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Sample records for alkali silicate glass

  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. 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).

  3. Structural and volume changes and their correlation in electron irradiated alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    Gavenda, Tadeáš; Gedeon, Ondrej; Jurek, Karel

    2017-04-01

    Two binary alkali silicate glasses (15K2O·85SiO2 - denoted as K15 and 15Li2O·85SiO2 - denoted as Li15) were irradiated by 50 keV electron beams with doses within the range of 2.1-15.9 kC/m2. Volume changes induced by electron irradiation were monitored by means of Atomic Force Microscopy (AFM). Raman spectra were taken from the irradiated spots to observe structural changes. Volume compaction observed at lower doses was correlated with the increase of the D2 peak. Volume expansion at higher doses was related to migration of alkali ions. Irradiated glasses were annealed at 400 °C and 500 °C for 60 min. After annealing irradiated spots were again examined by AFM and Raman spectroscopy in order to determine volume and structural relaxation of radiation induced changes. Annealing at higher temperatures resulted in the levelling of the pits created by irradiation, but only for doses below incubation dose. The pits created by doses above incubation dose were not levelled. Annealing caused decrease of D2 peak and shift of the Si-O-Si vibrations band in direction to original structure. Low-frequency region of annealed Li15 glass was undistinguishable from that of pristine glass, while annealing of K15 glass did not result in the full reversion to the original shape. The differences between glasses were attributed to higher Tg of K15 glass. Q-motives bands of both glasses were not completely restored after annealing due to the absence of alkali ions.

  4. Formation of alkali-metal nanoparticles in alkali-silicate glasses under electron irradiation and thermal processing

    NASA Astrophysics Data System (ADS)

    Bochkareva, E. S.; Sidorov, A. I.; Ignat'ev, A. I.; Nikonorov, N. V.; Podsvirov, O. A.

    2017-02-01

    Experiments and numerical simulation show that the irradiation of alkali-containing glasses using electrons at an energy of 35 keV and the subsequent thermal processing at a temperature above the vitrification point lead to the formation of spherical metal (lithium, sodium, and potassium) nanoparticles with oxide sheaths that exhibit plasmon resonances in the visible spectral range. Glasses containing two alkali metals exhibit mutual effect of metals on the formation of nanoparticles with two compositions due to the difference of ion radii and mobilities of metal ions.

  5. 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.

  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. 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.

  8. 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.

  9. Effects of chemical composition on the environments of D+ and H+ in alkali silicate glasses: with implications for D/H fractionation in magmatic processes

    NASA Astrophysics Data System (ADS)

    Le Losq, C.; Cody, G. D.; Mysen, B. O.

    2014-12-01

    The δD is an important probe for studying the cycle of water within the Earth and between planetary bodies. D/H fractionation between silicate melts, minerals, aqueous fluids and gases governed the δD-evolution of the various geochemical reservoirs. It is usually assumed that D+ and H+ have the same chemical properties and structural environments in silicate melts and aqueous fluids, so that the only mass-dependent fractionation takes place with values approaching 1 at magmatic temperatures. However, recent in situ studies reveal important D/H fractionation between silicate melts and aqueous fluids even at high temperature. H and D MAS NMR data from sodium silicate glasses also shown that D+ and H+ occupy different structural positions in the structure of silicate glasses. This suggests that mass-dependent fractionation is not the only factor governing D/H fractionation in magmatic systems. To assess how the chemical composition and the structure of alkali silicate glasses affect the environments of H+ and D+, the H and D MAS NMR spectra of M2Si4O9 glasses (M = Li, Na or K) with different concentrations of pure H2O or D2O (from 3.3 up to 17.6 mol%) were recorded. Other spectra were acquired from M2Si4O9 glasses with 17.6 mol%(1H,1D)2O. Signals at ~1, ~3.5, ~5, ~12 and ~16 ppm in 1H MAS NMR spectra are assigned to H+ in H2O molecules and Si-OH groups in the glasses. These five signals indicates protons distribution between at least five environments with O…O distances ranging from ~305 to ~240 pm. The ionic radius of alkali affects the distribution of H+ between those environments. D MAS NMR spectra reveal that by exchanging H+ with D+, the intensity of the 16 ppm NMR line increases, whereas the intensity of the 5 ppm line decreases. Consequently, D+ seems to be more concentrated than H+ in environments with small O...O distances. In other words, the structural environments of H+ and D+ in the silicate glasses, and hence in melts at their glass transition

  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. Improved alkali-metal/silicate binders

    NASA Technical Reports Server (NTRS)

    Schutt, J.

    1978-01-01

    Family of inorganic binders utilizes potassium or sodium oxide/silicate dispersion and employs high mole ratio of silicon dioxide to alkali-metal binder. Binders are stable, inexpensive, extremely water resistant, and easy to apply.

  12. Molecular dynamics simulation of silicate glasses and their surfaces

    NASA Astrophysics Data System (ADS)

    Yuan, Xianglong

    1999-12-01

    The bulk and surface structures of vitreous silica and silicate glasses have been modeled using the molecular dynamics technique. An extensive preliminary study, on the influences of different potential models and of different simulation approaches on the final bulk and surface structures, concludes that good result can be obtained using the constant volume simulation with a modified pair-wise potential from van Beest and coworkers, together with alkali-oxygen potential models developed in this study. Glass structures with the reliability factors, Rchi of 7.2% for vitreous silica and 5.6% for sodium silicate have been achieved. The environments of O, Si and Na in silicate glasses have been thoroughly examined. Considerable similarities in local structures exist between crystalline and the simulated glass structures. It is found that our simulated glasses more resemble high-pressured experimental glasses, which is implied by the existence of fivefold silicon species. Based on bulk structures studied, glass surfaces were created by a fracture process. It is speculated that surface defect concentrations depend on the topological characteristics of the network structure, and are essential for the viability of surfaces. Analysis of local structures for difference species implies that the sodium silicate surfaces resemble more the Na-rich regions in the bulk structures. An efficient algorithm for finding primitive rings in a topological network has been developed. Analysis using this algorithm shows that reconstruction of Na-rich regions occurs on extending simulation size, demonstrating simulation size influence on modeled glass structures. Finally, our detailed analysis of Si-O-Si bond angle distributions demonstrates that vitreous silica glass has a broader Si-O-Si BAD, whilst sodium silicate glasses favor narrower distributions.

  13. 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.

  14. Compositional dependence of in vitro response to commercial silicate glasses

    NASA Astrophysics Data System (ADS)

    Jedlicka, Amy B.

    Materials are often incorporated into the human body, interacting with surrounding fluids, cells and tissues. The reactions that occur between a material and this surrounding biological system are not fundamentally understood. Basic knowledge of material biocompatibility and the controlling processes is lacking. This thesis examines material biocompatibility of a series of silicate-based glasses on a primary level determining cell response to material composition and durability. The silicate glass system studied included two BioglassRTM compositions with known biologically favorable response, two fiberglass compositions, with demonstrated 'not-unfavorable' in vitro response, a ternary soda-lime-silicate glass, a binary alkali silicate glass, and pure silica. Chemical durability was analyzed in three different fluids through solution analysis and material characterization. In vitro response to the substrates was observed. Cell behavior was then directly correlated to the material behavior in cell culture medium under the same conditions as the in vitro test, yet in the absence of cells. The effect of several physical and chemical surface treatments on substrates with predetermined biocompatible behavior was subsequently determined. The chemically durable glasses with no added B2O3 elicited similar cell response as the control polystyrene substrate. The addition of B2O3 resulted in polygonal cell shape and restricted cell proliferation. The non-durable glasses presented a dynamic surface to the cells, which did not adversely affect in vitro response. Extreme dissolution of the binary alkali silicate glass in conjunction with increased pH resulted in unfavorable cell response. Reaction of the Bioglass RTM compositions, producing a biologically favorable calcium-phosphate surface film, caused enhanced cell attachment and spreading. Surface energy increase due to sterilization procedures did not alter cellular response. Surface treatment procedures influencing substrate

  15. High chloride content calcium silicate glasses.

    PubMed

    Chen, Xiaojing; Karpukhina, Natalia; Brauer, Delia S; Hill, Robert G

    2017-03-08

    Chloride is known to volatilize from silicate glass melts and until now, only a limited number of studies on oxychloride silicate glasses have been reported. In this paper we have synthesized silicate glasses that retain large amounts of CaCl2. The CaCl2 has been added to the calcium metasilicate composition (CaO·SiO2). Glasses were produced via a melt quench route and an average of 70% of the chloride was retained after melting. Up to 31.6 mol% CaCl2 has been successfully incorporated into these silicate glasses without the occurrence of crystallization. (29)Si MAS-NMR spectra showed the silicon being present mainly as a Q(2) silicate species. This suggests that chloride formed Cl-Ca(n) species, rather than Si-Cl bonds. Upon increasing the CaCl2 content, the Tg reduced markedly from 782 °C to 370 °C. Glass density and glass crystallization temperature decreased linearly with an increase in the CaCl2 content. However, both linear regressions revealed a breakpoint at a CaCl2 content just below 20 mol%. This might be attributed to a significant change in the structure and is also correlated with the nature of the crystallizing phases formed upon heat treatment. The glasses with less than 19.2 mol% CaCl2 crystallized to wollastonite, whilst the compositions with CaCl2 content equal to or greater than 19.2 mol% are thought to crystallize to CaCl2. In practice, the crystallization of CaCl2 could not occur until the crystallization temperature fell below the melting point of CaCl2. The implications of the results along with the high chloride retention are discussed.

  16. Dynamic Fatigue of a Titanium Silicate Glass

    NASA Technical Reports Server (NTRS)

    Tucker, Dennis S.; Nettles, Alan T.; Cagle, Holly A.; Smith, W. Scott (Technical Monitor)

    2002-01-01

    A dynamic fatigue study was performed on a Titanium Silicate Glass in order to assess its susceptibility to delayed failure. Fracture mechanics techniques were used to analyze the results for the purpose of making lifetime predictions for optical elements made from this material. The material has reasonably good resistance (N=23 to stress corrosion in ambient conditions).

  17. Alkali-metal silicate binders and methods of manufacture

    NASA Technical Reports Server (NTRS)

    Schutt, J. B. (Inventor)

    1979-01-01

    A paint binder is described which uses a potassium or sodium silicate dispersion having a silicon dioxide to alkali-metal oxide mol ratio of from 4.8:1 to 6.0:1. The binder exhibits stability during both manufacture and storage. The process of making the binder is predictable and repeatable and the binder may be made with inexpensive components. The high mol ratio is achieved with the inclusion of a silicon dioxide hydrogel. The binder, which also employs a silicone, is in the final form of a hydrogel sol.

  18. Water and the density of silicate glasses

    NASA Astrophysics Data System (ADS)

    Richet, Pascal; Whittington, Alan; Holtz, François; Behrens, Harald; Ohlhorst, Susanne; Wilke, Max

    A review of published and newly measured densities for 40 hydrous silicate glasses indicates that the room-temperature partial molar volume of water is 12.0+/-0.5cm3/mol. This value holds for simple or mineral compositions as well as for complex natural glasses, from rhyolite to tephrite compositions, prepared up to 10-20kbar pressures and containing up to 7wt% H2O. This volume does not vary either with the molar volume of the water-free silicate phase, with its degree of polymerization or with water speciation. Over a wide range of compositions, this constant value implies that the volume change for the reaction between hydroxyl ions and molecular water is zero and that, at least in glasses, speciation does not depend on pressure. Consistent with data from Ochs and Lange (1997, 1999), systematics in volume expansion for SiO2-M2O systems (M=H, Li, Na, K) suggests that the partial molar thermal expansion coefficient of H2O is about 4× 10-5 K-1 in silicate glasses.

  19. Silicate release from glass for pharmaceutical preparations.

    PubMed

    Bohrer, Denise; Bortoluzzi, Fabiana; Nascimento, Paulo Cícero; Carvalho, Leandro Machado; Ramirez, Adrian Gustavo

    2008-05-01

    Glass is made of polymeric silica and other minor components, which are necessary for turning the silica into a material more easily moldable and resistant to temperature changes. Glass containers for pharmaceutical usage are classified according to their resistance to a chemical attack, a test carried out in the presence of water and heat. The test is designed to show the released alkalinity, a variable dependent on the amount of sodium oxide, one of the minor components added to the glass mass. In this work, the release of silica from glass by action of constituents from pharmaceutical formulations was investigated. The study included products used in large volumes and usually stored in glass containers. Solutions of amino acids, electrolytes, glucose, oligoelements and others such as heparin and sodium bicarbonate were individually stored in glass containers and heated at 121 degrees C for 30min, as in the water attack test. The test was also carried out only with water, where the pH varied from 2 to 12. The released silicate was measured either by photometry or atomic absorption spectrometry, depending on the nature of the sample. The results showed that silicate is released during the heating cycle even if the contact is with pure water only. The pH exerts a considerable influence on the release, being that the higher the pH, the higher the silica dissolved. An elevated pH, however, is not the only factor responsible for silica dissolution. While in the solutions of NaCl, KCl, Mg Cl2 and ZnSO4 and in most of the amino acids, the concentration of silicate was as high as in pure water (0.1-1.0mg Si/L). In the solutions of sodium acetate, bicarbonate and gluconate, its concentration was much higher, over 30mg Si/L. These results were confirmed by the analysis of commercial products, where in solutions of amino acids the level of silicate ranged from 0.14 to 0.19mg Si/L. On the other hand, calcium gluconate, sodium bicarbonate and potassium phosphate presented

  20. Lead-silicate glass optical microbubble resonator

    SciTech Connect

    Wang, Pengfei; Ward, Jonathan; Yang, Yong; Chormaic, Síle Nic; Feng, Xian; Brambilla, Gilberto; Farrell, Gerald

    2015-02-09

    Microbubble whispering gallery resonators have the potential to become key components in a variety of active and passive photonic circuit devices by offering a range of significant functionalities. Here, we report on the fabrication, optical characterization, and theoretical analysis of lead-silicate glass and optical microbubble resonators. Evanescent field coupling to the microbubbles was achieved using a 1 μm diameter, silica microfiber at a wavelength of circa 775 nm. High Q-factor modes were efficiently excited in both single-stem and two-stem, lead-silicate glass, and microbubble resonators, with bubble diameters of 38 μm (single-stem) and 48 μm (two-stem). Whispering gallery mode resonances with Q-factors as high as 2.3 × 10{sup 5} (single-stem) and 7 × 10{sup 6} (two-stem) were observed. By exploiting the high-nonlinearity of the lead-silicate glass, this work will act as a catalyst for studying a range of nonlinear optical effects in microbubbles, such as Raman scattering and four-wave mixing, at low optical powers.

  1. The structure of alkali silicate gel by total scattering methods

    SciTech Connect

    Benmore, C.J.; Monteiro, Paulo J.M.

