceptable fit to the montmorillonite sorption data for Pu(V). In order to accurately predict Pu(IV) sorption to montmorillonite, the model required inclusion of ion exchange. The objective of this work is to measure the sorption of Pu(IV) and Pu(V) to silica, gibbsite, and smectite (montmorillonite). Aluminosilicate minerals are ubiquitous at the Nevada National Security Site and improving our understanding of Pu sorption to aluminosilicates (smectite clays in particular) is essential to the accurate prediction of Pu transport rates. These data will improve the mechanistic approach for modeling the hydrologic source term (HST) and provide sorption Kd parameters for use in CAU models. In both alluvium and tuff, aluminosilicates have been found to play a dominant role in the radionuclide retardation because their abundance is typically more than an order of magnitude greater than other potential sorbing minerals such as iron and manganese oxides (e.g. Vaniman et al., 1996). The sorption database used in recent HST models (Carle et al., 2006

  15. High-Intensity Plasma Glass Melter Final Technical Report

    SciTech Connect

    Gonterman, J. Ronald; Weinstein, Michael A.

    2006-10-27

    frits. Exploratory melts of non-glassy materials, such as wollastonite, zirconium silicate, and alumino-silicate melts were successfully done indicating that plasma melting has potential application beyond glass. Experimental results were generated that show the high quality of plasma-melted fiberglass compositions, such as E-glass, can result in good fiberizing performance. Fiberizing performance and tensile strength data were achieved during the project to support this conclusion. High seed counts are a feature of the current lab scale melter and must be dealt with via other means, since fining work was outside the scope of this project.

  16. Alkali-aggregate reaction in concrete containing high-alkali cement and granite aggregate

    SciTech Connect

    Owsiak, Z

    2004-01-01

    The paper discusses results of the research into the influence of high-alkali Portland cement on granite aggregate. The deformation of the concrete structure occurred after 18 months. The research was carried out by means of a scanning electron microscope equipped with a high-energy dispersive X-ray analyzer that allowed observation of unpolished sections of concrete bars exhibiting the cracking pattern typical of the alkali-silica reaction. Both the microscopic observation and the X-ray elemental analysis confirm the presence of alkali-silica gel and secondary ettringite in the cracks.

  17. Viscosity properties of sodium borophosphate glasses

    SciTech Connect

    Gaylord, S.; Tincher, B.; Petit, L. Richardson, K.

    2009-05-06

    The viscosity behavior of (1 - x)NaPO{sub 3}-xNa{sub 2}B{sub 4}O{sub 7} glasses (x = 0.05-0.20) have been measured as a function of temperature using beam-bending and parallel-plate viscometry. The viscosity was found to shift to higher temperatures with increasing sodium borate content. The kinetic fragility parameter, m, estimated from the viscosity curve, decreases from 52 to 33 when x increases from 0.05 to 0.20 indicating that the glass network transforms from fragile to strong with the addition of Na{sub 2}B{sub 4}O{sub 7}. The decrease in fragility with increasing x is due to the progressive depolymerization of the phosphate network by the preferred four-coordinated boron atoms present in the low alkali borate glasses. As confirmed by Raman spectroscopy increasing alkali borate leads to enhanced B-O-P linkages realized with the accompanying transition from solely four-coordinated boron (in BO{sub 4} units) to mixed BO{sub 4}/BO{sub 3} structures. The glass viscosity characteristics of the investigated glasses were compared to those of P-SF67 and N-FK5 commercial glasses from SCHOTT. We showed that the dependence of the viscosity of P-SF67 was similar to the investigated glasses due to similar phosphate network organization confirmed by Raman spectroscopy, whereas N-FK5 exhibited a very different viscosity curve and fragility parameter due to its highly coordinated silicate network.

  18. Recovery of alkali metal constituents from catalytic coal conversion residues

    DOEpatents

    Soung, W.Y.

    In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  19. Thermochemistry of glasses along the 2NdAlO3 3SiO2 join

    NASA Astrophysics Data System (ADS)

    Zhang, Yahong; Navrotsky, Alexandra; Tangeman, Jean A.; Weber, J. K. Richard

    2003-08-01

    Five Nd-aluminosilicate glasses along the 2NdAlO3-3SiO2 join were synthesized using conventional drop-quench techniques. A sixth glass, with the end-member NdAlO3 composition, required synthesis by containerless liquid-phase processing methods to avoid crystallization. Enthalpies of drop solution (DeltaHds) and formation (DeltaHf) for the Nd-aluminosilicate glasses and the NdAlO3-composition end-member glass were measured in molten 2PbO-B2O3 at 1078 K in a twin Calvet type calorimeter. Values for DeltaHds for the Nd-aluminosilicate glasses increase with decreasing silica content from 130.7 +/- 1.5 to 149.6 +/- 0.6 kJ mol-1. Similarly, values of DeltaHf increase with decreasing silica content from 41.0 +/- 2.0 to 59.0 +/- 1.6 kJ mol-1. Values of DeltaHds and DeltaHf for NdAlO3-composition glass were measured as 99.3 +/- 0.9 and 139.2 +/- 2.1 kJ mol-1, respectively. Using transposed temperature drop calorimetry, the enthalpy of vitrification for NdAlO3-composition glass was measured as 69.5 +/- 0.9 kJ mol-1 relative to the stable crystalline neodymium aluminium perovskite (NdAlO3) phase. Enthalpies of mixing were calculated based on amorphous end members; the strongly negative values support the absence of immiscibility in this system. Differential scanning calorimetry was used to determine glass transition (Tg) and crystallization (Tx) temperatures, as well as values for the configurational heat capacity (DeltaCP(Tg)) and the temperature range of the supercooled liquid interval (DeltaT(SCL)). The NdAlO3-composition glass showed no evidence of a glass transition prior to crystallization; only a single exotherm was observed, the onset of which occurred at 1045 K. For the Nd-aluminosilicates, values of Tg and DeltaT(SCL) increase with increasing silica content, from 1128 to 1139 K and from ~95 to ~175 K, respectively. Values of (DeltaCP(Tg)) increase with decreasing silica content, from ~27 to ~75 J/g fw lowastK, reflecting the increasing fragility and decreasing

  20. Contribution of aluminas and aluminosilicates to the formation of PCDD/Fs on fly ashes.

    PubMed

    Potter, Phillip M; Dellinger, Barry; Lomnicki, Slawomir M

    2016-02-01

    Chlorinated aromatics undergo surface-mediated reactions with metal oxides to form Environmentally Persistent Free Radicals (EPFRs) which can further react to produce polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Previous work using laboratory-made fly ash surrogates composed of transition metal oxides deposited on silica powder has confirmed their ability to mimic fly ash in the production of PCDD/Fs. However, little is known about the propensity of aluminas and aluminosilicates, other components of fly ash, to form PCDD/Fs. A fly ash sample containing both alumina and mullite, an aluminosilicate, was tested for PCDD/F formation ability and compared to PCDD/F yields from the thermal degradation of 2-monochlorophenol (2-MCP) precursor over γ-alumina, α-alumina, and mullite. A packed-bed flow reactor was used to investigate the thermal degradation of 2-MCP over the various catalysts at 200-600 °C. Fly ash gave similar PCDD/F yields to surrogates made with similar transition metal content. γ-alumina, which is thermodynamically unfavorable, was very catalytically active and gave low PCDD/F yields despite a high destruction of 2-MCP. Mullite and α-alumina, the thermodynamically favorable form of alumina, yielded higher concentrations of dioxins and products with a higher degree of chlorine substitution than γ-alumina. The data suggest that certain aluminas and aluminosilicates, commonly found in fly ash, are active catalytic surfaces in the formation of PCDD/Fs in the post-flame cool zones of combustion systems and should be considered as additional catalytic surfaces active in the process. PMID:26615490

  1. In vitro osteogenic/dentinogenic potential of an experimental calcium aluminosilicate cement

    PubMed Central

    Eid, Ashraf A.; Niu, Li-na; Primus, Carolyn M.; Opperman, Lynne A.; Watanabe, Ikuya; Pashley, David H.; Tay, Franklin R.

    2013-01-01

    Introduction Calcium aluminosilicate cements are fast-setting, acid-resistant, bioactive cements that may be used as root-repair materials. This study examined the osteogenic/dentinogenic potential of an experimental calcium aluminosilicate cement (Quick-Set) using a murine odontoblast-like cell model. Methods Quick-Set and white ProRoot MTA (WMTA) were mixed with the proprietary gel or deionized water, allowed to set completely in 100% relative humidity and aged in complete growth medium for 2 weeks until rendered non-cytotoxic. Similarly-aged Teflon discs were used as negative control. The MDPC-23 cell-line was used for evaluating changes in mRNA expressions of genes associated with osteogenic/dentinogenic differentiation and mineralization (qRT-PCR) alkaline phosphatase enzyme production and extracellular matrix mineralization (Alizarin red-S staining). Results After MDPC-23 cells were incubated with the materials in osteogenic differentiation medium for 1 week, both cements showed upregulation in ALP and DSPP expression. Fold increases in these two genes were not significantly different between Quick-Set and WMTA. Both cements showed no statistically significant upregulation/downregulation in RUNX2, OCN, BSP and DMP1 gene expression compared with Teflon. Alkaline phosphatase activity of cells cultured on Quick-Set and WMTA were not significantly different at 1 week or 2 weeks, but were significantly higher (p<0.05) than Teflon in both weeks. Both cements showed significantly higher calcium deposition compared with Teflon after 3 weeks of incubation in mineralizing medium (p<0.001). Differences between Quick-Set and WMTA were not statistically significant. Conclusions The experimental calcium aluminosilicate cement exhibits similar osteogenic/dentinogenic properties to WMTA and may be a potential substitute for commercially-available tricalcium silicate cements. PMID:23953291

  2. Metallic nanoparticles and their medicinal potential. Part II: aluminosilicates, nanobiomagnets, quantum dots and cochleates.

    PubMed

    Loomba, Leena; Scarabelli, Tiziano

    2013-09-01

    Metallic miniaturization techniques have taken metals to nanoscale size where they can display fascinating properties and their potential applications in medicine. In recent years, metal nanoparticles such as aluminium, silicon, iron, cadmium, selenium, indium and calcium, which find their presence in aluminosilicates, nanobiomagnets, quantum dots (Q-dots) and cochleates, have caught attention of medical industries. The increasing impact of metallic nanoparticles in life sciences has significantly advanced the production techniques for these nanoparticles. In this Review, the various methods for the synthesis of nanoparticles are outlined, followed by their physicochemical properties, some recent applications in wound healing, diagnostic imaging, biosensing, assay labeling, antimicrobial activity, cancer therapy and drug delivery are listed, and finally their toxicological impacts are revised. The first half of this article describes the medicinal uses of two noble nanoparticles - gold and silver. This Review provides further information on the ability of aluminum, silicon, iron, selenium, indium, calcium and zinc to be used as nanoparticles in biomedical sciences. Aluminosilicates find their utility in wound healing and antibacterial growth. Iron-oxide nanoparticles enhance the properties of MRI contrast agents and are also used as biomagnets. Cadmium, selenium, tellurium and indium form the core nanostructures of tiny Q-dots used in cellular assay labeling, high-resolution cell imaging and biosensing. Cochleates have the bivalent nano ions calcium, magnesium or zinc imbedded in their structures and are considered to be highly effective agents for drug and gene delivery. The aluminosilicates, nanobiomagnets, Q-dots and cochleates are discussed in the light of their properties, synthesis and utility. PMID:24024515

  3. Triple stack glass-to-glass anodic bonding for optogalvanic spectroscopy cells with electrical feedthroughs

    SciTech Connect

    Daschner, R.; Kübler, H.; Löw, R.; Pfau, T.; Baur, H.; Frühauf, N.

    2014-07-28

    We demonstrate the use of an anodic bonding technique for building a vacuum tight vapor cell for the use of Rydberg spectroscopy of alkali atoms with thin film electrodes on the inside of the cell. The cell is fabricated by simultaneous triple stack glass-to-glass anodic bonding at 300 °C. This glue-free, low temperature sealing technique provides the opportunity to include thin film electric feedthroughs. The pressure broadening is only limited by the vapor pressure of rubidium and the lifetime is at least four months with operating temperatures up to 230 °C.

  4. Triple stack glass-to-glass anodic bonding for optogalvanic spectroscopy cells with electrical feedthroughs

    NASA Astrophysics Data System (ADS)

    Daschner, R.; Kübler, H.; Löw, R.; Baur, H.; Frühauf, N.; Pfau, T.

    2014-07-01

    We demonstrate the use of an anodic bonding technique for building a vacuum tight vapor cell for the use of Rydberg spectroscopy of alkali atoms with thin film electrodes on the inside of the cell. The cell is fabricated by simultaneous triple stack glass-to-glass anodic bonding at 300 °C. This glue-free, low temperature sealing technique provides the opportunity to include thin film electric feedthroughs. The pressure broadening is only limited by the vapor pressure of rubidium and the lifetime is at least four months with operating temperatures up to 230 °C.

  5. Facile Fabrication of Uniform Polyaniline Nanotubes with Tubular Aluminosilicates as Templates

    NASA Astrophysics Data System (ADS)

    Zhang, Long; Liu, Peng

    2008-08-01

    The uniform polyaniline (PANI) nanotubes, with inner diameter, outer diameter, and tubular thickness of 40, 60, and 10 nm, respectively, were prepared successfully by using natural tubular aluminosilicates as templates. The halloysite nanotubes were coated with PANI via the in situ chemical oxidation polymerization. Then the templates were etched with HCl/HF solution. The PANI nanotubes were characterized using FTIR, X-ray diffraction, and transmission electron microscopy. The conductivity of the PANI nanotubes was found to be 1.752 × 10-5 (Ω·cm)-1.

  6. Monte Carlo simulations of phosphate polyhedron connectivity in glasses

    SciTech Connect

    ALAM,TODD M.

    2000-01-01

    Monte Carlo simulations of phosphate tetrahedron connectivity distributions in alkali and alkaline earth phosphate glasses are reported. By utilizing a discrete bond model, the distribution of next-nearest neighbor connectivities between phosphate polyhedron for random, alternating and clustering bonding scenarios was evaluated as a function of the relative bond energy difference. The simulated distributions are compared to experimentally observed connectivities reported for solid-state two-dimensional exchange and double-quantum NMR experiments of phosphate glasses. These Monte Carlo simulations demonstrate that the polyhedron connectivity is best described by a random distribution in lithium phosphate and calcium phosphate glasses.

  7. Monte Carlo Simulations of Phosphate Polyhedron Connectivity in Glasses

    SciTech Connect

    ALAM,TODD M.

    1999-12-21

    Monte Carlo simulations of phosphate tetrahedron connectivity distributions in alkali and alkaline earth phosphate glasses are reported. By utilizing a discrete bond model, the distribution of next-nearest neighbor connectivities between phosphate polyhedron for random, alternating and clustering bonding scenarios was evaluated as a function of the relative bond energy difference. The simulated distributions are compared to experimentally observed connectivities reported for solid-state two-dimensional exchange and double-quantum NMR experiments of phosphate glasses. These Monte Carlo simulations demonstrate that the polyhedron connectivity is best described by a random distribution in lithium phosphate and calcium phosphate glasses.

  8. Salts of alkali metal anions and process of preparing same

    DOEpatents

    Dye, James L.; Ceraso, Joseph M.; Tehan, Frederick J.; Lok, Mei Tak

    1978-01-01

    Compounds of alkali metal anion salts of alkali metal cations in bicyclic polyoxadiamines are disclosed. The salts are prepared by contacting an excess of alkali metal with an alkali metal dissolving solution consisting of a bicyclic polyoxadiamine in a suitable solvent, and recovered by precipitation. The salts have a gold-color crystalline appearance and are stable in a vacuum at -10.degree. C. and below.

  9. Topological principles of borosilicate glass chemistry.

    PubMed

    Smedskjaer, Morten M; Mauro, John C; Youngman, Randall E; Hogue, Carrie L; Potuzak, Marcel; Yue, Yuanzheng

    2011-11-10

    Borosilicate glasses display a rich complexity of chemical behavior depending on the details of their composition and thermal history. Noted for their high chemical durability and thermal shock resistance, borosilicate glasses have found a variety of important uses from common household and laboratory glassware to high-tech applications such as liquid crystal displays. In this paper, we investigate the topological principles of borosilicate glass chemistry covering the extremes from pure borate to pure silicate end members. Based on NMR measurements, we present a two-state statistical mechanical model of boron speciation in which addition of network modifiers leads to a competition between the formation of nonbridging oxygen and the conversion of boron from trigonal to tetrahedral configuration. Using this model, we derive a detailed topological representation of alkali-alkaline earth-borosilicate glasses that enables the accurate prediction of properties such as glass transition temperature, liquid fragility, and hardness. The modeling approach enables an understanding of the microscopic mechanisms governing macroscopic properties. The implications of the glass topology are discussed in terms of both the temperature and thermal history dependence of the atomic bond constraints and the influence on relaxation behavior. We also observe a nonlinear evolution of the jump in isobaric heat capacity at the glass transition when substituting SiO(2) for B(2)O(3), which can be accurately predicted using a combined topological and thermodynamic modeling approach. PMID:21950415

  10. Faraday rotation density measurements of optically thick alkali metal vapors

    NASA Astrophysics Data System (ADS)

    Vliegen, E.; Kadlecek, S.; Anderson, L. W.; Walker, T. G.; Erickson, C. J.; Happer, William

    2001-03-01

    We investigate the measurement of alkali number densities using the Faraday rotation of linearly polarized light. We find that the alkali number density may be reliably extracted even in regimes of very high buffer gas pressure, and very high alkali number density. We have directly verified our results in potassium using absorption spectroscopy on the second resonance (4 2S→5 2P).