    2010-06-15

    The structure of the alkali silicate gel (ASR) collected from the galleries of Furnas Dam in Brazil was determined by a pair distribution function (PDF) analysis of high energy X-ray diffraction data. Since this method is relatively new to concrete structure analysis a detailed introduction on the PDF method is given for glassy SiO{sub 2}. The bulk amorphous structure of the dam material is confirmed as no Bragg peaks are observed in the scattered intensity. The real space results show that the local structure of the amorphous material is similar to kanemite (KHSi{sub 2}O{sub 5}:3H{sub 2}O) however the long range layer structure of the crystal is broken up in the amorphous state, so that ordering only persists of the length scale of a few polyhedra. The silicate layer structure is a much more disordered than predicted by molecular dynamics models. The X-ray results are consistent with the molecular dynamics model of Kirkpatrick et al. (2005) [1] which predicts that most of the water resides in pores within the amorphous network rather than in layers. The total scattering data provide a rigorous basis against which other models may also be tested.

  2. The structure of alkali silicate gel by total scattering methods.

    SciTech Connect

    Benmore, C. J.; Monteiro, P. J. M.; X-Ray Science Division; Univ. of California at Berkeley

    2010-01-01

    The structure of the alkali silicate gel (ASR) collected from the galleries of Furnas Dam in Brazil was determined by a pair distribution function (PDF) analysis of high energy X-ray diffraction data. Since this method is relatively new to concrete structure analysis a detailed introduction on the PDF method is given for glassy SiO{sub 2}. The bulk amorphous structure of the dam material is confirmed as no Bragg peaks are observed in the scattered intensity. The real space results show that the local structure of the amorphous material is similar to kanemite (KHSi{sub 2}O{sub 5}:3H{sub 2}O) however the long range layer structure of the crystal is broken up in the amorphous state, so that ordering only persists of the length scale of a few polyhedra. The silicate layer structure is a much more disordered than predicted by molecular dynamics models. The X-ray results are consistent with the molecular dynamics model of Kirkpatrick et al. (2005) [1] which predicts that most of the water resides in pores within the amorphous network rather than in layers. The total scattering data provide a rigorous basis against which other models may also be tested.

  3. 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.

  4. 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.

  5. A theoretical interpretation of the chemical shift of 29Si NMR peaks in alkali borosilicate glasses

    NASA Astrophysics Data System (ADS)

    Nanba, Tokuro; Nishimura, Mitsunori; Miura, Yoshinari

    2004-12-01

    In 29Si-NMR, it has so far been accepted that the chemical shifts of Q n species (SiO 4 units containing n bridging oxygens) were equivalent between alkali borosilicate and boron-free alkali silicate glasses. In the sodium borosilicate glasses with low sodium content, however, a contradiction was confirmed in the estimation of alkali distribution; 11B NMR suggested that Na ions were entirely distributed to borate groups to form BO 4 units, whereas a -90 ppm component was also observed in 29Si-NMR spectra, which has been attributed to Q 3 species associated with a nonbridging oxygen (NBO). Then, cluster molecular orbital calculations were performed to interpret the -90 ppm component in the borosilicate glasses. It was found that a silicon atom which had two tetrahedral borons (B4) as its second nearest neighbors was similar in atomic charge and Si2p energy to the Q 3 species in boron-free alkali silicates. Unequal distribution of electrons in Si-O-B4 bridging bonds was also found, where much electrons were localized on the Si-O bonds. It was finally concluded that the Si-O-B4 bridges with narrow bond angle were responsible for the -90 ppm 29Si component in the borosilicate glasses. There still remained another interpretation; the Q 3 species were actually present in the glasses, and NBOs in the Q 3 species were derived from the tricluster groups, such as (O 3Si)O(BO 3) 2. In the glasses with low sodium content, however, it was concluded that the tricluster groups were not so abundant to contribute to the -90 ppm component.

  6. Computer simulation study of low-energy excitations of silicate glasses

    NASA Astrophysics Data System (ADS)

    Palin, Erika J.; Trachenko, Kostya O.; Dove, Martin T.

    2002-05-01

    Ten silicate and aluminosilicate glasses with different number densities and connectivities were studied by molecular dynamics simulation using the computer program DL_POLY [1]. The radial distribution functions, phonon densities of states and flexibilities of the glass networks were determined, and compared with those determined for silica [2]. The large-scale flexibility of silica was found to be similar to that of some of the glasses studied in this work, particularly in relation to rigid-unit-mode-type motions. The degree of localization of vibrations in fully networked glasses was found to be similar to that in silica, but the vibrations in glasses containing non-bridging oxygen atoms were found to be more localized. This is thought to be due to clustering of alkali cations, which in turn necessarily produces clusters of tetrahedra.

  7. ``Cooperativity blockage'' in the mixed alkali effect as revealed by molecular-dynamics simulations of alkali metasilicate glass

    NASA Astrophysics Data System (ADS)

    Habasaki, Junko; Ngai, K. L.; Hiwatari, Yasuaki

    2004-07-01

    The relaxation dynamics of a complex interacting system can be drastically changed when mixing with another component having different dynamics. In this work, we elucidate the effect of the less mobile guest ions on the dynamics of the more mobile host ions in mixed alkali glasses by molecular-dynamics (MD) simulations. One MD simulation was carried out on lithium metasilicate glass with the guest ions created by freezing some randomly chosen lithium ions at their initial locations at 700 K. A remarkable slowing down of the dynamics of the majority mobile Li ions was observed both in the self-part of the density-density correlation function, Fs(k,t), and in the mean-squared displacements. On the other hand, there is no significant change in the structure. The motion of the Li ions in the unadulterated Li metasilicate glass is dynamically heterogeneous. In the present work, the fast and slow ions were divided into two groups. The number of fast ions, which shows faster dynamics (Lévy flight) facilitated by cooperative jumps, decreases considerably when small amount of Li ions are frozen. Consequently there is a large overall reduction of the mobility of the Li ions. The result is also in accordance with the experimental finding in mixed alkali silicate glasses that the most dramatic reduction of ionic conductivity occurs in the dilute foreign alkali limit. Similar suppression of the cooperative jumps is observed in the MD simulation data of mixed alkali system, LiKSiO3. Naturally, the effect found here is appropriately described as "cooperativity blockage." Slowing down of the motion of Li ions also was observed when a small number of oxygen atoms chosen at random were frozen. The effect is smaller than the case of freezing some the Li ions, but it is not negligible. The cooperativity blockage is also implemented by confining the Li metasilicate glass inside two parallel walls formed by freezing Li ions in the same metasilicate glass. Molecular-dynamics simulations

  8. Sodium migration pathways in multicomponent silicate glasses: Car-Parrinello molecular dynamics simulations.

    PubMed

    Tilocca, Antonio

    2010-07-07

    The mechanism of sodium migration in low-silica alkali-alkaline earth silicate glasses is investigated through Car-Parrinello molecular dynamics (MD) simulations. The transport of sodium to the glass surface and its subsequent release is critical for the use of these glasses in biomedical applications. The analysis of the MD trajectory, mainly through a combination of space and time correlation functions, reveals a complex mechanism, with some common features to the migration in mixed-alkali silicate glasses and several important differences. The low site selectivity of Na cations in this glass allows them to use both Na and Ca sites in the migration process. The high fragmentation and the corresponding flexibility of the silicate network enable an additional mechanism for ion migration, not favorable in the more rigid network of common higher-silica glasses, involving the creation of empty transient sites through the correlated forward-backward motion of an Na or a Ca cation. We also show that because sodium migration must involve an undercoordinated intermediate, sharing of oxygen atoms in the initial and final coordination shells is a way to reduce the energetic cost of losing favorable Na-O interactions and Na migration proceeds between corner-sharing NaO(x) polyhedra, where x=5-7. For these low-silica compositions, the present simulations suggest that due to the participation of calcium in the Na migration, the latter will not be significantly hampered by extensive mixing with less mobile Ca ions, or, in any event, the effect will be less marked than for higher-silica glasses.

  9. Lithium and Sodium Resistance of Alkali Metal Vapor Resistant Glasses

    NASA Astrophysics Data System (ADS)

    Kishinevski, Anatoly; Hall, Matthew

    2014-05-01

    A common challenge in atomic physics is that of containing an alkali metal vapor at an elevated temperature and concurrently being able to excite and probe atomic transitions within. Typically glass is used as the material to construct the container, as it is easy to manipulate into any geometry and offers thermal, mechanical, and optical properties that no other material is capable. Unfortunately it has been well established that alkali metal gasses/vapors react readily with silica containing glass and results in a progressive darkening of the material. As the darkening reaction progresses, the optical transmission properties of the glass progressively degrade to an eventual point of uselessness. Alkali metals have been used extensively in frequency standards and magnetometers. The finite life of these alkali metal vapor-containing devices has been accepted despite varying attempts by different teams to solve this problem. As a viable solution, it has been identified there exist a family of glass compositions that contain a marginal amount of silica, may be lampworked using traditional glassblowing techniques, and that offer substantially better alkali vapor resistance. The evaluation of these glasses and their resistance to sodium and lithium vapor at varying pressures and temperatures are discussed.

  10. Optical and crystallization studies of titanium dioxide doped sodium and potassium silicate glasses

    NASA Astrophysics Data System (ADS)

    ElBatal, F. H.; Marzouk, M. A.; ElBatal, H. A.

    2016-10-01

    Combined optical and FTIR spectral analysis were used to investigate prepared invert two alkali silicate glasses (Na2O·SiO2sbnd K2O·SiO2) containing high titanium oxide content. Glass ceramic derivatives were prepared through thermal two step regime of the parent glasses and they were characterized by FTIR and X-ray diffraction measurements. Experimental optical spectra indicate the appearance of an additional UV band due to absorption of tetravalent titanium ions beside the UV bands due to trace ferric ions impurities. FT infrared absorption spectra reveal composite vibrational bands due to vibrational modes of both silicate groups and TiO4 or Sisbnd Osbnd Ti units. Such tetravalent groupings of titanium ions confirm the stability of such invert glasses containing as such two main glass forming oxides. FTIR spectra of the glass - ceramic derivatives show nearly the same IR vibrational modes as their parent glasses. X-ray diffraction analysis show the separation of crystalline sodium or potassium titanate phases beside a minor form of silica and the results confirm that TiO2 acts mainly as network forming units leading to the formation of crystalline titanate phases.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Inorganic phosphors in lead-silicate glass for white LEDs

    NASA Astrophysics Data System (ADS)

    Nikonorov, N. V.; Kolobkova, E. V.; Aseev, V. A.; Bibik, A. Yu.; Nekrasova, Ya. A.; Tuzova, Yu. V.; Novogran, A. I.

    2016-09-01

    Luminescent composites of the "phosphor-in-glass" type, based on a highly reflective lead-silicate matrix and fine-grained powders of YAG:Ce3+ and SiAlON:Eu2+ crystals, are developed and synthesized. Phosphor and glass powders are sintered at a temperature of 550°C to obtain phosphor samples for white LEDs. The composites are analyzed by X-ray diffraction and luminescence spectroscopy. The dependence of the light quantum yield on the SiAlON:Eu2+ content in the samples is investigated. A breadboard of a white LED is designed using a phosphor-in-glass composite based on lead-silicate glass with a low glasstransition temperature. The total emission spectra of a blue LED and glass-based composites are measured. The possibility of generating warm white light by choosing an appropriate composition is demonstrated.

  17. Durability of Silicate Glasses: An Historical Approach

    SciTech Connect

    Farges, Francois; Etcheverry, Marie-Pierre; Haddi, Amine; Trocellier, Patrick; Curti, Enzo; Brown, Gordon E., Jr.; /SLAC, SSRL

    2007-01-02

    We present a short review of current theories of glass weathering, including glass dissolution, and hydrolysis of nuclear waste glasses, and leaching of historical glasses from an XAFS perspective. The results of various laboratory leaching experiments at different timescales (30 days to 12 years) are compared with results for historical glasses that were weathered by atmospheric gases and soil waters over 500 to 3000 years. Good agreement is found between laboratory experiments and slowly leached historical glasses, with a strong enrichment of metals at the water/gel interface. Depending on the nature of the transition elements originally dissolved in the melt, increasing elemental distributions are expected to increase with time for a given glass durability context.

  18. 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.

  19. Nanogratings formation in multicomponent silicate glasses

    NASA Astrophysics Data System (ADS)

    Lancry, M.; Zimmerman, F.; Desmarchelier, R.; Tian, J.; Brisset, F.; Nolte, S.; Poumellec, B.

    2016-03-01

    We demonstrate the formation of porous nanogratings in various oxide glasses including TiO2-doped silica, GeO2 and alumino-borosilicate by near-IR femtosecond laser radiation. ULE and GeO2 glasses exhibit similar birefringence to pure silica, whereas Borofloat 33 reveals twice weaker amplitude. Using quantitative birefringence measurements, small-angle X-ray scattering and scanning electron microscopy, we correlate birefringence and porous nanolayers formation according to laser repetition rate and glass composition. We show that heat accumulation is a crucial parameter limiting the glass decomposition and thus nanogratings formation.

  20. Water and magmas: insights about the water solution mechanisms in alkali silicate melts from infrared, Raman, and 29Si solid-state NMR spectroscopies

    NASA Astrophysics Data System (ADS)

    Le Losq, Charles; Mysen, Bjorn O.; Cody, George D.

    2015-12-01

    Degassing of water during the ascent of hydrous magma in a volcanic edifice produces dramatic changes in the magma density and viscosity. This can profoundly affect the dynamics of volcanic eruptions. The water exsolution history, in turn, is driven by the water solubility and solution mechanisms in the silicate melt. Previous studies pointed to dissolved water in silicate glasses and melts existing as molecules (H2Omol species) and hydroxyl groups, OH. These latter OH groups commonly are considered bonded to Si4+ but may form other bonds, such as with alkali or alkaline-earth cations, for instance. Those forms of bonding influence the structure of hydrous melts in different ways and, therefore, their properties. As a result, exsolution of water from magmas may have different eruptive consequences depending on the initial bonding mechanisms of the dissolved water. However, despite their importance, the solution mechanisms of water in silicate melts are not clear. In particular, how chemical composition of melts affects water solubility and solution mechanism is not well understood. In the present experimental study, components of such information are reported via determination of how water interacts with the cationic network of alkali (Li, Na, and K) silicate quenched melts. Results from 29Si single-pulse magic-angle spinning nuclear magnetic resonance (29Si SP MAS NMR), infrared, and Raman spectroscopies show that decreasing the ionic radius of alkali metal cation in silicate melts results in decreasing fraction of water dissolved as OH groups. The nature of OH bonding also changes as the alkali ionic radius changes. Therefore, as the speciation and bonding of water controls the degree of polymerization of melts, water will have different effects on the transport properties of silicate melts depending on their chemical composition. This conclusion, in turn, may affect volcanic phenomena related to the viscous relaxation of hydrous magmas, such as for instance the

  1. Origin and consequences of silicate glass passivation by surface layers

    PubMed Central

    Gin, Stéphane; Jollivet, Patrick; Fournier, Maxime; Angeli, Frédéric; Frugier, Pierre; Charpentier, Thibault

    2015-01-01

    Silicate glasses are durable materials, but are they sufficiently durable to confine highly radioactive wastes for hundreds of thousands years? Addressing this question requires a thorough understanding of the mechanisms underpinning aqueous corrosion of these materials. Here we show that in silica-saturated solution, a model glass of nuclear interest corrodes but at a rate that dramatically drops as a passivating layer forms. Water ingress into the glass, leading to the congruent release of mobile elements (B, Na and Ca), is followed by in situ repolymerization of the silicate network. This material is at equilibrium with pore and bulk solutions, and acts as a molecular sieve with a cutoff below 1 nm. The low corrosion rate resulting from the formation of this stable passivating layer enables the objective of durability to be met, while progress in the fundamental understanding of corrosion unlocks the potential for optimizing the design of nuclear glass-geological disposal. PMID:25695377

  2. Petrography study of two siliceous limestones submitted to alkali-silica reaction

    SciTech Connect

    Monnin, Y. . E-mail: monnin@ensm-douai.fr; Degrugilliers, P.; Bulteel, D.; Garcia-Diaz, E.