  11. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  12. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  13. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  14. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  15. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  16. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  17. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  18. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  19. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  20. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  1. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  2. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  3. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  4. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  5. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  6. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  7. Laboratory testing of glasses for Lockheed Idaho Technology Company: Final report

    SciTech Connect

    Ellison, A.J.G.; Buck, E.C.; Dietz, N.L.; Ebert, W.L.; Luo, J.S.; Wolf, S.F.; Bates, J.K.

    1997-06-01

    Tests have been conducted at Argonne National Laboratory (ANL) in support of the efforts of Lockheed Idaho Technology Company (LITCO) to vitrify high-level waste calcines. Tests were conducted with three classes of LITCO glass formulations: Formula 127 (fluorine-bearing), Formula 532 (fluorine-free), and 630 series (both single- and mixed-alkali) glasses. The test matrices included, as appropriate, the Product Consistency Test Method B (PCT-B), the Materials Characterization Center Test 1 (MCC-1), and the Argonne vapor hydration test (VHT). Test durations ranged from 7 to 183 d. In 7-d PCT-Bs, normalized mass losses of major glass-forming elements for the LITCO glasses are similar to, or lower than, normalized mass losses obtained for other domestic candidate waste glasses. Formula 532 glasses form zeolite alteration phases relatively early in their reaction with water. The formation of those phases increased the dissolution rate. In contrast, the Formula 127 glass is highly durable and forms alteration phases only after prolonged exposure to water in tests with very high surface area to volume ratios; these alteration phases have a relatively small effect on the rate of glass corrosion. No alteration phases formed within the maximum test duration of 183 d in PCT-Bs with the 630 series glasses. The corrosion behavior of the mixed-alkali 630 series glasses is similar to that of 630 series glasses containing sodium alone. In VHTs, both single- and mixed-alkali glasses form zeolite phases that increase the rate of glass reaction. The original 630 series glasses and those based on a revised surrogate calcine formulation react at the same rate in PCT-Bs and form the same major alteration phases in VHTs.

  8. Computational studies of solid-state alkali conduction in rechargeable alkali-ion batteries

    DOE PAGESBeta

    Deng, Zhi; Mo, Yifei; Ong, Shyue Ping

    2016-03-25

    The facile conduction of alkali ions in a crystal host is of crucial importance in rechargeable alkali-ion batteries, the dominant form of energy storage today. In this review, we provide a comprehensive survey of computational approaches to study solid-state alkali diffusion. We demonstrate how these methods have provided useful insights into the design of materials that form the main components of a rechargeable alkali-ion battery, namely the electrodes, superionic conductor solid electrolytes and interfaces. We will also provide a perspective on future challenges and directions. Here, the scope of this review includes the monovalent lithium- and sodium-ion chemistries that aremore » currently of the most commercial interest.« less

  9. Alkali resistant optical coatings for alkali lasers and methods of production thereof

    DOEpatents

    Soules, Thomas F; Beach, Raymond J; Mitchell, Scott C

    2014-11-18

    In one embodiment, a multilayer dielectric coating for use in an alkali laser includes two or more alternating layers of high and low refractive index materials, wherein an innermost layer includes a thicker, >500 nm, and dense, >97% of theoretical, layer of at least one of: alumina, zirconia, and hafnia for protecting subsequent layers of the two or more alternating layers of high and low index dielectric materials from alkali attack. In another embodiment, a method for forming an alkali resistant coating includes forming a first oxide material above a substrate and forming a second oxide material above the first oxide material to form a multilayer dielectric coating, wherein the second oxide material is on a side of the multilayer dielectric coating for contacting an alkali.

  10. Terahertz radiation in alkali vapor plasmas

    SciTech Connect

    Sun, Xuan; Zhang, X.-C.

    2014-05-12

    By taking advantage of low ionization potentials of alkali atoms, we demonstrate terahertz wave generation from cesium and rubidium vapor plasmas with an amplitude nearly one order of magnitude larger than that from nitrogen gas at low pressure (0.02–0.5 Torr). The observed phenomena are explained by the numerical modeling based upon electron tunneling ionization.

  11. The Additive Coloration of Alkali Halides

    ERIC Educational Resources Information Center

    Jirgal, G. H.; and others

    1969-01-01

    Describes the construction and use of an inexpensive, vacuum furnace designed to produce F-centers in alkali halide crystals by additive coloration. The method described avoids corrosion or contamination during the coloration process. Examination of the resultant crystals is discussed and several experiments using additively colored crystals are…

  12. Hyaline membrane disease, alkali, and intraventricular haemorrhage.

    PubMed Central

    Wigglesworth, J S; Keith, I H; Girling, D J; Slade, S A

    1976-01-01

    The relation between intraventricular haemorrhage (IVH) and hyaline membrane disease (HMD) was studied in singletons that came to necropsy at Hammersmith Hospital over the years 1966-73. The incidence of IVH in singleton live births was 3-22/1000 and of HMD 4-44/1000. Although the high figures were partily due to the large number of low birthweight infants born at this hospital, the incidence of IVH in babies weighing 1001-1500 g was three times as great as that reported in the 1658 British Perinatal Mortality Survey. Most IVH deaths were in babies with HMD, but the higher frequency of IVH was not associated with any prolongation of survival time of babies who died with HMD as compared with the 1958 survey. IVH was seen frequently at gestations of up to 36 weeks in babies with HMD but was rare above 30 weeks' gestation in babies without HMD. This indicated that factors associated with HMD must cause most cases of IVH seen at gestations above 30 weeks. Comparison of clinical details in infants with HMD who died with or without IVH (at gestations of 30-37 weeks) showed no significant differences between the groups other than a high incidence of fits and greater use of alkali therapy in the babies with IVH. During the 12 hours when most alkali therapy was given, babies dying with IVD received a mean total alkali dosage of 10-21 mmol/kg and those dying without IVH 6-34 mmol/kg (P less than 0-001).There was no difference in severity of hypoxia or of metabolic acidosis between the 2 groups. Babies who died with HMD and germinal layer haemorrhage (GLH) without IVH had received significantly more alkali than those who died with HMD alone, whereas survivors of severe respiratory distress syndrome had received lower alkali doses than other groups. It is suggested that the greatly increased death rate from IVH in babies with HMD indicates some alteration of management of HMD (since 1958) as a causative factor. Liberal use of hypertonic alkali solutions is the common factor

  13. Glass lasers.

    PubMed

    Snitzer, E

    1966-10-01

    After a general discussion of the merits of glass vs. crystals as host materials for laser ions, a summary is given of the various glass lasers. Because of its importance as an efficient, room temperature laser the properties of neodymium are considered in greater detail. This includes the nonlaser properties of Nd(3+) in glass, the spectral and temporal emission characteristics of Nd(3+) lasers, and Nd(3+) laser configurations. Separate sections deal with the other two room temperature lasers which use Yb(3+) or Er(3+). The problem of thermal stability of laser cavities is also discussed. Finally, a survey is given of the glasses that are useful as Faraday rotators. PMID:20057584

  14. Low melting high lithia glass compositions and methods

    DOEpatents

    Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.

    2004-11-02

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

  15. Low melting high lithia glass compositions and methods

    DOEpatents

    Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.

    2003-10-07

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

  16. Low melting high lithia glass compositions and methods

    DOEpatents

    Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.

    2000-01-01

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

  17. Alkali activation processes for incinerator residues management.

    PubMed

    Lancellotti, Isabella; Ponzoni, Chiara; Barbieri, Luisa; Leonelli, Cristina

    2013-08-01

    Incinerator bottom ash (BA) is produced in large amount worldwide and in Italy, where 5.1 millionstons of municipal solid residues have been incinerated in 2010, corresponding to 1.2-1.5 millionstons of produced bottom ash. This residue has been used in the present study for producing dense geopolymers containing high percentage (50-70 wt%) of ash. The amount of potentially reactive aluminosilicate fraction in the ash has been determined by means of test in NaOH. The final properties of geopolymers prepared with or without taking into account this reactive fraction have been compared. The results showed that due to the presence of both amorphous and crystalline fractions with a different degree of reactivity, the incinerator BA geopolymers exhibit significant differences in terms of Si/Al ratio and microstructure when reactive fraction is considered. PMID:23756039

  18. Photochromic glass

    SciTech Connect

    Hoffmann, H.J.

    1990-12-31

    This article deals with the general properties of photochromic inorganic glasses and the darkening and regeneration dynamics as well as the main photochemical and photophysical reactions occurring in the glasses. It concludes with applications of photochromic systems to self-adjusting window panes. This controlled flow of radiant energy could lead to important energy savings by decreasing the cooling and heating loads in buildings and automobiles.

  19. Geochemistry of Darwin impact glass and target rocks

    SciTech Connect

    Meisel, T. ); Koeberl, C. Lunar and Planetary Institute, Houston, TX ); Ford, R.J. )

    1990-05-01

    The authors have analyzed the major and trace element composition of 18 Darwin glass samples and 7 target rocks from the Darwin crater area. On the basis of their data, and using statistical methods, 3 chemically distinct groups of Darwin glass were identified: A (low Fe, Al = LFe,Al, or average Darwin glass group), B (HFe,Al group), and C (HMg,Na group). The glasses of group C also show anomalous enrichments of several elements, e.g., Cr, Mn, Co, and Ni. Electron microprobe studies show that the glasses are inhomogeneous on the micrometer scale, which is typical for impact glasses. The geochemistry of all glasses is very similar to terrestrial sediments and thus supports the impact origin model. The authors have performed mixing calculations which show that in general Darwin glass can be formed by melting and mixing local target rocks. The analyses and mixing models demonstrate that volatile elements (e.g., Zn, Ga, Sb, and the alkalies) have been lost during production of the impact glasses, which can be expected because of the high formation temperature. We have furthermore tried to explain the enrichments of Cr, Mn, Co, and Ni in group C glasses by contributions from a non-sedimentary source, e.g., ultrabasic rocks, or from the impacting body. None of the mixtures provides a satisfactory fit. Thus, at the present time, we are not able to explain the enrichments of Cr, Mn, Co, and Ni in glasses of group C in a satisfactory way.

  20. A HIGH CURRENT DENSITY LI+ ALUMINO-SILICATE ION SOURCE FOR TARGET HEATING EXPERIMENTS

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.; Seidl, Peter A.; Waldron, William L.

    2011-03-23

    The NDCX-II accelerator for target heating experiments has been designed to use a large diameter ({approx_equal} 10.9 cm) Li{sup +} doped alumino-silicate source with a pulse duration of 0.5 {micro}s, and beam current of {approx_equal} 93 mA. Characterization of a prototype lithium alumino-silicate sources is presented. Using 6.35mm diameter prototype emitters (coated on a {approx_equal} 75% porous tungsten substrate), at a temperature of {approx_equal} 1275 C, a space-charge limited Li{sup +} beam current density of {approx_equal} 1 mA/cm{sup 2} was measured. At higher extraction voltage, the source is emission limited at around {approx_equal} 1.5 mA/cm{sup 2}, weakly dependent on the applied voltage. The lifetime of the ion source is {approx_equal} 50 hours while pulsing the extraction voltage at 2 to 3 times per minute. Measurements show that the life time of the ion source does not depend only on beam current extraction, and lithium loss may be dominated by neutral loss or by evaporation. The life time of a source is around {ge} 10 hours in a DC mode extraction, and the extracted charge is {approx_equal} 75% of the available Li in the sample. It is inferred that pulsed heating may increase the life time of a source.

  1. Effect of temperature and aluminium on calcium (alumino)silicate hydrate chemistry under equilibrium conditions

    SciTech Connect

    Myers, Rupert J.; L'Hôpital, Emilie; Provis, John L.; Lothenbach, Barbara

    2015-02-15

    There exists limited information regarding the effect of temperature on the structure and solubility of calcium aluminosilicate hydrate (C–A–S–H). Here, calcium (alumino)silicate hydrate (C–(A–)S–H) is synthesised at Ca/Si = 1, Al/Si ≤ 0.15 and equilibrated at 7–80 °C. These systems increase in phase-purity, long-range order, and degree of polymerisation of C–(A–)S–H chains at higher temperatures; the most highly polymerised, crystalline and cross-linked C–(A–)S–H product is formed at Al/Si = 0.1 and 80 °C. Solubility products for C–(A–)S–H were calculated via determination of the solid-phase compositions and measurements of the concentrations of dissolved species in contact with the solid products, and show that the solubilities of C–(A–)S–H change slightly, within the experimental uncertainty, as a function of Al/Si ratio and temperature between 7 °C and 80 °C. These results are important in the development of thermodynamic models for C–(A–)S–H to enable accurate thermodynamic modelling of cement-based materials.

  2. The plumber's nightmare: a new morphology in block copolymer-ceramic nanocomposites and mesoporous aluminosilicates.

    PubMed

    Finnefrock, Adam C; Ulrich, Ralph; Toombes, Gilman E S; Gruner, Sol M; Wiesner, Ulrich

    2003-10-29

    A novel cubic bicontinuous morphology is found in polymer-ceramic nanocomposites and mesoporous aluminosilicates that are derived by an amphiphilic diblock copolymer, poly(isoprene-b-ethylene oxide) (PI-b-PEO), used as a structure-directing agent for an inorganic aluminosilicate. Small-angle X-ray scattering (SAXS) was employed to unambiguously identify the Im(-)3m crystallographic symmetry of the materials by fitting individual Bragg peak positions in the two-dimensional X-ray images. Structure factor calculations, in conjunction with results from transmission electron microscopy, were used to narrow the range of possible structures consistent with the symmetry and showed the plumber's nightmare morphology to be consistent with the data. The samples are made by deposition onto a substrate that imposes a strain field, generating a lattice distortion. This distortion is quantitatively analyzed and shown to have resulted in shrinkage of the crystallites by approximately one-third in a direction perpendicular to the substrate, in both as-made composites and calcined ceramic materials. Finally, the observation of the bicontinuous block-copolymer-derived hybrid morphology is discussed in the context of a pseudo-ternary morphology diagram and compared to existing studies of ternary phase diagrams of amphiphiles in a mixture of two solvents. The calcined mesoporous materials have potential applications in the fields of catalysis, separation technology, and microelectronics. PMID:14570481

  3. Investigating the Heating of a Potassium-Doped Aluminosilicate Ion Source Using a 1 Micron Laser

    SciTech Connect

    Schmitt, R C; Meier, W R; Kwan, J W; Abbott, R P; Latkowski, J F

    2004-12-14

    The heavy ion fusion (HIF) program is interested in developing a high brightness ion source for high energy density physics (HEDP) experiments. One possible approach to obtaining higher brightness may be to raise the surface temperature of the ion source just prior to extraction. The current ion source material being studied is a layer of potassium-doped aluminosilicate bonded to a tungsten substrate. It is speculated that if the surface temperature of the source is raised above 1200 C (from a steady-state temperature of 900 C) for time periods on the order of 100's of nanoseconds, current densities of greater than 100 mA/cm{sup 2} of ions may be achievable. Typical aluminosilicate sources produce ion current densities (either K+ or Na+ ions) of {approx}10 mA/cm{sup 2} (at 1100 C). A number of heating methods might be possible, including lasers, diode arrays, and flash lamps. Here we assume laser heating. In this preliminary study, we used the LLNL RadHeat code to model the time-temperature history of the surface when hit by laser pulses and illustrate how RadHeat can be used to optimize the surface temperature response. Also of interest is the temperature history of the interface temperature between the ceramic and the metal layers. This is also investigated.

  4. Aqueous dissolution, solubilities and thermodynamic stabilities of common aluminosilicate clay minerals: Kaolinite and smectites

    USGS Publications Warehouse

    May, Howard M.; Klnniburgh, D.G.; Helmke, P.A.; Jackson, M.L.

    1986-01-01

    Determinations of the aqueous solubilities of kaolinite at pH 4, and of five smectite minerals in suspensions set between pH 5 and 8, were undertaken with mineral suspensions adjusted to approach equilibrium from over- and undersaturation. After 1,237 days, Dry Branch, Georgia kaolinite suspensions attained equilibrium solubility with respect to the kaolinite, for which Keq = (2.72 ?? 0.35) ?? 107. The experimentally determined Gibbs free energy of formation (??Gf,2980) for the kaolinite is -3,789.51 ?? 6.60 kj mol-1. Equilibrium solubilities could not be determined for the smectites because the composition of the solution phase in the smectite suspensions appeared to be controlled by the formation of gibbsite or amorphous aluminum hydroxide and not by the smectites, preventing attempts to determine valid ??Gf0 values for these complex aluminosilicate clay minerals. Reported solubility-based ??Gf0 determinations for smectites and other variable composition aluminosilicate clay minerals are shown to be invalid because of experimental deficiencies and of conceptual flaws arising from the nature of the minerals themselves. Because of the variable composition of smectites and similar minerals, it is concluded that reliable equilibrium solubilities and solubility-derived ??Gf0 values can neither be rigorously determined by conventional experimental procedures, nor applied in equilibriabased models of smectite-water interactions. ?? 1986.

  5. The effects of surface modification on the speciation of metal ions intercalated into aluminosilicates

    SciTech Connect

    Wasserman, S.R.; Giaquinta, D.M.; Yuchs, S.E.; Soderholm, L.

    1996-12-31

    Microporous aluminosilicates, including clay minerals and zeolites, are ion-exchange materials. In their most common forms, they have the ability to incorporate cationic species within their matrices. Because of this property, microporous aluminosilicates have been proposed as storage media for hazardous waste. In this paper the authors use X-ray absorption spectroscopy (XAS) to examine the structure of cations held within smectite clay minerals and to determine how modification of the surface of the clay using an organic monolayer affects the coordination of the stored cation. The effects of hydrothermal and thermal processing on the coordination of the ions contained within these systems are also investigated. The presence of the monolayer changes the surface of the clay from hydrophilic to hydrophobic. It inhibits the interlayer ions from exchanging freely into environmental water and reduces the leach rate of cations out of the clay by approximately a factor of 20. Significant changes are observed when these coated samples are treated under hydrothermal and thermal conditions. Reductions of uranium (VI), in the form of uranyl, and cupric ions occur. In addition, the uranium aggregates, forming small particles that appear similar to UO{sub 2}. Comparable conglomeration occurs with lead cations and with the reduced copper species.