    2006-08-15

    This study presents the contribution of petrography to the comprehension of the alkali-silica reaction mechanism applied to two siliceous limestones. A petrography study was made on the two aggregates before reaction to define their relative proportions and types of reactive silica and to observe their distribution in the microstructure. Then a model reactor, constituted by the reactive siliceous limestone aggregate, portlandite and NaOH, was used to measure the swelling due to reaction of the silica with alkalis and the free expansion of the aggregates. The volume evolution between both aggregates was very different and could be explained by the preliminary petrographic study. It appears that the swelling of the aggregates is conditioned by the microstructure of the carbonated matrix, the quantity and the distribution of the reactive silica.

  3. 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)

  4. LOW VELOCITY SHPERE IMPACT OF SODA LIME SILICATE GLASS

    SciTech Connect

    Morrissey, Timothy G; Fox, Ethan E; Wereszczak, Andrew A; Vuono, Daniel J

    2012-01-01

    This report summarizes TARDEC-sponsored work at Oak Ridge National Laboratory (ORNL) during the FY11 involving low velocity ( 30 m/s or 65 mph) ball impact testing of Starphire soda lime silicate glass. The intent was to better understand low velocity impact response in the Starphire for sphere densities that bracketed that of rock. Five sphere materials were used: borosilicate glass, soda-lime silicate glass, steel, silicon nitride, and alumina. A gas gun was fabricated to produce controlled velocity delivery of the spheres against Starphire tile targets. Minimum impact velocities to initiate fracture in the Starphire were measured and interpreted in context to the kinetic energy of impact and the elastic property mismatch between the any of the five sphere-Starphire-target combinations.

  5. 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.

  6. Carbonate-silicate immiscibility and extremely peralkaline silicate glasses from Nasira cone and recent eruptions at Oldoinyo Lengai Volcano, Tanzania

    NASA Astrophysics Data System (ADS)

    Mitchell, Roger H.; Dawson, J. Barry

    2012-11-01

    Phenocrysts of garnet, pyroxene and nepheline in peralkaline nephelinite from the Nasira parasitic cones at Oldoinyo Lengai contain quenched immiscible silicate (peralkalinity = 2-13) and Na-Ca-carbonate melts. Their bulk compositions further define the limits of liquid immiscibility for peralkaline carbonated nephelinite magmas and confirm this process was operative at Oldoinyo Lengai during older stages of activity. Groundmass glasses in Nasira nephelinites are peralkaline (peralkalinity = 5.5-9.5) but less evolved than melt inclusion glasses (peralkalinity = 8-13) in nepheline phenocrysts, implying that these magmas are hybrids formed by magma mixing. Groundmass glass in diverse peralkaline combeite nephelinite ash clasts with and without melilite and/or wollastonite formed in the January-June 2008 eruptions of Oldoinyo Lengai are also exceptionally peralkaline. Two trends in their compositions are evident: (1) increasing peralkalinity from 6 to 10 with SiO2 decreasing from 42 to 33 wt.%; (2) increasing peralkalinity from 6 to 16 with SiO2 decreasing from 45 to 40 wt.%. All recent glasses are considered to be more evolved than groundmass glass in Nasira combeite nephelinite. These data indicate that several varieties of nephelinite exist at Oldoinyo Lengai. Their parental magmas are considered to have been initially enriched in alkalis during partial melting of their metasomatized asthenospheric sources and further by subsequent assimilation, or re-solution, of previously exsolved natrocarbonatite melt in the magma chamber(s) underlying Oldoinyo Lengai. On this basis, none of the bulk compositions of peralkaline stage II lavas at Oldoinyo Lengai, including Nasira, are considered to represent those of liquids as their compositions are determined by rheological factors (phenocryst accumulation; cumulate disruption) and assimilation processes. The formation of combeite is considered to be a consequence of natrocarbonatite melt assimilation.

  7. 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.

  8. Study of Alkali-Metal Vapor Diffusion into Glass Materials

    NASA Astrophysics Data System (ADS)

    Sato, Kiminori

    2013-08-01

    To investigate nanodispersion of alkali metals into glass materials, potassium vapor diffusion is conducted using SiO2 glass under well-controlled temperature conditions. It is found that potassium vapor significantly diffuses into the bulk of SiO2 glass with less precipitation on the surface when the host material is kept at a temperature slightly higher than that of the guest material. Positron annihilation spectroscopy reveals that angstrom-scale open spaces in the SiO2 matrix contribute to potassium vapor diffusion. The analysis of potassium concentration obtained by electron probe microanalysis (EPMA) mapping with Fick's second law yields an extremely low potassium diffusion coefficient of 5.1×10-14 cm2 s-1, which arises from the overall diffusion from open spaces of various sizes. The diffusion coefficient attributable to angstrom-scale open spaces is thus expected to be less than ˜10-14 cm2 s-1. The present findings imply that angstrom-scale open spaces play an important role in loading alkali metals into glass materials.

  9. Environmental effects on initiation and propagation of surface defects on silicate glasses: scratch and fracture toughness study

    NASA Astrophysics Data System (ADS)

    Surdyka, Nicholas D.; Pantano, Carlo G.; Kim, Seong H.

    2014-08-01

    The glass composition and surrounding environment can play an important role in the initiation and propagation of surface defects, which affect the practical strength of glass. We have studied how the environment and glass composition affect the tribological and indentation properties of multicomponent silicate glasses. Soda lime silica and aluminosilicate glasses were studied to compare the effects of the alkali ion and glass network type on surface defect formation. Although both glasses contained leachable sodium ions, the surface wear of soda lime glass decreased with increasing humidity while sodium aluminosilicate glass had an observable increase in surface wear. This indicated that sodium ion and water activity on/in glass surfaces vary depending on the glass network structure. The exchange of Na+ with K+ in aluminosilicate glass increased the elastic modulus, hardness, and resistance to fracture substantially; however, it did not improve the surface scratch resistance in humid environments. This suggested that the improved fracture toughness for the K-exchanged aluminosilicate glass is mainly due to the improved bulk properties; surface wear can readily take place regardless of Na/K-exchange.

  10. Structure and dynamics of iron doped and undoped silicate glasses

    NASA Astrophysics Data System (ADS)

    Santos, Cristiane N.; Meneses, Domingos D. S.; Echegut, Patrick; Lecomte, Emmanuel

    2010-03-01

    The optical properties of common silicate glass compositions are well known at room temperature. However, their radiative properties and structural evolution of these glasses with temperature are still largely unexplored. In this work we have measured the emissivity of a set of iron doped and undoped silicate and borosilicate glasses over an unprecedented temperature (up to 1700 K) and spectral range (40 -- 20000 cm-1). This was achieved by means of a home-made apparatus composed of a CO2 laser as the heat source, a black-body reference and two spectrometers. The optical functions were assessed using a dielectric function model [1], and the structure and dynamics of the glassy network, as well the absorption of iron species in different redox states were evidenced. We believe that these new data will help to understand the heat transfer in molten silicates. [4pt] [1] D. D. S. Meneses, G. Gruener, M. Malki, and P. Echegut, J. Non-Cryst. Solids 351, 124 (2005)

  11. 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.

  12. Conduction mechanism in bismuth silicate glasses containing titanium

    NASA Astrophysics Data System (ADS)

    Dult, Meenakshi; Kundu, R. S.; Murugavel, S.; Punia, R.; Kishore, N.

    2014-11-01

    Bismuth silicate glasses mixed with different concentrations of titanium dioxide having compositions xTiO2-(60-x)Bi2O3-40SiO2 with x=0, 5, 10, 15 and 20 were prepared by the normal melt quench technique. The frequency dependence of the ac electrical conductivity of different compositions of titanium bismuth silicate glasses has been studied in the frequency range 10-1 Hz to 10 MHz and in the temperature range 623-703 K. The temperature and frequency dependent conductivity is found to obey Jonscher's universal power law for all the compositions of titanium bismuth silicate glass system. The dc conductivity (σdc), so called crossover frequency (ωH), and frequency exponent (s) have been estimated from the fitting of experimental data of ac conductivity with Jonscher's universal power law. Enthalpy to dissociate the cation from its original site next to a charge compensating center (Hf) and enthalpy of migration (Hm) have also been estimated. The conductivity data have been analyzed in terms of different theoretical models to determine the possible conduction mechanism. Analysis of the conductivity data and the frequency exponent shows that the correlated barrier hopping of electrons between Ti3+ and Ti4+ ions in the glasses is the most favorable mechanism for ac conduction. The temperature dependent dc conductivity has been analyzed in the framework of theoretical variable range hopping model (VRH) proposed by Mott which describe the hopping conduction in disordered semiconducting systems. The various polaron hopping parameters have also been deduced. Mott's VRH model is found to be in good agreement with experimental data and the values of inverse localization length of s-like wave function (α) obtained by this model with modifications suggested by Punia et al. are close to the ones reported for a number of oxide glasses.

  13. Sintering and foaming of barium silicate glass powder compacts

    NASA Astrophysics Data System (ADS)

    Mueller, Ralf; Reinsch, Stefan; Agea-Blanco, Boris

    2016-10-01

    The manufacture of sintered glasses and glass-ceramics, glass matrix composites and glass-bounded ceramics or pastes is often affected by gas bubble formation. Against this background, we studied sintering and foaming of barium silicate glass powders used as SOFC sealants using different powder milling procedures. Sintering was measured by means of heating microscopy backed up by XPD, DTA, Vacuum Hot Extraction (VHE) and optical and electron microscopy. Foaming increased significantly as milling progressed. For moderately milled glass powders, subsequent storage in air could also promote foaming. Although the powder compacts were uniaxially pressed and sintered in air, the milling atmosphere sig¬ni¬ficantly affected foaming. The strength of this effect increased in the order Ar ? N2 < air < CO2. Conformingly, VHE studies revealed that the pores of foamed samples predominantly encapsulated CO2, even for powders milled in Ar and N2. Results of this study thus indicate that foaming is caused by carbonaceous species trapped on the glass powder surface. Foaming could be substantially reduced by milling in water and 10 wt% HCl.

  14. 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).

  15. Silicate melt inclusions and glasses in lunar soil fragments from the Luna 16 core sample

    USGS Publications Warehouse

    Roedder, E.; Weiblen, P.W.

    1972-01-01

    More than 2000 fragments were studied microscopically, and electron microprobe analyses were made of 39 selected areas, from a few square mm of polished surface, through 75- to 425-??m fragments of lunar soil from two samples of the Luna 16 core. The silicate melt inclusions and glasses differ in important details from those observed earlier in the Apollo samples. Melt inclusions in olivine contain epitaxially oriented daughter crystals, but also show a similar epitaxy around the outside of the crystals not observed in previous lunar samples. Melt inclusions in ilmenite suggest trapping at successive stages in a differentiation sequence. There is abundant evidence for late-stage silicate liquid immiscibility, with melt compositions similar but not identical to those from Apollo 11 and 12. A comparison of the alkali ratio of any given bulk rock analysis with that of its late-stage, high-silica melt shows gross differences for different rocks. This is pertinent to understanding late-stage differentiation processes. Glass fragments and spherules exhibit a wide range of crystallization textures, reflecting their wide range of compositions and cooling histories. No significant differences were found between the two portions of core examined (Zones A and D). ?? 1972.

  16. 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.

  17. 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.

  18. SON68 glass dissolution driven by magnesium silicate precipitation

    NASA Astrophysics Data System (ADS)

    Fleury, Benjamin; Godon, Nicole; Ayral, André; Gin, Stéphane

    2013-11-01

    Experimental results are reported on the effect of magnesium silicate precipitation on the mechanisms and rate of borosilicate glass dissolution. Leaching experiments with SON68 glass, a borosilicate containing no Mg, were carried out in initially deionized water at 50 °C with a glass-surface-area-to-solution-volume ratio of 20,000 m-1. After 29 days of alteration the experimental conditions were modified by the addition of Mg to trigger the precipitation of Mg-silicate. Additional experiments were conducted to investigate the importance of other parameters such as pH or dissolved silica on the mechanisms of precipitation of Mg-silicates and their consequences on the glass dissolution rate. Mg-silicates precipitate immediately after Mg is added. The amount of altered glass increases with the quantity of added Mg, and is smaller when silicon is added in solution. A time lag is observed between the addition of magnesium and the resumption of glass alteration because silicon is first provided by partial dissolution of the previously formed alteration gel. It is shown that nucleation does not limit Mg-silicate precipitation. A pH above 8 is necessary for the phase to precipitate under the investigated experimental conditions. On the other hand the glass alteration kinetics limits the precipitation if the magnesium is supplied in solution at a non-limiting rate. The concentration of i in solution was analyzed as well as that of boron. The quantity of i released from the glass is estimated with the assumption that i and B are released congruently at the glass dissolution front. The remained quantity of the element i is then supposed to be in the gel or in the secondary phase. In this paper, we do not make a difference between gel and hydrated glass using the same word 'gel' whereas Gin et al. [40] makes this difference. Recent papers [40,41] discussed about different key issues related to the passivation properties of the alteration layer including the hydrated glass

  19. Infrared Spectroscopy and Stable Isotope Geochemistry of Hydrous Silicate Glasses

    SciTech Connect

    Stolper, Edward

    2007-03-05

    The focus of this DOE-funded project has been the study of volatile components in magmas and the atmosphere. Over the twenty-one year period of this project, we have used experimental petrology and stable isotope geochemistry to study the behavior and properties of volatile components dissolved in silicate minerals and melts and glasses. More recently, we have also studied the concentration and isotopic composition of CO2 in the atmosphere, especially in relation to air quality issues in the Los Angeles basin.

  20. Enzyme stabilization by glass-derived silicates in glass-exposed aqueous solutions

    USGS Publications Warehouse

    Ives, J.A.; Moffett, J.R.; Arun, P.; Lam, D.; Todorov, T.I.; Brothers, A.B.; Anick, D.J.; Centeno, J.; Namboodiri, M.A.A.; Jonas, W.B.