  6. Ordered hexagonal mesoporous aluminosilicates with low Si/Al ratio: synthesis, characterization, and catalytic application.

    PubMed

    Liu, Aifeng; Che, Hongwei; Liu, Chuanzhi; Fu, Quanrong; Jiang, Ruijiao; Wang, Cheng; Wang, Liang

    2014-06-01

    Ordered hexagonal mesoporous aluminosilicates with lower Si/Al ratio below 5 have been successfully synthesized via the co-assembly of preformed aluminosilicate precursors with Gemini surfactant [C12H25N+(CH3)2(CH2)6N+(CH3)2C12H25] x 2Br(-) as the template. Powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, N2 adsorption-desorption isotherm measurements, Fourier transform infrared spectroscopy, 27Al nuclear magnetic resonance, thermogravimetric analysis, and temperature-programmed desorption of cyclohexylamine are employed to characterize the resulting samples. The phenol alkylation reaction is carried out to evaluate their catalytic performances. These studies indicate that the sample with a low Si/Al ratio of 3 still retains a highly ordered hexagonal mesoporous structure. And it also possesses the highest acidity of 0.96 mmol among the samples with lower Si/Al ratios below 5 due to its higher specific surface area together with more content of tetrahedrally coordinated Al in the framework. The catalytic tests confirm that the acidity of the samples plays a key role in determining their catalytic performances. PMID:24738433

  7. Development of a New Ferrous Aluminosilicate Refractory Material for Investment Casting of Aluminum Alloys

    NASA Astrophysics Data System (ADS)

    Yuan, Chen; Jones, Sam; Blackburn, Stuart

    2012-12-01

    Investment casting is a time-consuming, labour intensive process, which produces complex, high value-added components for a variety of specialised industries. Current environmental and economic pressures have resulted in a need for the industry to improve current casting quality, reduce manufacturing costs and explore new markets for the process. Alumino-silicate based refractories are commonly used as both filler and stucco materials for ceramic shell production. A new ceramic material, norite, is now being produced based on ferrous aluminosilicate chemistry, having many potential advantages when used for the production of shell molds for casting aluminum alloy. This paper details the results of a direct comparison made between the properties of a ceramic shell system produced with norite refractories and a typical standard refractory shell system commonly used in casting industry. A range of mechanical and physical properties of the systems was measured, and a full-scale industrial casting trial was also carried out. The unique properties of the norite shell system make it a promising alternative for casting aluminum based alloys in the investment foundry.

  8. Corrosion behavior of a glass-bonded sodalite ceramic waste form and its constituents.

    SciTech Connect

    Lewis, M. A.; Ebert, W. L.; Morss, L.

    1999-06-18

    A ceramic waste form (CWF) of glass bonded sodalite is being developed as a waste form for the long-term immobilization of fission products and transuranic elements from the U.S. Department of Energy's activities on spent nuclear fuel conditioning. A durable waste form was prepared by hot isostatic pressing (HIP) a mixture of salt-loaded zeolite powders and glass frit. During HIP the zeolite is converted to sodalite, and the resultant CWF is been completed for durations of up to 182 days. Four dissolution modes were identified: dissolution of free salt, dissolution of the aluminosilicate matrix of sodalite and the accompanying dissolution of occluded salt, dissolution of the boroaluminosilicate matrix of the glass, and ion exchange. Synergies inherent to the CWF were identified by comparing the results of the tests with pure glass and sodalite with those of the composite CWF.

  9. Chromium liquid waste inertization in an inorganic alkali activated matrix: leaching and NMR multinuclear approach.

    PubMed

    Ponzoni, Chiara; Lancellotti, Isabella; Barbieri, Luisa; Spinella, Alberto; Saladino, Maria Luisa; Martino, Delia Chillura; Caponetti, Eugenio; Armetta, Francesco; Leonelli, Cristina

    2015-04-01

    A class of inorganic binders, also known as geopolymers, can be obtained by alkali activation of aluminosilicate powders at room temperature. The process is affected by many parameters (curing time, curing temperature, relative humidity etc.) and leads to a resistant matrix usable for inertization of hazardous waste. In this study an industrial liquid waste containing a high amount of chromium (≈ 2.3 wt%) in the form of metalorganic salts is inertized into a metakaolin based geopolymer matrix. One of the innovative aspects is the exploitation of the water contained in the waste for the geopolymerization process. This avoided any drying treatment, a common step in the management of liquid hazardous waste. The evolution of the process--from the precursor dissolution to the final geopolymer matrix hardening--of different geopolymers containing a waste amount ranging from 3 to 20%wt and their capability to inertize chromium cations were studied by: i) the leaching tests, according to the EN 12,457 regulation, at different curing times (15, 28, 90 and 540 days) monitoring releases of chromium ions (Cr(III) and Cr(VI)) and the cations constituting the aluminosilicate matrix (Na, Si, Al); ii) the humidity variation for different curing times (15 and 540 days); iii) SEM characterization at different curing times (28 and 540 days); iv) the trend of the solution conductivity and pH during the leaching test; v) the characterization of the short-range ordering in terms of TOT bonds (where T is Al or Si) by (29)Si and (27)Al solid state magic-angle spinning nuclear magnetic resonance (ss MAS NMR) for geopolymers containing high amounts of waste (10-20%wt). The results show the formation of a stable matrix after only 15 days independently on the waste amount introduced; the longer curing times increase the matrices stabilities and their ability to immobilize chromium cations. The maximum amount of waste that can be inertized is around 10 wt% after a curing time of 28 days

  10. Physics and chemistry of alkali-silica reactions

    SciTech Connect

    Diamond, S.; Barneyback, R.S. Jr.; Struble, L.J.

    1981-01-01

    The philosophy underlying recent research on alkali-silica reactions is reviewed and illustrations of recent results are provided. It has been possible to follow the kinetics of the chemical reaction between dissolved alkalis and opal in mortars by monitoring the rate at which alkalis are removed from the pore solutions of reacting mortars. Studies of the expansion behavior of synthetic alkali silica gels under controlled conditions were carried out and show no obvious correlation to chemical composition. The alkali reaction in mortars was found to produce changes in the appearance of opal grains documentable by the use of a scanning electron microscope.

  11. Calcium-Alkali Syndrome in the Modern Era

    PubMed Central

    Patel, Ami M.; Adeseun, Gbemisola A.; Goldfarb, Stanley

    2013-01-01

    The ingestion of calcium, along with alkali, results in a well-described triad of hypercalcemia, metabolic alkalosis, and renal insufficiency. Over time, the epidemiology and root cause of the syndrome have shifted, such that the disorder, originally called the milk-alkali syndrome, is now better described as the calcium-alkali syndrome. The calcium-alkali syndrome is an important cause of morbidity that may be on the rise, an unintended consequence of shifts in calcium and vitamin D intake in segments of the population. We review the pathophysiology of the calcium-alkali syndrome. PMID:24288027

  12. Properties of Desert Sand and CMAS Glass

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Choi, Sung R.

    2014-01-01

    As-received desert sand from a Middle East country has been characterized for its phase composition and thermal stability. X-ray diffraction analysis showed the presence of quartz (SiO2), calcite (CaCO3), gypsum (CaSO4.2H2O), and NaAlSi3O8 phases in as-received desert sand and showed weight loss of approx. 35 percent due to decomposition of CaCO3 and CaSO4.2H2O when heated to 1400 C. A batch of as-received desert sand was melted into calcium magnesium aluminosilicate (CMAS) glass at approx. 1500 C. From inductively coupled plasma-atomic emission spectrometry, chemical composition of the CMAS glass was analyzed to be 27.8CaO-4MgO-5Al2O3-61.6SiO2-0.6Fe2O3-1K2O (mole percent). Various physical, thermal and mechanical properties of the glass have been evaluated. Bulk density of CMAS glass was 2.69 g/cc, Young's modulus 92 GPa, Shear modulus 36 GPa, Poisson's ratio 0.28, dilatometric glass transition temperature (T (sub g)) 706 C, softening point (T (sub d)) 764 C, Vickers microhardness 6.3 +/- 0.4 GPa, indentation fracture toughness 0.75 +/- 0.15 MPa.m (sup 1/2), and coefficient of thermal expansion (CTE) 9.8 x 10 (exp -6)/degC in the temperature range 25 to 700 C. Temperature dependence of viscosity has also been estimated from various reference points of the CMAS glass using the Vogel-Fulcher-Tamman (VFT) equation. The glass remained amorphous after heat treating at 850 C for 10 hr but crystallized into CaSiO3 and Ca-Mg-Al silicate phases at 900 C or higher temperatures. Crystallization kinetics of the CMAS glass has also been investigated by differential thermal analysis (DTA). Activation energies for the crystallization of two different phases in the glass were calculated to be 403 and 483 kJ/mol, respectively.