    2010-01-01

    Objectives: To analyze the solutes leaching from glass containers into aqueous solutions, and to show that these solutes have enzyme activity stabilizing effects in very dilute solutions. Methods: Enzyme assays with acetylcholine esterase were used to analyze serially succussed and diluted (SSD) solutions prepared in glass and plastic containers. Aqueous SSD preparations starting with various solutes, or water alone, were prepared under several conditions, and tested for their solute content and their ability to affect enzyme stability in dilute solution. Results: We confirm that water acts to dissolve constituents from glass vials, and show that the solutes derived from the glass have effects on enzymes in the resultant solutions. Enzyme assays demonstrated that enzyme stability in purified and deionized water was enhanced in SSD solutions that were prepared in glass containers, but not those prepared in plastic. The increased enzyme stability could be mimicked in a dose-dependent manner by the addition of silicates to the purified, deionized water that enzymes were dissolved in. Elemental analyses of SSD water preparations made in glass vials showed that boron, silicon, and sodium were present at micromolar concentrations. Conclusions: These results show that silicates and other solutes are present at micromolar levels in all glass-exposed solutions, whether pharmaceutical or homeopathic in nature. Even though silicates are known to have biological activity at higher concentrations, the silicate concentrations we measured in homeopathic preparations were too low to account for any purported in vivo efficacy, but could potentially influence in vitro biological assays reporting homeopathic effects. ?? 2009 The Faculty of Homeopathy.

  1. 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.

  2. Fabrication of wound capacitors using flexible alkali-free glass

    DOE PAGES

    Wilke, Rudeger H. T.; Baker, Amanda; Brown-Shaklee, Harlan; ...

    2016-10-01

    Here, alkali-free glasses, which exhibit high energy storage densities (~35 J/cc), present a unique opportunity to couple high temperature stability with high breakdown strength, and thus provide an avenue for capacitor applications with stringent temperature and power requirements. Realizing the potential of these materials in kilovolt class capacitors with >1 J/cc recoverable energy density requires novel packaging strategies that incorporate these extremely fragile dielectrics. In this paper, we demonstrate the feasibility of fabricating wound capacitors using 50-μm-thick glass. Two capacitors were fabricated from 2.8-m-long ribbons of thin (50 μm) glass wound into 125-140-mm-diameter spools. The capacitors exhibit a capacitance ofmore » 70-75 nF with loss tangents below 1%. The wound capacitors can operate up to 1 kV and show excellent temperature stability to 150 °C. By improving the end terminations, the self-resonance can be shifted to above 1 MHz, indicating that these materials may be useful for pulsed power applications with microsecond discharge times.« less

  3. Fabrication of wound capacitors using flexible alkali-free glass

    SciTech Connect

    Wilke, Rudeger H. T.; Baker, Amanda; Brown-Shaklee, Harlan; Johnson-Wilke, Raegan; Hettler, Chad; Murata, Takashi; O'Malley, Patrick; Perini, Steve; Lanagan, Michael

    2016-10-01

    Here, alkali-free glasses, which exhibit high energy storage densities (~35 J/cc), present a unique opportunity to couple high temperature stability with high breakdown strength, and thus provide an avenue for capacitor applications with stringent temperature and power requirements. Realizing the potential of these materials in kilovolt class capacitors with >1 J/cc recoverable energy density requires novel packaging strategies that incorporate these extremely fragile dielectrics. In this paper, we demonstrate the feasibility of fabricating wound capacitors using 50-μm-thick glass. Two capacitors were fabricated from 2.8-m-long ribbons of thin (50 μm) glass wound into 125-140-mm-diameter spools. The capacitors exhibit a capacitance of 70-75 nF with loss tangents below 1%. The wound capacitors can operate up to 1 kV and show excellent temperature stability to 150 °C. By improving the end terminations, the self-resonance can be shifted to above 1 MHz, indicating that these materials may be useful for pulsed power applications with microsecond discharge times.

  4. Coordination chemistry of Ti(IV) in silicate glasses and melts: III. Glasses and melts from ambient to high temperatures

    NASA Astrophysics Data System (ADS)

    Farges, François; Brown, Gordon E.; Navrotsky, Alexandra; Gan, Hao; Rehr, John R.

    1996-08-01

    The local structural environment of Ti in five Na-, K-, and Ca-titanosilicate glass/melts with TiO 2 concentrations ranging from 2.7-30.5 wt% has been determined by in situ Ti K-edge x-ray absorption fine structure (XAFS) spectroscopy at temperatures ranging from 293-1650 K. In parallel, two Ti-model compounds (Ni 2.6Ti 0.7O 4 spinel and TiO 2 rutile) were studied under the same conditions to better understand the effects of temperature (anharmonicity) on the XAFS spectra. Temperature-induced anharmonicity was found to vary, largely as a function of the Ti-coordination, and increases significantly around Ti with increasing temperature when present as [6]Ti. In contrast, anharmonicity appears negligible around [4]Ti at temperatures below 1200 K. We predict that anharmonicity should be weak around [5]Ti as well. No clear evidence was found for a significant change in the average nearest-neighbor coordination environment of Ti in the Na- and K-titanosilicate glasses and melts that exhibit anomalous heat capacities variations just above their glass transition temperatures, Tg (860-930 K). The small (predicted and measured) linear thermal expansion of the ( [5]TiO 2+) sbnd O bond in these systems at high temperature is expected to have an insignificant effect on the local environment of [5]Ti during the glass-to-supercooled liquid transition. In the most dilute Ti-glass studied (KS1; 2.7 wt% TiO 2), the local environment around [4]Ti (especially the second-neighbor alkalis) is relatively ordered at ambient temperature, but this order decreases dramatically above Tg. Lower quench rates appear to favor [4]Ti over [5]Ti. The origin of the observed anomalous positive variations in heat capacities of these melts may be related to significant changes in the medium-range environment around Ti above Tg including the disappearance of percolation domains involving interfaces between alkali-rich and network-former rich regions during structural relaxation at Tg; these percolation

  5. Enhanced bioactivity of glass ionomer cement by incorporating calcium silicates.

    PubMed

    Chen, Song; Cai, Yixiao; Engqvist, Håkan; Xia, Wei

    2016-01-01

    Glass ionomer cements (GIC) are known as a non-bioactive dental cement. During setting the GIC have an acidic pH, driven by the acrylic acid component. It is a challenge to make GIC alkaline without disturbing its mechanical properties. One strategy was to add slowly reacting systems with an alkaline pH. The aim of the present study is to investigate the possibility of forming a bioactive dental material based on the combination of glass ionomer cement and calcium silicates. Two types of GIC were used as control. Wollastonite (CS also denoted β-CaSiO3) or Mineral Trioxide Aggregate (MTA) was incorporated into the 2 types of GIC. The material formulations' setting time, compressive strength, pH and bioactivity were compared between modified GIC and GIC control. Apatite crystals were found on the surfaces of the modified cements but not on the control GIC. The compressive strength of the cement remained with the addition of 20% calcium silicate or 20% MTA after one day immersion. In addition, the compressive strength of GIC modified with 20% MTA had been increased during the 14 d immersion (p < 0 .05).

  6. Enhanced bioactivity of glass ionomer cement by incorporating calcium silicates

    PubMed Central

    Chen, Song; Cai, Yixiao; Engqvist, Håkan; Xia, Wei

    2016-01-01

    Abstract Glass ionomer cements (GIC) are known as a non-bioactive dental cement. During setting the GIC have an acidic pH, driven by the acrylic acid component. It is a challenge to make GIC alkaline without disturbing its mechanical properties. One strategy was to add slowly reacting systems with an alkaline pH. The aim of the present study is to investigate the possibility of forming a bioactive dental material based on the combination of glass ionomer cement and calcium silicates. Two types of GIC were used as control. Wollastonite (CS also denoted β-CaSiO3) or Mineral Trioxide Aggregate (MTA) was incorporated into the 2 types of GIC. The material formulations’ setting time, compressive strength, pH and bioactivity were compared between modified GIC and GIC control. Apatite crystals were found on the surfaces of the modified cements but not on the control GIC. The compressive strength of the cement remained with the addition of 20% calcium silicate or 20% MTA after one day immersion. In addition, the compressive strength of GIC modified with 20% MTA had been increased during the 14 d immersion (p < 0 .05). PMID:26787304

  7. DNA adsorption onto calcium aluminate and silicate glass surfaces.

    PubMed

    Carlson, Krista; Flick, Lisa; Hall, Matthew

    2014-05-01

    A common technique for small-scale isolation of genomic DNA is via adsorption of the DNA molecules onto a silica scaffold. In this work, the isolation capacities of calcium aluminate based glasses were compared against a commercially available silica scaffold. Silica scaffolds exhibit a negative surface at the physiological pH values used during DNA isolation (pH 5-9), while the calcium aluminate glass microspheres exhibit a positive surface charge. Isolation data demonstrates that the positively charged surface enhanced DNA adsorption over the negatively charged surface. DNA was eluted from the calcium aluminate surface by shifting the pH of the solution to above its IEP at pH 8. Iron additions to the calcium aluminate glass improved the chemical durability without compromising the surface charge. Morphology of the glass substrate was also found to affect DNA isolation; 43-106 μm diameter soda lime silicate microspheres adsorbed a greater quantity of genomic DNA than silica fibers with an average diameter of ∼2 μm.

  8. Study of Luminescence Characteristics of Trivalent Terbium in Silicate Glass

    NASA Technical Reports Server (NTRS)

    West, Mike S.; Armagan, Guzin; Winfree, William P.

    1995-01-01

    An important use of silicate glasses doped with terbium oxide (Tb2O3) is their use as fiber optic sensors for high-resolution imaging applications requiring the detection of x-rays (e.g. tomography and radiography). The x-ray radiation is absorbed by the glass, producing electron-hole pairs (excitons). The excitons migrate through the glass matrix and then recombine, emitting characteristic Tb(3+) luminescence in the optical wavelength region. This emission is due to forbidden transitions of 4f electrons and therefore has a long decay time. Long decay time is undesirable when imaging transient events since it results in blurring in time of the images. It has been reported elsewhere that in crystals Tb(3+) ions can act both as luminescence centers and as fluorescence traps. These traps can capture excitons and delay their recombination. This delayed fluorescence is seen as a long lived, secondary component to the luminescence decay curve, or afterglow. Such a secondary decay component to the luminescence decay of Tb(3+) has been observed before in soda glass following pulsed optical excitation. In order to determine the conditions under which afterglow occurs, an understanding of the material's luminescent properties is required.

  9. Pockels effect of silicate glass-ceramics: Observation of optical modulation in Mach–Zehnder system

    PubMed Central

    Yamaoka, Kazuki; Takahashi, Yoshihiro; Yamazaki, Yoshiki; Terakado, Nobuaki; Miyazaki, Takamichi; Fujiwara, Takumi

    2015-01-01

    Silicate glass has been used for long time because of its advantages from material’s viewpoint. In this paper, we report the observation of Pockels effect by Mach–Zehnder interferometer in polycrystalline ceramics made from a ternary silicate glass via crystallization due to heat-treatment, i.e., glass-ceramics. Since the silicate system is employed as the precursor, merits of glass material are fully utilized to fabricate the optical device component, in addition to that of functional crystalline material, leading us to provide an electro-optic device, which is introducible into glass-fiber network. PMID:26184722

  10. Lifetime Predictions of a Titanium Silicate Glass with Machined Flaws

    NASA Technical Reports Server (NTRS)

    Tucker, Dennis S.; Nettles, Alan T.; Cagle, Holly

    2003-01-01

    A dynamic fatigue study was performed on a Titanium Silicate glass to assess its susceptibility to delayed failure and to compare the results with those of a previous study. Fracture mechanics techniques were used to analyze the results for the purpose of making lifetime predictions. The material strength and lifetime was seen to increase due to the removal of residual stress through grinding and polishing. Influence on time-to-failure is addressed for the case with and without residual stress present. Titanium silicate glass otherwise known as ultra-low expansion (ULE)* glass is a candidate for use in applications requiring low thermal expansion characteristics such as telescope mirrors. The Hubble Space Telescope s primary mirror was manufactured from ULE glass. ULE contains 7.5% titanium dioxide which in combination with silica results in a homogenous glass with a linear expansion coefficient near zero. delayed failure . This previous study was based on a 230/270 grit surface. The grinding and polishing process reduces the surface flaw size and subsurface damage, and relieves residual stress by removing the material with successively smaller grinding media. This results in an increase in strength of the optic during the grinding and polishing sequence. Thus, a second study was undertaken using samples with a surface finish typically achieved for mirror elements, to observe the effects of surface finishing on the time-to-failure predictions. An allowable stress can be calculated for this material based upon modulus of rupture data; however, this does not take into account the problem of delayed failure, most likely due to stress corrosion, which can significantly shorten lifetime. Fortunately, a theory based on fracture mechanics has been developed enabling lifetime predictions to be made for brittle materials susceptible to delayed failure. Knowledge of the factors governing the rate of subcritical flaw growth in a given environment enables the development of

  11. Glass formation, properties, and structure of soda-yttria-silicate glasses

    NASA Technical Reports Server (NTRS)

    Angel, Paul W.; Hann, Raiford E.

    1991-01-01

    The glass formation region of the soda yttria silicate system was determined. The glasses within this region were measured to have a density of 2.4 to 3.1 g/cu cm, a refractive index of 1.50 to 1.60, a coefficient of thermal expansion of 7 x 10(exp -6)/C, softening temperatures between 500 and 780 C, and Vickers hardness values of 3.7 to 5.8 GPa. Aqueous chemical durability measurements were made on select glass compositions while infrared transmission spectra were used to study the glass structure and its effect on glass properties. A compositional region was identified which exhibited high thermal expansion, high softening temperatures, and good chemical durability.

  12. Low Velocity Sphere Impact of a Soda Lime Silicate Glass

    SciTech Connect

    Wereszczak, Andrew A; Fox, Ethan E; Morrissey, Timothy G; Vuono, Daniel J

    2011-10-01

    This report summarizes TARDEC-sponsored work at Oak Ridge National Laboratory (ORNL) during the FY11 involving low velocity (< 30 m/s or < 65 mph) ball impact testing of Starphire soda lime silicate glass. The intent was to better understand low velocity impact response in the Starphire for sphere densities that bracketed that of rock. Five sphere materials were used: borosilicate glass, soda-lime silicate glass, steel, silicon nitride, and alumina. A gas gun was fabricated to produce controlled velocity delivery of the spheres against Starphire tile targets. Minimum impact velocities to initiate fracture in the Starphire were measured and interpreted in context to the kinetic energy of impact and the elastic property mismatch between the any of the five sphere-Starphire-target combinations. The primary observations from this low velocity (< 30 m/s or < 65 mph) testing were: (1) Frictional effects contribute to fracture initiation. (2) Spheres with a lower elastic modulus require less force to initiate fracture in the Starphire than spheres with a higher elastic modulus. (3) Contact-induced fracture did not initiate in the Starphire SLS for impact kinetic energies < 150 mJ. Fracture sometimes initiated or kinetic energies between {approx} 150-1100 mJ; however, it tended to occur when lower elastic modulus spheres were impacting it. Contact-induced fracture would always occur for impact energies > 1100 mJ. (4) The force necessary to initiate contact-induced fracture is higher under dynamic or impact conditions than it is under quasi-static indentation conditions. (5) Among the five used sphere materials, silicon nitride was the closest match to 'rock' in terms of both density and (probably) elastic modulus.