  13. Alkali metal recovery from carbonaceous material conversion process

    DOEpatents

    Sharp, David W.; Clavenna, LeRoy R.; Gorbaty, Martin L.; Tsou, Joe M.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced in the gasifier or similar reaction zone, alkali metal constitutents are recovered from the particles by withdrawing and passing the particles from the reaction zone to an alkali metal recovery zone in the substantial absence of molecular oxygen and treating the particles in the recovery zone with water or an aqueous solution in the substantial absence of molecular oxygen. The solution formed by treating the particles in the recovery zone will contain water-soluble alkali metal constituents and is recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preventing contact of the particles with oxygen as they are withdrawn from the reaction zone and during treatment in the recovery zone avoids the formation of undesirable alkali metal constituents in the aqueous solution produced in the recovery zone and insures maximum recovery of water-soluble alkali metal constituents from the alkali metal residues.

  14. Effect of variable valence impurities on the formation of bismuth-related optical centres in a silicate glass

    SciTech Connect

    Galagan, B I; Denker, B I; Lili Hu; Sverchkov, S E; Shulman, I L; Dianov, Evgenii M

    2012-10-31

    We have studied the effect of variable valence impurities (cerium and iron) on the formation of bismuth-related IR luminescence centres and the optical loss between 1000 and 1300 nm in a magnesium aluminosilicate glass. The results demonstrate that additional doping of the glass with ceria leads to effective bleaching in a wide spectral range, including the luminescence range of the bismuth centres. At the same time, ceria reduces the concentration of luminescence centres. Gamma irradiation of the glass bleached by cerium restores the luminescence centres but leads to a background loss in a wide spectral range. Iron is shown to be a very harmful impurity in bismuth-doped active media: even trace levels of iron prevent the formation of bismuth-related active centres in the glass and produce a strong, broad absorption band centred near 1 {mu}m. (luminescence of glasses)

  15. Geopolymers prepared from DC plasma treated air pollution control (APC) residues glass: properties and characterisation of the binder phase.

    PubMed

    Kourti, Ioanna; Devaraj, Amutha Rani; Bustos, Ana Guerrero; Deegan, David; Boccaccini, Aldo R; Cheeseman, Christopher R

    2011-11-30

    Air pollution control (APC) residues have been blended with glass-forming additives and treated using DC plasma technology to produce a high calcium aluminosilicate glass (APC glass). This has been used to form geopolymer-glass composites that exhibit high strength and density, low porosity, low water absorption, low leaching and high acid resistance. The composites have a microstructure consisting of un-reacted residual APC glass particles imbedded in a complex geopolymer and C-S-H gel binder phase, and behave as particle reinforced composites. The work demonstrates that materials prepared from DC plasma treated APC residues have potential to be used to form high quality pre-cast products. PMID:21963174

  16. Ultrapure glass optical waveguide development in microgravity by the sol-gel process

    NASA Technical Reports Server (NTRS)

    Mukherjee, S. P.

    1980-01-01

    The alkali-borosilicate system was selected as the glass system for the preparation of ultrapure low loss glasses suitable for optical communication. The effect of different oxide contents on the absorption loss was critically reviewed. One composition was chosen to develop the gel preparation procedure in the alkali-borosilicate system. In addition, several procedures for the preparation of gels based on two different approaches were developed. The influence of different preparation parameters were investigated qualitatively. Several conclusions are drawn from the results.

  17. Subtask 6.6 - SiAION Coatings for Alkali-Resistant Silicon Nitride. Topical report

    SciTech Connect

    1997-02-25

    The efficiency of a gas turbine can be improved by increasing operating temperature. Construction materials should both meet high strength requirements and exhibit hot alkali corrosion resistance. Structural ceramics based on silicon nitride are promising candidates for high temperature engineering applications because of their high strength and good resistance to corrosion. Their performance varies significantly with the mechanical properties of boundary phases which, in turn, depend on their chemical composition, thickness of the amorphous phase, and the deformation process. To make silicon nitride ceramics tough, SiAlON ceramics were developed with controlled crystallization of the amorphous grain boundary phase. Crystallization of the grain boundary glass improves the high temperature mechanical properties of silicon nitride ceramics. Thus, the knowledge of silicon oxynitride ceramics corrosion behavior in Na{sub 2}SO{sub 4} becomes important for engineers in designing appropriate part for turbines working at high temperatures. So far there has been no report concerning alkali attack on SiAlON ceramics in the presence of SO{sub 2} and chlorine in flue gas. The goal of this project was to investigate alkali corrosion of SiAlON-Y structural ceramics under combustion conditions in the presence of sodium derived components.

  18. Effect of alkali lignins with different molecular weights from alkali pretreated rice straw hydrolyzate on enzymatic hydrolysis.

    PubMed

    Li, Yun; Qi, Benkun; Luo, Jianquan; Wan, Yinhua

    2016-01-01

    This study investigated the effect of alkali lignins with different molecular weights on enzymatic hydrolysis of lignocellulose. Different alkali lignins fractions, which were obtained from cascade ultrafiltration, were added into the dilute acid pretreated (DAP) and alkali pretreated (AP) rice straws respectively during enzymatic hydrolysis. The results showed that the addition of alkali lignins enhanced the hydrolysis and the enhancement for hydrolysis increased with increasing molecular weights of alkali lignins, with maximum enhancement being 28.69% for DAP and 20.05% for AP, respectively. The enhancement was partly attributed to the improved cellulase activity, and filter paper activity increased by 18.03% when adding lignin with highest molecular weight. It was found that the enhancement of enzymatic hydrolysis was correlated with the adsorption affinity of cellulase on alkali lignins, and the difference in surface charge and hydrophobicity of alkali lignins were responsible for the difference in affinity between cellulase and lignins. PMID:26496216

  19. Removal of Retired Alkali Metal Test Systems

    SciTech Connect

    BREHM, W.F.

    2003-01-01

    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  20. Removal of Retired Alkali Metal Test Systems

    SciTech Connect

    Brehm, W. F.; Church, W. R.; Biglin, J. W.

    2003-02-26

    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  1. Crack-resistant Al2O3-SiO2 glasses.

    PubMed

    Rosales-Sosa, Gustavo A; Masuno, Atsunobu; Higo, Yuji; Inoue, Hiroyuki

    2016-01-01

    Obtaining "hard" and "crack-resistant" glasses have always been of great important in glass science and glass technology. However, in most commercial glasses both properties are not compatible. In this work, colorless and transparent xAl2O3-(100-x)SiO2 glasses (30 ≤ x ≤ 60) were fabricated by the aerodynamic levitation technique. The elastic moduli and Vickers hardness monotonically increased with an increase in the atomic packing density as the Al2O3 content increased. Although a higher atomic packing density generally enhances crack formation in conventional oxide glasses, the indentation cracking resistance increased by approximately seven times with an increase in atomic packing density in binary Al2O3-SiO2 glasses. In particular, the composition of 60Al2O3 • 40SiO2 glass, which is identical to that of mullite, has extraordinary high cracking resistance with high elastic moduli and Vickers hardness. The results indicate that there exist aluminosilicate compositions that can produce hard and damage-tolerant glasses. PMID:27053006

  2. Crack-resistant Al2O3–SiO2 glasses

    PubMed Central

    Rosales-Sosa, Gustavo A.; Masuno, Atsunobu; Higo, Yuji; Inoue, Hiroyuki

    2016-01-01

    Obtaining “hard” and “crack-resistant” glasses have always been of great important in glass science and glass technology. However, in most commercial glasses both properties are not compatible. In this work, colorless and transparent xAl2O3–(100–x)SiO2 glasses (30 ≤ x ≤ 60) were fabricated by the aerodynamic levitation technique. The elastic moduli and Vickers hardness monotonically increased with an increase in the atomic packing density as the Al2O3 content increased. Although a higher atomic packing density generally enhances crack formation in conventional oxide glasses, the indentation cracking resistance increased by approximately seven times with an increase in atomic packing density in binary Al2O3–SiO2 glasses. In particular, the composition of 60Al2O3•40SiO2 glass, which is identical to that of mullite, has extraordinary high cracking resistance with high elastic moduli and Vickers hardness. The results indicate that there exist aluminosilicate compositions that can produce hard and damage-tolerant glasses. PMID:27053006

  3. Crack-resistant Al2O3–SiO2 glasses

    NASA Astrophysics Data System (ADS)

    Rosales-Sosa, Gustavo A.; Masuno, Atsunobu; Higo, Yuji; Inoue, Hiroyuki

    2016-04-01

    Obtaining “hard” and “crack-resistant” glasses have always been of great important in glass science and glass technology. However, in most commercial glasses both properties are not compatible. In this work, colorless and transparent xAl2O3–(100–x)SiO2 glasses (30 ≤ x ≤ 60) were fabricated by the aerodynamic levitation technique. The elastic moduli and Vickers hardness monotonically increased with an increase in the atomic packing density as the Al2O3 content increased. Although a higher atomic packing density generally enhances crack formation in conventional oxide glasses, the indentation cracking resistance increased by approximately seven times with an increase in atomic packing density in binary Al2O3–SiO2 glasses. In particular, the composition of 60Al2O3•40SiO2 glass, which is identical to that of mullite, has extraordinary high cracking resistance with high elastic moduli and Vickers hardness. The results indicate that there exist aluminosilicate compositions that can produce hard and damage-tolerant glasses.