  13. Alkali-silicate admixture for cement composites incorporating pozzolan or blast furnace slag

    SciTech Connect

    Zivica, V. . Inst. of construction and Architecture)

    1993-09-01

    This research was devoted to the study of the influence of the developed alkali-silicate admixture (AS admixture) on mortar properties. The obtained results shown that the admixture significantly increased the strength of the mortars made from portland cement (PC) and silica fume (SF) or blast furnace slag (SL). For example after 24 h hardening of mortar (30% SF + 70% PC), with the admixture, reached value of compression strength 18,7 MPa opposite to the value of 5.6 MPa of control mortar (100% PC). The same accelerating effect of AS admixture was observed also with mortar incorporating slag and with slag mortar (100% SL). Further results show that the mortars with AS admixture had an increased content of hydration products and substantially more dense pore structure than mortars of the same composition, but without the admixture.

  14. Tin-containing silicates: alkali salts improve methyl lactate yield from sugars.

    PubMed

    Tolborg, Søren; Sádaba, Irantzu; Osmundsen, Christian M; Fristrup, Peter; Holm, Martin S; Taarning, Esben

    2015-02-01

    This study focuses on increasing the selectivity to methyl lactate from sugars using stannosilicates as heterogeneous catalyst. All group I ions are found to have a promoting effect on the resulting methyl lactate yield. Besides, the alkali ions can be added both during the preparation of the catalyst or directly to the solvent mixture to achieve the highest reported yield of methyl lactate (ca. 75 %) from sucrose at 170 °C in methanol. The beneficial effect of adding alkali to the reaction media applies not only to highly defect-free Sn-Beta prepared through the fluoride route, but also to materials prepared by post-treatment of dealuminated commercial Beta zeolites, as well as ordered mesoporous stannosilicates, in this case Sn-MCM-41 and Sn-SBA-15. These findings open the door to the possibility of using other preparation methods or different Sn-containing silicates with equally high methyl lactate yields as Sn-Beta.

  15. Preparation of calcium silicate absorbent from recycled glass

    SciTech Connect

    Arthur, L.F.; Rochelle, G.T.

    1998-09-01

    Calcium silicate hydrates were prepared from hydrated lime and post-consumer recycled glass in an aqueous slurry. These high surface area solids have shown promise as alkaline sorbents for environmental gas cleaning applications. Surface area was monitored at a variety of reaction conditions. The rate of surface area formation was found to be directly proportional to the initial surface area of the glass. At 92 C, the addition of gypsum to the system had a significant positive effect, forming solids with surface areas up to 125 m{sup 2}/g over long reaction times. Increasing the temperature from 92 C to 120 C increased the initial rate of surface area formation, however the rate decreased over time and the ultimate surface area was higher at 92 C. The addition of gypsum or calcium chloride to the reaction at 120 C increased the ultimate surface area, but not to the extent of the 92 C product. Up to a surface area of {approximately}100 m{sup 2}/g, sorbents formed at 92 C with gypsum were not affected by agitation, nor by solids content between 20--50% under non-agitated conditions. At reaction times after this point, surface area increased slightly with water content and more significantly with agitation. In addition, the dissolution of silica from glass was measured and was found to be faster than the rate of sorbent formation.

  16. Neutron-scattering studies of Yb-bearing silicate glasses

    SciTech Connect

    Ellison, A.J.G.; Loong, C.K.; Wagner, J.

    1993-09-01

    The static and dynamic magnetic response of the Yb{sup 3+} ions in 2Na{sub 2}O{center_dot}Yb{sub 2}O{sub 3}{center_dot}6SiO{sub 2} glass and the isochemical crystalline silicate Na{sub 3}YbSi{sub 3}O{sub 9} has been studied by neutron diffraction, inelastic magnetic-scattering, and magnetic susceptibility measurements. The rare earth sites in the glass have an average coordination number of 5.6 {plus_minus} 0.5 and give a mean rare earth-oxygen bond length of 2.23 {Angstrom}; average Si-O and O-O coordination numbers and bond distances are comparable to those in vitreous SiO{sub 2}. The magnetic excitation spectrum of the Na{sub 3}YbSi{sub 3}O{sub 9} material was analyzed by a crystal-field model using a method of descending symmetry. The magnetic susceptibility and the excitation spectrum of the Yb glasses can be described by a distribution of ligand-field effects on the Yb{sup 3+} ions that are similar to the nominal crystal field in crystalline Na{sub 3}YbSi{sub 3}O{sub 9}.

  17. Intrinsic laser-induced breakdown of silicate glasses

    NASA Astrophysics Data System (ADS)

    Glebov, Leonid B.

    2002-03-01

    This paper is a survey of experimental results in laser- induced damage observed mainly at State Optical Institute (St. Petersburg, Russia; at School of Optics/CREOL (Orlando, FL) which expounds conditions of observation of an intrinsic breakdown of high-purity silicate glasses and proposes the general idea of its mechanism. It is shown that the surface laser-induced breakdown of dielectrics is resulted from photo- and thermo-ionization of surface defects but not from interaction of laser radiation with dielectric material itself. Conditions of thermal ionization of the volume of dielectric materials are determined in dependence on features of absorption of material and temporal features of laser radiation. Statistical properties of laser-induced breakdown of high-purity glasses are caused by statistical properties of laser radiation while the breakdown itself is a deterministic process. Elimination of impact of self-focusing on the results of the breakdown threshold measurements is observed if the spot size of laser radiation in focal plane is less than the wavelength. No photoionization of glass matrix is detected before laser- induced breakdown, and there is no effect of photoionization of impurities and defects on intrinsic breakdown. A mechanism of intrinsic laser-induced breakdown is proposed which is a spasmodic transformation of the electronic level structure in a wide-bandgap dielectric caused by the electric field of laser radiation. This is a collective process converting a transparent material to the opaque state but not an individual process of any type of ionization.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    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/m3) 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.

  19. IR-ATR investigation of surface anisotropy in silicate glasses

    NASA Astrophysics Data System (ADS)

    Ivanovski, Vladimir; Mayerhöfer, Thomas G.; Kriltz, Antje; Popp, Jürgen

    2017-02-01

    Several samples of flat soda-lime silicate glass were investigated by the Infrared Attenuated Total Reflection (IR-ATR) spectroscopy technique. The specular reflectance spectra together with the results of the performed dispersion analysis and the generated reflectance spectra, using Fresnel equations, suggest that the samples are isotropic. In contrast, spectra recorded by the ATR technique suggest an anisotropic structure on the surface of the specimen different from that in the bulk. This is established through differences in the s- and p-polarized IR-ATR spectra, which cannot be simply transformed into one another employing Fresnel formula for an isotropic case. It appears that this thin film having a structure different from the bulk is larger than the ATR effective penetration depth of the evanescent ray for each incidence angle above the critical one. The investigation suggests C2 symmetry of the SiO4 unit.

  20. Antimony and silicon environments in antimony silicate glasses

    SciTech Connect

    Mee, M.; Davies, B.C.; Orman, R.G.; Thomas, M.F.; Holland, D.

    2010-09-15

    Antimony silicate glasses, of general formula xSb{sub 2}O{sub 3}.(1-x)SiO{sub 2} (0.1{<=}x{<=}0.78), have been prepared by melt-quenching and their structures studied using {sup 29}Si MAS NMR spectroscopy, {sup 121}Sb Moessbauer spectroscopy and Raman spectroscopy. Oxidation during melting gives rise to Sb{sup 5+} in concentrations, which increase linearly with x to give a value of {approx}10% when x=0.78. {sup 121}Sb Moessbauer spectra show Moessbauer shifts and quadrupole splittings consistent with Sb{sup 3+} in a [:SbO{sub 3}] trigonal pyramid, similar to that in crystalline Sb{sub 2}O{sub 3}. A broad band in the Raman spectrum at {approx}410 cm{sup -1} is due to the vibrations of such a unit. The dependence of the silicon Q{sup n} speciation on x can be interpreted by the formation of Sb-O-Sb links possibly to form rings of 4 [:SbO{sub 3}] units such as are found in valentinite. - Graphical abstract: Antimony silicate glasses have been shown to contain Sb{sup 3+} in [:SbO{sub 3}] trigonal pyramid units using {sup 121}Sb Moessbauer spectroscopy and Raman spectroscopy. {sup 29}Si magic-angle-spinning NMR has shown silicon Q{sup n} speciation which can be interpreted as formation of rings of 4 [:SbO{sub 3}] units such as are found in valentinite.

  1. Modifier cation effects on (29)Si nuclear shielding anisotropies in silicate glasses.

    PubMed

    Baltisberger, Jay H; Florian, Pierre; Keeler, Eric G; Phyo, Pyae A; Sanders, Kevin J; Grandinetti, Philip J

    2016-07-01

    We have examined variations in the (29)Si nuclear shielding tensor parameters of SiO4 tetrahedra in a series of seven alkali and alkaline earth silicate glass compositions, Cs2O·4.81 SiO2, Rb2O·3.96 SiO2, Rb2O·2.25 SiO2, K2O·4.48 SiO2, Na2O·4.74 SiO2, BaO·2.64 SiO2, and SrO·2.36 SiO2, using natural abundance (29)Si two-dimensional magic-angle flipping (MAF) experiments. Our analyses of these 2D spectra reveal a linear dependence of the (29)Si nuclear shielding anisotropy of Q((3)) sites on the Si-non-bridging oxygen bond length, which in turn depends on the cation potential and coordination of modifier cations to the non-bridging oxygen. We also demonstrate how a combination of Cu(2+) as a paramagnetic dopant combined with echo train acquisition can reduce the total experiment time of (29)Si 2D NMR measurements by two orders of magnitude, enabling higher throughput 2D NMR studies of glass structure.

  2. Modifier cation effects on 29Si nuclear shielding anisotropies in silicate glasses

    NASA Astrophysics Data System (ADS)

    Baltisberger, Jay H.; Florian, Pierre; Keeler, Eric G.; Phyo, Pyae A.; Sanders, Kevin J.; Grandinetti, Philip J.

    2016-07-01

    We have examined variations in the 29Si nuclear shielding tensor parameters of SiO4 tetrahedra in a series of seven alkali and alkaline earth silicate glass compositions, Cs2O · 4.81 SiO2, Rb2O · 3.96 SiO2, Rb2O · 2.25 SiO2, K2O · 4.48 SiO2, Na2O · 4.74 SiO2, BaO · 2.64 SiO2, and SrO · 2.36 SiO2, using natural abundance 29Si two-dimensional magic-angle flipping (MAF) experiments. Our analyses of these 2D spectra reveal a linear dependence of the 29Si nuclear shielding anisotropy of Q(3) sites on the Si-non-bridging oxygen bond length, which in turn depends on the cation potential and coordination of modifier cations to the non-bridging oxygen. We also demonstrate how a combination of Cu2+ as a paramagnetic dopant combined with echo train acquisition can reduce the total experiment time of 29Si 2D NMR measurements by two orders of magnitude, enabling higher throughput 2D NMR studies of glass structure.

  3. Barium boron aluminum silicate glass system for solid state optical gas sensors

    NASA Astrophysics Data System (ADS)

    Da Silva, M. J.; Karczewski, J.; Jasinski, P.; Chrzan, A.; Kalinowski, P.; Szymczewska, D.; Jasinski, G.

    2016-11-01

    Recent increasing demand for new eco-friendly materials and for low cost fabrication process for use in optical sensors field, raise concern about alternative materials for this application. We have designed two glass-ceramics compositions from the quaternary ROAl2O3- SiO2-B2O3(R=Ba) alkali-earth aluminum silicate system, labeled B72 and B69, with high refractive index (>1.6), large values of Abbe number (94.0 and 53.0, respectively), and free of lead and arsenic. We present an analysis and discussion of experimental optical properties, thermal and thermo-chemical stability along with important properties such as transition temperature (Tg), onset of crystallization (Tx) as well transport properties as ionic conductivity behavior in the quaternary glass-ceramic system containing boron for use as optical sensors. Complex Impedance Spectra (Bode Plot) and Potentiodynamic Polarization curves (Tafel plots) measurements were carried out in the temperature range of 600 to 850°C. The most probable conductivity mechanism is a thermally activated process of mobile ions overcoming a potential barrier (EA), according to the Arrhenius regime. Here we report that charge transfer is caused by the flux of electrons, in the region of elevated temperatures (>700°C), and is affected by immiscibility of crystals, nucleation and growth type, that causes phase separation. We found conductivity (σ) values from 10-9 to 10-5 S/cm at temperatures between 700 and 850°C. Our results highlight a need for research on ion mobility in the glassy network above the transition range, and the effect cause by metastable immiscibility in the alkaline-earth glasses are exposed. The two glass compositions B72 and B69 can be tailored by proper use as glassy optical sensor.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Osteogenic capacity of alkali-free bioactive glasses. In vitro studies.

    PubMed

    Brito, Ana F; Antunes, Brígida; Dos Santos, Francisco; Fernandes, Hugo R; Ferreira, José M F

    2016-08-16

    The high alkali content bioactive glasses commonly used to regenerate bone in dental, orthopedic, and maxillofacial surgeries induce some cytotoxicity in surrounding tissues. The present study aims the ability of some alkali-free bioactive glasses compositions, recently developed by our research group, to stimulate human mesenchymal stem cells (hMSCs) differentiation into osteoblasts in comparison to 45S5 Bioglass(®) . The obtained results demonstrated that alkali-free bioactive glasses possess higher stimulating towards differentiation of hMSCs in comparison to the control 45S5 Bioglass(®) . The von Kossa assay demonstrated that all bioactive glasses studied were able to induce the appearance of calcium deposits even when the cells were cultured in DMEM, proving that these biomaterials per se induce hMSCs cell differentiation. It was also observed that in both cell culture medium used (DMEM, and osteogenesis differentiation medium) alkali-free bioactive glasses clearly induced the appearance of more calcium deposits than the 45S5 Bioglass(®) , indicating their greater ability to induce cell differentiation. In summary, these results indicate that alkali-free bioactive glasses are a safe and valid alternative to 45S5 Bioglass(®) . © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2016.

  9. Optical analysis of samarium doped sodium bismuth silicate glass

    NASA Astrophysics Data System (ADS)

    Thomas, V.; Sofin, R. G. S.; Allen, M.; Thomas, H.; Biju, P. R.; Jose, G.; Unnikrishnan, N. V.

    2017-01-01

    Samarium doped sodium bismuth silicate glass was synthesized using the melt quenching method. Detailed optical spectroscopic studies of the glassy material were carried out in the UV-Vis-NIR spectral range. Using the optical absorption spectra Judd-Ofelt (JO) parameters are derived. The calculated values of the JO parameters are utilized in evaluating the various radiative parameters such as electric dipole line strengths (Sed), radiative transition probabilities (Arad), radiative lifetimes (τrad), fluorescence branching ratios (β) and the integrated absorption cross- sections (σa) for stimulated emission from various excited states of Sm3 +‡ ion. The principal fluorescence transitions are identified by recording the fluorescence spectrum. Our analysis revealed that the novel glassy system has the optimum values for the key parameters viz. spectroscopic quality factor, optical gain, stimulated emission cross section and quantum efficiency, which are required for a high performance optical amplifier. Calculated chromaticity co-ordinates (0.61, 0.38) also confirm its application potential in display devices.

  10. 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.

  11. Increases in leach rate due to possible cracking in silicate glasses

    SciTech Connect

    Sang, J.C.; Barkatt, A.; Talmy, I.G.; Norr, M.K.

    1993-12-31

    Comparative studies of two multi-component silicate glasses have confirmed the observation that glasses with a relatively low SiO{sub 2} + AlO{sub 3/2} content may exhibit temporary increases in leach rate during the initial stages of their exposure to water. SEM studies of the leached glass surfaces strongly support the assumption that this phenomenon is due to cracking of the leached glass and a consequent increase of the exposed surface area.

  12. Effect of silicate module of water glass on rheological parameters of poly(sodium acrylate)/sodium silicate hydrogels

    NASA Astrophysics Data System (ADS)

    Mastalska-Popiawska, J.; Izak, P.

    2017-01-01

    The poly(sodium acrylate)/sodium silicate hydrogels were synthesized in the presence of sodium thiosulphate and potassium persulphate as the redox initiators and N,N’-methylene-bisacrylamide as the cross-linking monomer. 20 wt% aqueous solution of sodium acrylate was polymerized together with water glass with different silicate modules (M) from 1.74 to 2.29, in three mass ratio of the monomer solution to the water glass 2:1, 1:1 and 1:2. Such obtained hybrid composites were rheologically tested using the oscillation method. It allowed to designate the crossover point during polymerization, as well as to define the viscoelastic properties of the casted hydrogel samples one week after the reaction. The obtained results of the oscillation measurements showed that cross-linking reaction proceeds very quickly and the lower the silicate module is, the process starts faster. After the completion of the reaction the silicate-polymer hydrogels are strongly elastic materials and the highest elasticity characterizes systems with the mass ratio 1:2, i.e. with the highest water glass content.

  13. 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

  14. X-ray fluorescence analysis with micro glass beads using milligram-scale siliceous samples for archeology and geochemistry

    NASA Astrophysics Data System (ADS)

    Ichikawa, Shintaro; Nakamura, Toshihiro

    2014-06-01

    A micro glass bead technique was developed to assay precious siliceous samples for geochemical and archeological analyses. The micro-sized (approximately 3.5 mm in diameter and 0.8 mm in height) glass beads were prepared by mixing and fusing 1.1 mg of the powdered sample and 11.0 mg of the alkali lithium tetraborate flux for wavelength-dispersive X-ray fluorescence determination of major oxides (Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, MnO, and total Fe2O3). The preparation parameters, including temperature and agitation during the fusing process, were optimized for the use of a commercial platinum crucible rather than a custom-made crucible. The procedure allows preparation of minute sample amounts of siliceous samples using conventional fusing equipment. Synthetic calibration standards were prepared by compounding chemical reagents such as oxides, carbonates, and diphosphates. Calibration curves showed good linearity with r values > 0.997, and the lower limits of detection were in the 10s to 100s of μg g- 1 range (e.g., 140 μg g- 1 for Na2O, 31 μg g- 1 for Al2O3, and 8.9 μg g- 1 for MnO). Using the present method, we determined ten major oxides in igneous rocks, stream sediments, ancient potteries, and obsidian. This was applicable to siliceous samples with various compositions, because of the excellent agreement between the analytical and recommended values of six geochemical references. This minimal-scale analysis may be available for precious and limited siliceous samples (e.g., rock, sand, soil, sediment, clay, and archeological ceramics) in many fields such as archeology and geochemistry.

  15. XRD, lead equivalent and UV-VIS properties study of Ce and Pr lead silicate glasses

    SciTech Connect

    Alias, Nor Hayati Abdullah, Wan Shafie Wan Isa, Norriza Mohd Isa, Muhammad Jamal Md Zali, Nurazila Mat; Abdullah, Nuhaslinda Ee; Muhammad, Azali

    2014-02-12

    In this work, Cerium (Ce) and Praseodymium (Pr) containing lead silicate glasses were produced with 2 different molar ratios low (0.2 wt%) and high (0.4wt%). These types of glasses can satisfy the characteristics required for radiation shielding glasses and minimize the lead composition in glass. The radiation shielding properties of the synthesized glasses is explained in the form of lead equivalent study. The XRD diffraction and UV-VIS analysis were performed to observe the structural changes of the synthesis glasses at 1.5 Gy gamma radiation exposures.

  16. XRD, lead equivalent and UV-VIS properties study of Ce and Pr lead silicate glasses

    NASA Astrophysics Data System (ADS)

    Alias, Nor Hayati; Abdullah, Wan Shafie Wan; Isa, Norriza Mohd; Isa, Muhammad Jamal Md; Muhammad, Azali; Zali, Nurazila Mat; Abdullah, Nuhaslinda Ee

    2014-02-01

    In this work, Cerium (Ce) and Praseodymium (Pr) containing lead silicate glasses were produced with 2 different molar ratios low (0.2 wt%) and high (0.4wt%). These types of glasses can satisfy the characteristics required for radiation shielding glasses and minimize the lead composition in glass. The radiation shielding properties of the synthesized glasses is explained in the form of lead equivalent study. The XRD diffraction and UV-VIS analysis were performed to observe the structural changes of the synthesis glasses at 1.5 Gy gamma radiation exposures.

  17. Speciation of Iron in Silicic Glasses: Inferences From Spectroscopic Methods and TEM

    NASA Astrophysics Data System (ADS)

    Galoisy, L.; Calas, G.; Menguy, N.

    2007-05-01

    Iron environment in silicic glasses has been investigated using optical absorption spectroscopy (OAS), X-ray Absorption Near Edge Structure (XANES), Electron Paramagnetic Resonance (EPR) and TEM. The samples are calco-alkaline silicic glasses from different localities and containing 0.5 to 2 wt% Fe. The redox state of iron in silicate glasses and the local environment around Fe2+ and Fe3+ is known to influence properties such as color or viscosity and crystal-liquid element partitioning, for glasses and melts, respectively. Considering eruption conditions, this information can give a better understanding of the cooling conditions and setting of lava flows. The spectra of silicic glasses are strongly different from that of synthetic glasses and tektites. All spectroscopic methods show the presence of Fe3+ and Fe2+ cations belonging to the glassy network associated with clustered superparamagnetic Fe-oxides. TEM data indicate that nanometric Fe-oxide clusters are poorly crystallized. The spectroscopic data on obsidians have been compared to those recorded on magnetite and synthetic glasses to assess the importance of Fe oxide clusters. These clusters are responsible for the variety of coloration of these obsidians. The speciation of iron in these glasses and associated clusters will be discussed in terms of formation conditions.

  18. 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

  19. Investigation of synthesized Be-bearing silicate glass as laboratory reference sample at X-ray electron probe microanalysis of silicates

    NASA Astrophysics Data System (ADS)

    Belozerova, Olga Yu.; Mikhailov, Mikhail A.; Demina, Tamara V.

    2017-01-01

    The article discusses estimates of the stability and homogeneity in Be-Mg-Al-silicate glass produced by the authors and its applicability as a laboratory reference sample for X-ray electron probe microanalysis (EPMA) of Be-bearing silicate matters: crystals and quenching melt (glasses), silicates and oxides. The results were obtained using Superprobe-733 and Superprobe JXA-8200 (JEOL Ltd, Japan) devices. The sample homogeneity was studied on macro (10-100 μm) and micro (1-10 μm) levels and was evaluated by the scheme of dispersion analysis. The applicability of Be-bearing silicate glass as a reference sample for Mg, Al, Si determinations was tested on the international certified reference glasses and laboratory reference samples of minerals with a known composition. The obtained experimental metrological characteristics correspond to the "applied geochemistry" type of analysis (second category) and suggest that Be-bearing silicate glass is appropriate as a laboratory reference sample for EPMA of Be-bearing silicate matters, silicates and oxides. Using Be-Mg-Al-silicate glass as a reference sample we obtained satisfactory data on the composition of both some minerals including cordierite and beryllium cordierite, beryllium indialite, beryl and metastable phases (chrysoberyl, compounds with structure of β-quartz and petalite).

  20. Interactions of silicate glasses with aqueous environments under conditions of prolonged contact and flow

    NASA Technical Reports Server (NTRS)

    Barkatt, Aaron; Saad, E. E.; Adiga, R. B.; Sousanpour, W.; Barkatt, AL.; Feng, X.; O'Keefe, J. A.; Alterescu, S.

    1988-01-01

    This paper discusses mechanisms involving saturation and reactions that lead to the formation of altered phases in silicate glasses considered for use in geologic repositories for nuclear waste. It is shown that the rate of dissolution of silicate glasses exposed to a broad range of contact times, leachant compositions, and surface-to-volume ratios is strongly affected by the presence of reactive species such as Al, Mg, and Fe. The reactive materials may originate in the leachant or, under conditions of high surface-to-volume ratio, in the glass itself. The effects of glass composition on the course of the corrosion process can be viewed in terms of the formation of a surface layer on the leached glass; the type, composition, and structure of this layer control the dissolution behavior of the glass.

  1. Removal of lead from cathode ray tube funnel glass by generating the sodium silicate.

    PubMed

    Hu, Biao; Zhao, Shuangshuang; Zhang, Shuhao

    2015-01-01

    In the disposal of electronic waste, cathode ray tube (CRT) funnel glass is an environmental problem of old television sets. Removal of the lead from CRT funnel glass can prevent its release into the environment and allow its reuse. In this research, we reference the dry progress productive technology of sodium silicate, the waste CRT glass was dealt with sodium silicate frit melted and sodium silicate frit dissolved. Adding a certain amount of Na ₂CO₃to the waste CRT glass bases on the material composition and content of it, then the specific modulus of sodium silicate frit is obtained by melting progress. The silicon, potassium and sodium compounds of the sodium silicate frit are dissolved under the conditions of high temperature and pressure by using water as solvent, which shows the tendency that different temperature, pressure, liquid-solid ratio and dissolving time have effect on the result of dissolving. At 175°C(0.75MPa), liquid-solid ratio is 1.5:1, the dissolving time is 1h, the dissolution rate of sodium silicate frit is 44.725%. By using sodium sulfide to separate hydrolysis solution and to collect lead compounds in the solution, the recovery rate of lead in dissolving reached 100% and we can get clean sodium silicate and high purity of lead compounds. The method presented in this research can recycle not only the lead but also the sodium, potassium and other inorganic minerals in CRT glass and can obtain the comprehensive utilization of leaded glass.

  2. 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.

  3. MAS-NMR study of lithium zinc silicate glasses and glass-ceramics with various ZnO content

    NASA Astrophysics Data System (ADS)

    Goswami, Madhumita; Kothiyal, Govind P.; Montagne, Lionel; Delevoye, Laurent

    2008-02-01

    Lithium zinc silicate glasses of composition (mol%): 17.5Li 2O-(72- x)SiO 2- xZnO-5.1Na 2O-1.3P 2O 5-4.1B 2O 3, 5.5⩽ x⩽17.7, were prepared by conventional melt-quenched technique and converted to glass-ceramic by controlled crystallization process. 29Si and 31P MAS-NMR was used to characterize the structure of both glass and glass-ceramic samples. Despite the complex glass composition, Q2, Q3 and Q4 sites are identified from 29Si MAS-NMR, which relative intensities are found to vary with the ZnO content, indicating a network depolymerization by ZnO. Moreover, well separated Q3 and Q4 resonances for low ZnO content indicates the occurrence of phase separation. From 31P MAS-NMR, it is seen that phosphorus is mainly present in the form of ortho-( Q0) and pyro-phosphate ( Q1) structural units and variation of ZnO content did not have much effect on these resonances, which provides an additional evidence for phase separation in the glass. On conversion to glass-ceramics, lithium disilicate (Li 2Si 2O 5), lithium zinc ortho-silicate (Li 3Zn 0.5SiO 4), tridymite (SiO 2) and cristobalite (SiO 2) were identified as major silicate crystalline phases. Using 29Si MAS-NMR, quantification of these silicate crystalline phases is carried out and correlated with the ZnO content in the glass-ceramics samples. In addition, 31P spectra unambiguously revealed the presence of crystalline Li 3PO 4 and (Na,Li) 3PO 4 in the glass-ceramics.

  4. The effect of alkalis and polymerization on the solubility of H2O and CO2 in alkali-rich silicate melts

    NASA Astrophysics Data System (ADS)

    Vetere, Francesco; Holtz, Francois; Behrens, Harald; Botcharnikov, Roman E.; Fanara, Sara

    2014-05-01

    The effect of alkalis on the solubility of H2O and CO2 in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H2O/(H2O + CO2) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/ T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H2O solubility (melt equilibrated with pure H2O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO2 content in melts equilibrated with CO2-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/ T = 0.17) to 0.45 wt % for shoshonite (NBO/ T = 0.38) to 0.90 wt % for AH2 (NBO/ T = 0.55). The highest CO2 contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/ T, CO2 solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO2 solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO2 solubility at 500 MPa and 1,100-1,300 °C in various silicate melts as a function of the NBO/ T, (Na + K)/∑cations and Na/(Na + K) parameters: This model is valid for melt compositions with NBO/ T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz-fayalite-magnetite buffer and above.

  5. Surface Morphology and Structure of Double-Phase Magnetic Alkali Borosilicate Glasses

    NASA Astrophysics Data System (ADS)

    Andreeva, N. V.; Naberezhnov, A. A.; Tomkovich, M. V.; Nacke, B.; Kichigin, V.; Rudskoy, A. I.; Filimonov, A. V.

    2016-11-01

    The surface morphology of double-phase magnetic alkali borosilicate glasses of four types obtained by induction melting is studied by the methods of atomic-force and scanning electron microscopy. The distribution of elements over the surface and the elemental composition of the glasses are determined. It is shown that a dendritic system of interrelated channels required for formation of porous matrixes with controlled mean pore diameter may be obtained in these objects depending on the heat treatment mode.