  4. Preparation and characterization of cesium-137 aluminosilicate pellets for radioactive source applications

    SciTech Connect

    Schultz, F.J.; Tompkins, J.A.; Haff, K.W.; Case, F.N.

    1981-07-01

    Twenty-seven fully loaded /sup 137/Cs aluminosilicate pellets were fabricated in a hot cell by the vacuum hot pressing of a cesium carbonate/montmorillonite clay mixture at 1500/sup 0/C and 570 psig. Four pellets were selected for characterization studies which included calorimetric measurements, metallography, scanning electron microscope and electron backscattering (SEM-BSE), electron microprobe, x-ray diffraction, and cesium ion leachability measurements. Each test pellet contained 437 to 450 curies of /sup 137/Cs as determined by calorimetric measurements. Metallographic examinations revealed a two-phase system: a primary, granular, gray matrix phase containing large and small pores and small pore agglomerations, and a secondary fused phase interspersed throughout the gray matrix. SEM-BSE analyses showed that cesium and silicon were uniformly distributed throughout both phases of the pellet. This indicated that the cesium-silicon-clay reaction went to completion. Aluminum homogeneity was unconfirmed due to the high background noise associated with the inherent radioactivity of the test specimens. X-ray diffraction analyses of both radioactive and non-radioactive aluminosilicate pellets confirmed the crystal lattice structure to be pollucite. Cesium ion quasistatic leachability measurements determined the leach rates of fully loaded /sup 137/Cs sectioned pollucite pellets to date to be 4.61 to 34.4 x 10/sup -10/ kg m/sup -2/s/sup -1/, while static leach tests performed on unsectioned fully loaded pellets showed the leach rates of the cesium ion to date to be 2.25 to 3.41 x 10/sup -12/ kg m/sup -2/s/sup -1/. The cesium ion diffusion coefficients through the pollucite pellet were calculated using Fick's first and second laws of diffusion. The diffusion coefficients calculated for three tracer level /sup 137/Cs aluminosilicate pellets were 1.29 x 10/sup -16/m/sup 2/s/sup -1/, 6.88 x 10/sup -17/m/sup 2/s/sup -1/, and 1.35 x 10/sup -17/m/sup 2/s/sup -1/, respectively.

  5. The Valence State of Silicon and Redox Dynamics in Aluminosilicate Melts

    NASA Astrophysics Data System (ADS)

    Cooper, R. F.; Pettersen, C.; Everman, R. L.

    2005-12-01

    Physicists have long been aware of the many valence states of Si and the roles these play in the kinetics of thermal oxidation of Si single crystals and the molecular structure of the amorphous oxide film (e.g., Borman et al., 1991). Similarly, the dynamics of oxidation and of vaporization of SiC are also affected by the presence of Si2+ in the amorphous silica surface film (e.g., Dunham et al., 1998; Mendybaev et al., 2002). Nevertheless, Si2+,4+ heterovalency is little considered in redox studies of silicate melts as reported in the petrology literature. We have performed experiments in which a liquid bronze (Cu,Sn) alloy was reacted with (1) a magnesium aluminosilicate melt and (2) a Zn2+-doped magnesium aluminosilicate melt, all done at a low oxygen fugacity (sufficient to keep the metal alloy from oxidizing in reaction with the gas environment). The driving potential for metal melt-silicate melt reaction has two components: (a) reduction of the silicate melt and oxidation of the metal alloy; (b) formation of a homogeneous silicate solution that incorporates ionic Cu and Sn. The reaction morphologies present compelling evidence that Si4+ in the silicate melt is reduced in part to Si2+, initially so as to incorporate Cu+,2+ into the melt; as the reaction proceeds, however, the Si2+ mobility becomes important in charge-compensation of the "inward" flux of Sn2+. Addition of Zn2+ to the starting silicate melt forces a spatially periodic variation in the silicate melt structure (as suggested by the chemistry) as the reaction proceeds. In separate experiments, reduction of an FeO-bearing calcium-magnesium aluminosilicate melt in a CO-rich environment creates a reaction morphology suggestive of reduction of Si4+ to facilitate the incorporation of carbonate ions into the melt. These experiments are perhaps exotic; nevertheless, they provoke the consideration of the potential role(s) played by silicon valence in any "self-buffering" process associated with the evolution

  6. Technical improvements in 19th century Belgian window glass production

    NASA Astrophysics Data System (ADS)

    Lauriks, Leen; Collette, Quentin; Wouters, Ine; Belis, Jan

    Glass was used since the Roman age in the building envelope, but it became widely applied together with iron since the 19th century. Belgium was a major producer of window glass during the nineteenth century and the majority of the produced window glass was exported all over the world. Investigating the literature on the development of 19th century Belgian window glass production is therefore internationally relevant. In the 17th century, wood was replaced as a fuel by coal. In the 19th century, the regenerative tank furnace applied gas as a fuel in a continuous glass production process. The advantages were a clean production, a more constant and higher temperature in the furnace and a fuel saving. The French chemist Nicolas Leblanc (1787-1793) and later the Belgian chemist Ernest Solvay (1863) invented processes to produce alkali out of common salt. The artificial soda ash improved the quality and aesthetics of the glass plates. During the 19th century, the glass production was industrialized, influencing the operation of furnaces, the improvement of raw materials as well as the applied energy sources. Although the production process was industrialized, glassblowing was still the work of an individual. By improving his work tools, he was able to create larger glass plates. The developments in the annealing process followed this evolution. The industry had to wait until the invention of the drawn glass in the beginning of the 20th century to fully industrialise the window glass manufacture process.

  7. Quantum magnetism of alkali Rydberg atoms

    NASA Astrophysics Data System (ADS)

    Malinovskaya, Svetlana; Liu, Gengyuan

    2016-05-01

    We discuss a method to control dynamics in many-body spin states of 87Rb Rydberg atoms. The method permits excitation of cold gases and form ordered structures of alkali atoms. It makes use of a two-photon excitation scheme with circularly polarized and linearly chirped pulses. The method aims for controlled quantum state preparation in large ensembles. It is actual for experiments studding the spin hopping dynamics and realization of quantum random walks.

  8. Alkali Metal Heat Pipe Life Issues

    NASA Technical Reports Server (NTRS)

    Reid, Robert S.

    2004-01-01

    One approach to space fission power system design is predicated on the use of alkali metal heat pipes, either as radiator elements, thermal management components, or as part of the core primary heat-transfer system. This synopsis characterizes long-life core heat pipes. References are included where more detailed information can be found. Specifics shown here are for demonstrational purposes and do not necessarily reflect current Project Prometheus point designs.

  9. Alkali metal protective garment and composite material

    SciTech Connect

    Ballif, J.L.; Yuan, W.W.

    1980-09-16

    A protective garment and composite material providing satisfactory heat resistance and physical protection for articles and personnel exposed to hot molten alkali metals, such as sodium are described. Physical protection is provided by a continuous layer of nickel foil. Heat resistance is provided by an underlying backing layer of thermal insulation. Overlying outer layers of fireproof woven ceramic fibers are used to protect the foil during storage and handling.

  10. Alkali metal protective garment and composite material

    SciTech Connect

    Ballif, III, John L.; Yuan, Wei W.

    1980-01-01

    A protective garment and composite material providing satisfactory heat resistance and physical protection for articles and personnel exposed to hot molten alkali metals, such as sodium. Physical protection is provided by a continuous layer of nickel foil. Heat resistance is provided by an underlying backing layer of thermal insulation. Overlying outer layers of fireproof woven ceramic fibers are used to protect the foil during storage and handling.

  11. The influence of fiber/matrix interface on the mechanical behavior of Nicalon SiC fiber reinforced glass-ceramic composites

    SciTech Connect

    Liu, Y.M.; Mitchell, T.E.; Wadley, H.N.G.

    1996-11-01

    Mechanical properties of unidirectional Nicalon SiC fiber reinforced Ca aluminosilicate (CAS/SiC) and Mg aluminosilicate (MAS/SiC) glass-ceramic composites were investigated by tensile testing and nondestructive laser-ultrasound technique. The Ba-stuffed MAS was either undoped or doped with 5% borosilicate glass. Degradation of elastic stiffness constant C{sub 11} in transverse direction due to interface damage was monitored in situ by measuring the laser- generated ultrasound wave velocity. The three composite materials show different characteristics of macroscopic deformation behavior, which is correlated strongly to interface degradation. A stronger reduction trend of the elastic constant C{sub 11} is associated with a larger degree of inelastic deformation. The fracture surfaces also reveal the close relation between fiber pullout length and interfacial characteristics. Interfaces of these composites were studied by TEM; their influence on inhibiting and deflecting matrix cracks is discussed.