  6. MAS-NMR investigations of the crystallization behaviour of lithium aluminum silicate (LAS) glasses containing P 2O 5 and TiO 2 nucleants

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

    Lithium aluminum silicate (LAS) glass of composition (mol%) 20.4Li 2O-4.0Al 2O 3-68.6SiO 2-3.0K 2O-2.6B 2O 3-0.5P 2O 5-0.9TiO 2 was prepared by melt quenching. The glass was then nucleated and crystallized based on differential thermal analysis (DTA) data and was characterized by 29Si, 31P, 11B and 27Al MAS-NMR. XRD and 29Si NMR showed that lithium metasilicate (Li 2SiO 3) is the first phase to c form followed by cristobalite (SiO 2) and lithium disilicate (Li 2Si 2O 5). 29Si MAS-NMR revealed a change in the network structure already for the glasses nucleated at 550 °C. Since crystalline Li 3PO 4, as observed by 31P MAS-NMR, forms concurrently with the silicate phases, we conclude that crystalline Li 3PO 4 does not act as a nucleating agent for lithium silicate phases. Moreover, 31P NMR indicates the formation of M-PO 4 ( M=B, Al or Ti) complexes. The presence of BO 3 and BO 4 structural units in all the glass/glass-ceramic samples is revealed through 11B MAS-NMR. B remains in the residual glass and the crystallization of silicate phases causes a reduction in the number of alkali ions available for charge compensation. As a result, the number of trigonally coordinated B (BO 3) increases at the expense of tetrahedrally coordinated B (BO 4). The 27Al MAS-NMR spectra indicate the presence of tetrahedrally coordinated Al species, which are only slightly perturbed by the crystallization.

  7. XAS study of Cl and K speciation in glasses quenched from alkalic silicate and carbonate-silicate melts at high-pressure

    NASA Astrophysics Data System (ADS)

    Shiryaev, Andrei; Safonov, Oleg; Huthwelker, Thomas

    2010-05-01

    Data on microinclusions in kimberlitic diamonds and experimental results indicate that potassic Cl-bearing silicate and carbonate-silicate melts could be potential media for diamond nucleation and precursors of carbonatite-kimberlite magmatism in the Earth's mantle. These HP melts were presumably formed in equilibrium immiscible chloride or chloride-carbonate liquids [1, 2]. The immiscibility results from structural properties of the melts, in particular, from K and Cl speciation in them. We report preliminary results on X-ray absorption study of K and Cl local environments in the glasses quenched from melts in the systems NaAlSi2O6-KCl and CaMgSi2O6-CaCO3-Na2CO3-KCl at pressure 5 GPa. Experimental study of the system NaAlSi2O6-KCl [3] revealed a very strong shift of equilibrium between immiscible aluminosilicate and (K,Na)Cl melts NaAlSi2O6+ KCl = KAlSi2O6+ NaCl to the right, resulting in formation of the K-rich (up to 16 wt. % of K2O) aluminosilicate melt with 1.6-1.8 wt.% of Cl. It indicates active separation of K and Cl, which implies different structural positions of these ions in the aluminosilicate melt. Cl XAS spectra in most cases are fairly similar to the spectra of crystalline KCl with minor contribution of NaCl. Thus, chlorine is totally segregated into K(Na)Cl-like clusters of different sizes. K XAS spectra of the glasses could be represented as superposition of contributions from KCl and KAlSi3O8-NaAlSi3O8 glass [4]; the second component is dominant. Thus, in the glasses (and, presumably, in corresponding melts) K is predominantly bound to silicate units, represented by 4-membered rings as follows from Raman spectroscopy. Its CN is higher, than in crystalline leucite (>6). In contrast, Cl is coordinated exclusively by alkali ions in chloride clusters. System CaMgSi2O6-CaCO3-Na2CO3-KCl at 5 GPa shows a wide miscibility gap between Cl-bearing carbonate-silicate and Si-saturated chloride-carbonate melts [1], which converge with a decrease of the SiO2

  8. Titanium induced structural modifications in bismuth silicate glasses

    NASA Astrophysics Data System (ADS)

    Kundu, R. S.; Dult, Meenakshi; Punia, R.; Parmar, Rajesh; Kishore, N.

    2014-04-01

    Glass system with compositions xTiO2·(60 - x)Bi2O3·40SiO2 has been prepared by standard melt quench technique. The amorphous nature of the glass samples has been ascertained by the X-ray diffraction. It is observed that density and molar volume of the studied glasses decrease with increase in TiO2 content whereas the glass transition temperature shows the reverse trend; indicating the increase in compactness of the glass structure with increase in TiO2 content. The Raman and FTIR studies reveal that on addition of TiO2, some of SiO4 tetrahedra units with three non-bridging oxygens (NBOs) per silicon are converted into SiO4 tetrahedral units with four NBO per silicon and number of network forming BiO3 pyramidal units goes on decreasing and no BiO3 pyramidal units are observed in glass composition with x = 20. Bismuth plays the role of network modifier with BiO6 octahedral units for all the studied glass compositions. TiO2 acts as network former with TiO4 tetrahedral units in all the glass compositions having titanium besides acting as network modifier TiO6 octahedral units in glass compositions with x = 10, 15 and 20. However, the glass composition with x = 15 has maximum number of TiO4 structural units among all the studied glass compositions.

  9. High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of mixed-alkali metals uranyl silicates

    SciTech Connect

    Chen, Yi-Hsin; Liu, Hsin-Kuan; Chang, Wen-Jung; Tzou, Der-Lii; Lii, Kwang-Hwa

    2016-04-15

    Three mixed-alkali metals uranyl silicates, Na{sub 3}K{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}]·2H{sub 2}O (1), Na{sub 3}Rb{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}] (2), and Na{sub 6}Rb{sub 4}[(UO{sub 2}){sub 4}Si{sub 12}O{sub 33}] (3), have been synthesized by high-temperature, high-pressure hydrothermal reactions at 550 °C and 1440 bar, and characterized by single-crystal X-ray diffraction, photoluminescence, and thermogravimetric analysis. Compound 1 and 2 are isostructural and contain layers of uranyl disilicate. The smaller cation, Na{sup +}, is located in the intralayer channels, whereas the larger cations, K{sup +} and Rb{sup +}, and water molecule are located in the interlayer region. The absence of lattice water in 2 can be understood according to the valence-matching principle. The structure is related to that of a previously reported mixed-valence uranium(V,VI) silicate. Compound 3 adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain with the structural formula {uB,4"1_∞}[{sup 3}Si{sub 12}O{sub 33}] formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. The connectivity of the Si atoms in the Si{sub 12}O{sub 33}{sup 18−} anion can be interpreted on the basis of Zintl–Klemm concept. Crystal data for compound 1: triclinic, P-1, a=5.7981(2) Å, b=7.5875(3) Å, c=12.8068(5) Å, α=103.593(2)°, β=102.879(2)°, γ=90.064(2)°, V=533.00(3) Å{sup 3}, Z=1, R1=0.0278; compound 2: triclinic, P-1, a=5.7993(3) Å, b=7.5745(3) Å, c=12.9369(6) Å, α=78.265(2)°, β=79.137(2)°, γ=89.936(2)°, V=546.02(4) Å{sup 3}, Z=1, R1=0.0287; compound 3: monoclinic, C2/m, a=23.748(1) Å, b=7.3301(3) Å, c=15.2556(7) Å, β=129.116(2)°, V=2060.4(2) Å{sup 3}, Z=2, R1=0.0304. - Graphical abstract: Three mixed-alkali metals uranyl silicates were synthesized under hydrothermal conditions at 550 °C and 1400 bar and structurally characterized by single-crystal X-ray diffraction. Two of them have a layer structure

  10. Optical absorption and photoluminescence properties of Er3+ doped mixed alkali borate glasses.

    PubMed

    Ratnakaram, Y C; Kumar, A Vijaya; Naidu, D Tirupathi; Rao, J L

    2005-07-01

    An investigations of the optical absorption and fluorescence spectra of 0.2 mol% Er2O3 in mixed alkali borate glasses of the type 67.8B2O3 x xLi2O(32-x)Na2O, 67.8B2O3 x xLi2O(32-x)K2O and 67.8B2O3 x xNa2O(32-x)K2O (where x = 8, 12, 16, 20 and 24) are presented. The glasses were obtained by quenching melts consisting of H3BO3, Li2CO3, Na2CO3, K2CO3 and Er2O3 (950-1100 degrees C, 1.5-2 h) between two brass plates. Spectroscopic parameters like Racah (E1, E2 and E3), spin-orbit (xi(4f)) and configuration interaction (alpha) parameters are deduced as function of x. Using Judd-Ofelt theory, Judd-Ofelt intensity parameters (omega2, omega4 and omega6) are obtained. Radiative and non-radiative transition rates (A(T) and W(MPR)), radiative lifetimes (tauR), branching ratios (beta) and integrated absorption cross-sections (sigma) have been computed for certain excited states of Er3+ in these mixed alkali borate glasses. Emission spectra have been studied for all the three Er3+ doped mixed alkali borate glasses. The present paper throws light on the trends observed in the intensity parameters, radiative lifetimes, branching ratios and emission cross-sections as a function of x in these borate glasses, keeping in view the effect of mixed alkalies in borate glasses.

  11. Influence of mixed alkalies on absorption and emission properties of Sm 3+ ions in borate glasses

    NASA Astrophysics Data System (ADS)

    Ratnakaram, Y. C.; Thirupathi Naidu, D.; Vijaya Kumar, A.; Gopal, N. O.

    2005-04-01

    The present work aims to study the variation of Judd-Ofelt intensity parameters, radiative transition probabilities, absorption and emission cross sections with alkali content in three different Sm 3+-doped mixed alkali borate glasses. Mixed alkali borate glasses in the composition 67H 3BO 3· xLi 2CO 3(32- x)Na 2CO 3·1Sm 2O 3, 67H 3BO 3· xLi 2CO 3(32- x)K 2CO 3·1Sm 2O 3 and 67H 3BO 3· xNa 2CO 3(32- x)K 2CO 3·1Sm 2O 3 with x=8, 12, 16, 20 and 24 mol% were prepared by quenching melts consisting of the above chemicals (850-950 °C, 1-2 h) between two brass plates. Judd-Ofelt theory is used to study the spectral properties and to calculate the radiative transition probabilities and branching ratios. The predicted radiative transition probabilities ( Aed), branching ratios ( β) and integrated absorption cross-sections ( Σ) for certain transitions are reported. From the emission spectra, emission cross-sections ( σ) are obtained for the four transitions, 4G 5/2→ 6H 5/2, 4G 5/2→ 6H 7/2, 4G 5/2→ 6H 9/2 and 4G 5/2→ 6H 11/2 of Sm 3+ ion in these mixed alkali borate glasses. Optical band gaps ( Eopt) and absorption edges are reported for the three Sm 3+-doped mixed alkali borate glasses.

  12. Float processing of high-temperature complex silicate glasses and float baths used for same

    NASA Technical Reports Server (NTRS)

    Cooper, Reid Franklin (Inventor); Cook, Glen Bennett (Inventor)

    2000-01-01

    A float glass process for production of high melting temperature glasses utilizes a binary metal alloy bath having the combined properties of a low melting point, low reactivity with oxygen, low vapor pressure, and minimal reactivity with the silicate glasses being formed. The metal alloy of the float medium is exothermic with a solvent metal that does not readily form an oxide. The vapor pressure of both components in the alloy is low enough to prevent deleterious vapor deposition, and there is minimal chemical and interdiffusive interaction of either component with silicate glasses under the float processing conditions. Alloys having the desired combination of properties include compositions in which gold, silver or copper is the solvent metal and silicon, germanium or tin is the solute, preferably in eutectic or near-eutectic compositions.

  13. Iron modified structural and optical spectral properties of bismuth silicate glasses

    NASA Astrophysics Data System (ADS)

    Parmar, Rajesh; Kundu, R. S.; Punia, R.; Aghamkar, P.; Kishore, N.

    2014-10-01

    Iron bismuth silicate glasses have been successfully synthesized by melt quenching technique. The amorphous nature of the glass samples is ascertained by the XRD patterns. The values of density, molar volume and crystalline volume have been measured and are found to decrease with increase in iron content. The glass transition temperature measured using Differential Scanning Calorimetry (DSC) also varies with increase in Fe2O3 content. The Raman and FTIR spectra of the studied glass system taken at room temperature suggests that Fe2O3 modifies the structure of bismuth silicate glasses and it acts as both network modifier as well as network former. Bismuth also plays the role of both network modifier (BiO6 octahedra) as well as network former (BiO3 pyramids) and SiO2 exists in SiO4 tetrahedral structural units with two non-bridging oxygens. The Hydrogenic excitonic model is found to be applicable to the studied glass compositions. The variation in Urbach energy value observed for the studied glass samples suggests the possibility of increase in the number of glass defects. The metallization criterion for the synthesized glass samples is determined and found to be in the range 0.30-0.38.

  14. Structural features of alkali and barium aluminofluorophosphate glasses studied by IR spectroscopy

    SciTech Connect

    Urusovskaya, L.N.; Smirnova, E.V.

    1995-03-01

    IR reflection spectra of the Al(PO{sub 3}){sub 3}-MeF{sub x} glasses (Me=Li, Na, K, Ba) with the maximum content of fluoride varied for each specific glass within certain concentration limits are considered. Analysis of the spectra for glasses obtained upon variation in the content of alkali metal fluoride introduced into these glasses has demonstrated that the increase in the MeF{sub x} content leads to breaking the chain groupings and forming the [PO{sub 3}F]{sup 2-} groups, whereas the rise in concentration of barium fluoride in the Al(PO{sub 3}){sub 3}-BaF{sub 2} glasses brings about the stabilization of the chain structures.

  15. Structure and luminescence of intrinsic localized states in sodium silicate glasses

    NASA Astrophysics Data System (ADS)

    Konstantinou, Konstantinos; Duffy, Dorothy M.; Shluger, Alexander L.

    2016-11-01

    Sodium silicate glasses exhibit a characteristic luminescence with a maximum at about 3.4 eV, which is thought to be determined by optical excitation of local glass structures, called L centers. To investigate the atomic and electronic structures of these centers, we calculated the electronic properties of the ground and excited states of a sodium silicate glass using classical and ab initio methods. Classical molecular dynamics was used to generate glass models of Na2O -3 SiO2 molar composition, and the density functional theory (DFT), with hybrid functionals, was used to identify and characterize the geometric and electronic structures of L centers. The ground and excited L* center states are studied, and their calculated excitation and luminescence transition energies are in good agreement with experimental data. The results confirm that the lowest triplet excited states in sodium silicate glass are associated with small clusters of Na ions and nonbridging oxygen atoms. These clusters serve as structural precursors for the localization of the excited states, and the broad distribution of the luminescence energies is correlated with the short-range order of the Na cations. The atomic and electronic structures of the electron E1- and hole H1+ centers are also studied. These results provide a more detailed insight into the atomistic structure of localized states in these important glasses.

  16. NMR evidence for five-coordinated silicon in a silicate glass at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Stebbins, Jonathan F.

    1991-06-01

    KNOWLEDGE of the structure of liquid silicates is essential to understanding the properties of materials ranging from magmas in lava flows to melts in glass processing. At 1 atmosphere pressure, a wide range of evidence indicates that most silicon cations in these systems are coordinated by four oxygens in a tetrahedral configuration (SiIV). Molecular dynamics computer simulations of these liquids have, however, predicted that defect complexes (of relatively low abundance) consisting of silicon with five oxygen neighbours (SiV) are of key importance in the mechanism by which viscous flow takes place1-5. I present here direct experimental evidence from 29Si NMR studies of K2Si4O9 glass that SiV does exist in silicate liquids at low pressures, and that the abundance of this species increases with temperature, supporting the idea that SiV defects contribute to 'weakening' of the structure of molten silicates.