  12. Study of superconducting state parameters of alkali alkali binary alloys by a pseudopotential

    NASA Astrophysics Data System (ADS)

    Vora, Aditya M.

    2006-12-01

    A detailed study of the superconducting state parameters (SSP) viz. electron-phonon coupling strength λ, Coulomb pseudopotential μ∗, transition temperature TC, isotope effect exponent α and effective interaction strength N OV of ten alkali-alkali binary alloys i.e. Li 1- xNa x, Li 1- xK x, Li 1- xRb x, Li 1- xCs x, Na 1- xK x, Na 1- xRb x, Na 1- xCs x, K 1- xRb x, K 1- xCs x and Rb 1- xCs x are made within the framework of the model potential formalism and employing the pseudo-alloy-atom (PAA) model for the first time. We use the Ashcroft’s empty core (EMC) model potential for evaluating the superconducting properties of alkali alloys. Five different forms of local field correction functions viz. Hartree (H), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F) and Sarkar et al. (S) are used to incorporate the exchange and correlation effects. A considerable influence of various exchange and correlation functions on λ and μ∗ is found from the present study. Reasonable agreement with the theoretical values of the SSP of pure components is found (corresponding to the concentration x = 0 or 1). It is also concluded that nature of the SSP strongly depends on the value of the atomic volume Ω0 of alkali-alkali binary alloys.

  13. Transport properties of alkali metal doped fullerides

    SciTech Connect

    Yadav, Daluram Yadav, Nishchhal

    2015-07-31

    We have studied the intercage interactions between the adjacent C{sub 60} cages and expansion of lattice due to the intercalation of alkali atoms based on the spring model to estimate phonon frequencies from the dynamical matrix for the intermolecular alkali-C{sub 60} phonons. We considered a two-peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. Coulomb repulsive parameter and the electron phonon coupling strength are obtained within the random phase approximation. Transition temperature, T{sub c}, is obtained in a situation when the free electrons in lowest molecular orbital are coupled with alkali-C{sub 60} phonons as 5 K, which is much lower as compared to reported T{sub c} (20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. The importance of the present study, the pressure effect and normal state transport properties are calculated within the same model leading superconductivity.

  14. Transport properties of alkali metal doped fullerides

    NASA Astrophysics Data System (ADS)

    Yadav, Daluram; Yadav, Nishchhal

    2015-07-01

    We have studied the intercage interactions between the adjacent C60 cages and expansion of lattice due to the intercalation of alkali atoms based on the spring model to estimate phonon frequencies from the dynamical matrix for the intermolecular alkali-C60 phonons. We considered a two-peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. Coulomb repulsive parameter and the electron phonon coupling strength are obtained within the random phase approximation. Transition temperature, Tc, is obtained in a situation when the free electrons in lowest molecular orbital are coupled with alkali-C60 phonons as 5 K, which is much lower as compared to reported Tc (20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. The importance of the present study, the pressure effect and normal state transport properties are calculated within the same model leading superconductivity.

  15. Ion Pairing in Alkali Nitrate Electrolyte Solutions.

    PubMed

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin

    2016-03-10

    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 < NaNO3 < KNO3. Such results explain the salt activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities. PMID:26901167

  16. Pinhole Glasses

    NASA Astrophysics Data System (ADS)

    Colicchia, Giuseppe; Hopf, Martin; Wiesner, Hartmut; Zollman, Dean

    2008-01-01

    Eye aberrations are commonly corrected by lenses that restore vision by altering rays before they pass through the cornea. Some modern promoters claim that pinhole glasses are better than conventional lenses in correcting all kinds of refractive defects such as myopia (nearsighted), hyperopia (farsighted), astigmatisms, and presbyopia. Do pinhole glasses really give better vision? Some ways to use this question for motivation in teaching optics have been discussed. For this column we include a series of experiments that students can complete using a model of the eye and demonstrate issues related to pinhole vision correction.

  17. Structure and Chemistry in Halide Lead-Tellurite Glasses

    SciTech Connect

    McCloy, John S.; Riley, Brian J.; Lipton, Andrew S.; Windisch, Charles F.; Washton, Nancy M.; Olszta, Matthew J.; Rodriguez, Carmen P.

    2013-02-11

    A series of TeO2-PbO glasses were fabricated with increasing fractions of mixed alkali, alkaline earth, and lanthanide chlorides. The glass and crystal structure was studied with Raman spectroscopy, nuclear magnetic resonance (NMR), X-ray diffraction, and electron microscopy. As the chloride fraction increased, the medium-range order in the glass decreased up to a critical point (~14 mass% of mixed chlorides), above which the glasses became phase-separated. Resulting phases are a TeO2/PbO-rich phase and a crystalline phase rich in alkali chlorides. The 125Te NMR indicates, contrary to previous studies, that Te site distribution did not change with increased concentrations of M+, M2+, and M3+ cations, but rather is controlled by the Te/Pb molar ratio. The 207Pb NMR shows that two Pb species exist and their relative concentration changes nearly linearly with addition of the mixed chlorides, indicating that the additives to the TeO2-PbO glass are accommodated by changing the Pb species. The 23Na and 35Cl NMR indicate that Na and Cl are distributed in the single-phase glass phase up to the critical point, and at higher concentrations partition to crystalline phases. Transmission electron microscopy shows that the sample at the critical point contains ~10 nm seed nuclei that increase in size and concentration with exposure to the electron beam.

  18. Constraining 17O and 27Al NMR spectra of high-pressure crystals and glasses: New data for jadeite, pyrope, grossular, and mullite

    USGS Publications Warehouse

    Kelsey, K.E.; Stebbins, J.F.; Du, L.-S.; Hankins, B.

    2007-01-01

    The 17O NMR spectra of glasses quenched from melts at high pressure are often difficult to interpret due to overlapping peaks and lack of crystalline model compounds. High-pressure aluminosilicate glasses often contain significant amounts of [5]Al and [6]Al, thus these high-pressure glasses must contain oxygen bonded to high-coordinated aluminum. The 17O NMR parameters for the minerals jadeite, pyrope, grossular, and mullite are presented to assist interpretation of glass spectra and to help test quantum chemical calculations. The 17O NMR parameters for jadeite and grossular support previous peak assignments of oxygen bonded to Si and high-coordinated Al in high-pressure glasses as well as quantum chemical calculations. The oxygen tricluster in mullite is very similar to the previously observed tricluster in grossite (CaAl4 O7) and suspected triclusters in glasses. We also present 27Al NMR spectra for pyrope, grossular, and mullite.

  19. Interactions between C.I. Basic Blue 41 and aluminosilicate sorbents.

    PubMed

    Roulia, Maria; Vassiliadis, Alexandros A

    2005-11-01

    Four aluminosilicate sorbents (montmorillonite, bentonite, raw perlite, and expanded perlite) were employed for retention of the cationic dye C.I. Basic Blue 41. Interactions between the clay and the dyestuff were investigated at several temperatures and clay:dye ratios. The mechanism behind the adsorption involves the formation of H-aggregates of the dye on both clays, followed by dye migration into the interlayer in the case of montmorillonite. Time-dependent absorbance spectra revealed the presence of various dye species in montmorillonite. Introduction of the dye molecules into the interlamellar space occurs more rapidly in bentonite than in montmorillonite. The dye molecules inserted between the clay leaves adopt different orientations and, eventually, stack in layers at increased dye loadings for both montmorillonite and bentonite. Higher dye aggregates are then present as suggested by diffuse reflectance spectroscopy. Dye sorption on both raw and expanded perlite proceeds via H-aggregate formation as well. PMID:15990108

  20. A facile strategy to recycle template P123 from mesoporous aluminosilicates by ultrasonic extraction.

    PubMed

    Jin, Jun-su; Cao, Li; Su, Guang-xun; Xu, Chun-yan; Zhang, Ze-ting; Gao, Xiong-hou; Liu, Hong-hai; Liu, Hong-tao

    2014-09-01

    High synthesis cost of mesoporous aluminosilicates (MA) limits their practical application. Recycling of copolymer template employed in preparation of MA is an effective way to reduce the synthesis cost. An ultrasonic extraction strategy for recycling of organic template P123 in MAs is reported. Effects of different extraction parameters on P123 recovery are investigated and the optimum conditions are obtained. 75.0% P123 is recovered from MAs within 10 min by one-step ultrasonication. Characterizations indicated that the resulting P123-free MA (MA-U) exhibits excellent properties compared with that of calcined products. Moreover, recovered P123 can be employed to synthesize high hydrothermally stable MA. This investigation provides a facile strategy to recycle P123 from MA. PMID:24703432