  17. Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

    NASA Technical Reports Server (NTRS)

    Ming, Douglas W.; Golden, D. C.

    2004-01-01

    Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

  18. 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.

  19. Manganese modified structural and optical properties of bismuth silicate glasses

    NASA Astrophysics Data System (ADS)

    Dult, Meenakshi; Kundu, R. S.; Berwal, Neelam; Punia, R.; Kishore, N.

    2015-06-01

    Glass system with compositions xMnO2-(60-x) Bi2O3-40SiO2 have been synthesized by standard melt quench technique. X-ray diffraction patterns confirm the amorphous nature of as-prepared glass samples. The values of density have been measured and molar volume determined is found to decrease with increase in MnO2 content. Theoretical calculations of crystalline volume (Vc) have also been made. The glass transition temperature (Tg) determined using differential scanning calorimetry (DSC) is observed to increase with increase in MnO2 content. The structural analysis has been carried out using FTIR and Raman spectroscopy. In the present glass system, MnO2 acts as network modifier and exists in MnO6 structural units. Bismuth acts both as network former with BiO3 pyramidal units as well as network modifier with BiO6 octahedral units in the present glass system. SiO2 exists in form of SiO4 tetrahedral structural units with two non-bridging oxygens (NBO's). The optical band gap energy (Eg) has been estimated from Tauc's plot for direct transitions, it decreases with increase in manganese content.

  20. Potential Applications of Alkali-Activated Alumino-Silicate Binders in Military Operations

    DTIC Science & Technology

    1985-11-01

    silica/alumina compounds ( cancrinites ) will not crystallize unless a template compound (sodium sulfate or nitrate) is present in solution to fill the...used in waste dis- posal. The compounds that form in low-temperature clay-alkali reactions (zeo- lites and cancrinites ) are large cage-like crystals that

  1. Mixed alkali effect in glasses containing MnO{sub 2}

    SciTech Connect

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

    2013-02-05

    Glass systems of the composition xLi{sub 2}O-(25-x)K{sub 2}O-70(0.4ZnO+0.6P{sub 2}O{sub 5})+5MnO{sub 2} (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%Li{sub 2}O. 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 Mn{sup 2+} ions in these glasses showed strong broad absorption band at 514 nm corresponding to the transition {sup 6}A{sub 1g}(S){yields}{sup 4}T{sub 1g}(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%Li{sub 2}O glass.

  2. The microstructure of soda-lime silicate glasses detected by electron microscopy

    NASA Astrophysics Data System (ADS)

    Krajczyk, L.; Suszynska, M.

    2003-01-01

    Transmission electron microscopy and selected area electron diffraction performances were used to characterise the microstructure of a multicomponent soda-lime silicate glass, the composition of which corresponds to the miscibility gap in the SiO2-Na2O system. It has been stated that phase separation already exists in as prepared specimens, and the Na2O-rich phase occurs in the form of nearly spherical droplets. The microstructure of these glasses was modified by high-temperature annealing in air and hydrogen, by irradiation with soft X- and gamma-irradiation and by mechanical stretching. In this way the quantity, size, shape and distribution of these particles was changed. A variety of induced changes affects the structure-sensitive properties of commercial soda lime silicate glasses, which can be potentially useful for new applications.

  3. Monitoring ageing of alkali resistant glass fiber reinforced cement (GRC) using guided ultrasonic waves

    NASA Astrophysics Data System (ADS)

    Eiras, J. N.; Amjad, U.; Mahmoudabadi, E.; Payá, J.; Bonilla, M.; Kundu, T.

    2013-04-01

    Glass fiber reinforced cement (GRC) is a Portland cement based composite with alkali resistant (AR) glass fibers. The main drawback of this material is the ageing of the reinforcing fibers with time and especially in presence of humidity in the environment. Until now only destructive methods have been used to evaluate the durability of GRC. In this study ultrasonic guided wave inspection of plate shaped specimens has been carried out. The results obtained here show that acoustic signatures are capable of discerning ageing in GRC. Therefore, the ultrasonic guided wave based inspection technique is a promising method for the nondestructive evaluation of the durability of the GRC.

  4. Nanometre-scale evidence for interfacial dissolution-reprecipitation control of silicate glass corrosion

    NASA Astrophysics Data System (ADS)

    Hellmann, Roland; Cotte, Stéphane; Cadel, Emmanuel; Malladi, Sairam; Karlsson, Lisa S.; Lozano-Perez, Sergio; Cabié, Martiane; Seyeux, Antoine

    2015-03-01

    Silicate glasses are durable solids, and yet they are chemically unstable in contact with aqueous fluids—this has important implications for numerous industrial applications related to the corrosion resistance of glasses, or the biogeochemical weathering of volcanic glasses in seawater. The aqueous dissolution of synthetic and natural glasses results in the formation of a hydrated, cation-depleted near-surface alteration zone and, depending on alteration conditions, secondary crystalline phases on the surface. The long-standing accepted model of glass corrosion is based on diffusion-coupled hydration and selective cation release, producing a surface-altered zone. However, using a combination of advanced atomic-resolution analytical techniques, our data for the first time reveal that the structural and chemical interface between the pristine glass and altered zone is always extremely sharp, with gradients in the nanometre to sub-nanometre range. These findings support a new corrosion mechanism, interfacial dissolution-reprecipitation. Moreover, they also highlight the importance of using analytical methods with very high spatial and mass resolution for deciphering the nanometre-scale processes controlling corrosion. Our findings provide evidence that interfacial dissolution-reprecipitation may be a universal reaction mechanism that controls both silicate glass corrosion and mineral weathering.

  5. Nanometre-scale evidence for interfacial dissolution-reprecipitation control of silicate glass corrosion.

    PubMed

    Hellmann, Roland; Cotte, Stéphane; Cadel, Emmanuel; Malladi, Sairam; Karlsson, Lisa S; Lozano-Perez, Sergio; Cabié, Martiane; Seyeux, Antoine

    2015-03-01

    Silicate glasses are durable solids, and yet they are chemically unstable in contact with aqueous fluids-this has important implications for numerous industrial applications related to the corrosion resistance of glasses, or the biogeochemical weathering of volcanic glasses in seawater. The aqueous dissolution of synthetic and natural glasses results in the formation of a hydrated, cation-depleted near-surface alteration zone and, depending on alteration conditions, secondary crystalline phases on the surface. The long-standing accepted model of glass corrosion is based on diffusion-coupled hydration and selective cation release, producing a surface-altered zone. However, using a combination of advanced atomic-resolution analytical techniques, our data for the first time reveal that the structural and chemical interface between the pristine glass and altered zone is always extremely sharp, with gradients in the nanometre to sub-nanometre range. These findings support a new corrosion mechanism, interfacial dissolution-reprecipitation. Moreover, they also highlight the importance of using analytical methods with very high spatial and mass resolution for deciphering the nanometre-scale processes controlling corrosion. Our findings provide evidence that interfacial dissolution-reprecipitation may be a universal reaction mechanism that controls both silicate glass corrosion and mineral weathering.

  6. 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.

  7. Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals.

    PubMed

    Wang, Yifeng; Jove-Colon, Carlos F; Kuhlman, Kristopher L

    2016-07-22

    Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruent dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). Our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.

  8. Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

    PubMed Central

    Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

    2016-01-01

    Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruent dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). Our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications. PMID:27443508

  9. Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

    DOE PAGES

    Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

    2016-07-22

    Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruentmore » dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). In conclusion, our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.« less

  10. Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

    SciTech Connect

    Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

    2016-07-22

    Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruent dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). In conclusion, our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.

  11. Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

    NASA Astrophysics Data System (ADS)

    Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

    2016-07-01

    Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruent dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). Our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.

  12. Effect of alkaline-earth ions on the dynamics of alkali ions in bismuthate glasses

    NASA Astrophysics Data System (ADS)

    Dutta, A.; Ghosh, A.

    2005-12-01

    The effect of alkaline earth ions on the dynamics of Li+ ions in bismuthate glasses has been studied in the temperature range 353-503K and in the frequency range 10Hz-2MHz . The dc conductivity increases and activation energy decreases with the increase of a particular alkaline earth content for the glasses with a fixed alkali content. The increased modification of the network due to the increase in alkaline earth content in the compositions is responsible for the increasing conductivity. Also the compositions with smaller alkaline earth ions were found to exhibit higher conductivity. Although the conductivity increases with the decrease of ionic radii of alkaline earth ions, the activation energy shows a maximum for the Sr ion. The electric modulus and the conductivity formalisms have been employed to study the relaxation dynamics of charge carriers in these glasses. The alkali ions were observed to change their dynamics with the change of the alkaline earth ions. The same anomalous trend for activation energy for the conductivity relaxation frequency and the hopping frequency was also observed for glasses containing SrO. It was also observed that the mobile lithium ion concentrations are independent of nature of alkaline earth ions in these glasses.

  13. Vibrational interactions of tetrahedra in silicate glasses and crystals

    NASA Astrophysics Data System (ADS)

    Dowty, Eric

    1987-02-01

    Normal coordinate calculations, producing synthetic infrared and Raman spectra, were carried out on melilites, pyroxenes, silica polymorphs and feldspars. Atomic motions are complex in the high-frequency Raman modes of melilites and aluminous pyroxenes. The symmetric T-Onb stretching vibrations of Si and Al tetrahedra with different numbers of bridging oxygens are separate from each other, but may combine individually with oscillation of bridging oxygens between Si and Al tetrahedra. The latter type of vibration tends to dominate as Al/Si increases. The frequencies of these vibrational components and the degree of such intermixing depend on T-O force constants, which vary greatly depending on local bonding configurations; individual bands in the high-frequency Raman cannot in general be assigned to single structural entities or fixed combinations thereof. Calculations confirm that in some Al-Si glasses such as jadeite and spodumene, i.e. those in which all Al can be tetrahedral without non-bridging oxygens, Al-O-Al linkages or linkage of more than two tetrahedra by a single oxygen, aluminum is predominantly in tetrahedral coordination. Other Al-Si glasses which are richer in aluminum or which have non-bridging oxygens may contain Al tetrahedral triclusters, non-tetrahedral Al, or both. On the basis of distinctive 450 750 cm-1 infrared bands, both silica and feldspar glasses resemble tridymite and related stuffed derivatives, not other crystalline silica polymorphs or feldspars. Either these glasses have a structure like that of tridymite on a local scale, or the disorder of the glasses causes drastic modification to the vibrations in question.

  14. 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.

  15. A composition-independent quantitative determination of the water content in silicate glasses and silicate melt inclusions by confocal Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zajacz, Zoltán; Halter, Werner; Malfait, Wim J.; Bachmann, Olivier; Bodnar, Robert J.; Hirschmann, Marc M.; Mandeville, Charles W.; Morizet, Yann; Müntener, Othmar; Ulmer, Peter; Webster, James D.

    2005-12-01

    A new approach was developed to measure the water content of silicate glasses using Raman spectroscopy, which is independent of the glass matrix composition and structure. Contrary to previous studies, the compositional range of our studied silicate glasses was not restricted to rhyolites, but included andesitic, basaltic and phonolitic glasses. We used 21 glasses with known water contents for calibration. To reduce the uncertainties caused by the baseline removal and correct for the influence of the glass composition on the spectra, we developed the following strategy: (1) application of a frequency-dependent intensity correction of the Raman spectra; (2) normalization of the water peak using the broad T-O and T-O-T vibration band at 850-1250 cm-1 wavenumbers (instead of the low wavenumber T-O-T broad band, which appeared to be highly sensitive to the FeO content and the degree of polymerization of the melt); (3) normalization of the integrated Si-O band area by the total number of tetrahedral cations and the position of the band maximum. The calibration line shows a ±0.4 wt% uncertainty at one relative standard deviation in the range of 0.8-9.5 wt% water and a wide range of natural melt compositions. This method provides a simple, quick, broadly available and cost-effective way for a quantitative determination of the water content of silicate glasses. Application to silicate melt inclusions yielded data in good agreement with SIMS data.

  16. Relationship between microstructure and efficiency of lithium silicate scintillating glasses: The effect of alkaline earths

    SciTech Connect

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

    1996-12-31

    Lithium silicate glasses containing Ce{sup 3+} are known to be scintillators. Glasses in this family in which the Li is enriched ({sup 6}Li) are used as neutron detectors. The addition of Mg to this glass is known to increase the scintillation efficiency. We have found that substituting other alkaline earths results in a monotonic decrease of the scintillation efficiency with increasing atomic number. The total variation in scintillation efficiency from Mg to Ba is nearly a factor of 3. Prior experiments with this glass family show small differences in Raman and fluorescence spectra; evidence from thermoluminescence experiments indicates that the scintillation efficiency is most strongly correlated with structural effects in the neighborhood of the Ce{sup 3+} activator ion. The results of low-temperature studies of fluorescence and thermoluminescence of these glasses will be reported.

  17. Water as a dense icelike component in silicate glasses

    PubMed

    Richet; Polian

    1998-07-17

    Density and Brillouin-scattering measurements of hydrous andesite glasses at ambient conditions showed that dissolved water has a concentration-independent partial molar volume of 12 +/- 0.5 cubic centimeters per mole and a bulk modulus of 18 +/- 3 gigapascals. Dissolved as hydroxyl ions or as molecular water, water has volume properties similar to those of ice VII, the densest form of ice. These properties point to hydrogen bonding as an important factor in water dissolution, and they indicate that changes of water speciation are driven by the entropy and not by the volume of the system. Water in a concentration greater than 1 percent by weight also causes a marked decrease of the shear modulus of the glass.

  18. Elaboration And Characterization Of Foam Glass Based On Cullet With Addition Of Soluble Silicates

    NASA Astrophysics Data System (ADS)

    Ayadi, A.; Stiti, N.; Benhaoua, F.; Boumchedda, K.; Lerari, Y.

    2011-01-01

    The politics of the energy saving and of the acoustic comfort buildings is at the heart of the research of new compounds permitting to improve the materials performance actually commercialised. With this aim in view, we'll purpose to elaborate a porous material (foam glass) with addition of soluble silicates (up to 40%) of which the principal material is the waste glass in order to recycle it and improving the present laws about the waste products in closed circuit: (Finished products ← waste products← finished products). The investigations have shown that grinding waste glass to particle size less than 0.1 mm and adding 1% of Ca CO3 content provide production of material with the following properties: particle density 0,5 g/cm3, strength 17,50 MPa and water adsorption 95%, the temperature for foaming ranges were determined at 850° C. The microstructures are homogenous, with pore sizes up to 2 mm. The addition of soluble silicates (up to 40%) has resulted in the foam glass of very high porosity. The foam glass is counted among the new glass products meeting certain requirements sought comfort in the building industry in particular (thermal and acoustic insulation). The product obtained present of excellent properties thermal (λ = 0,031 W/m° C) and acoustic (R = 15 dB).

  19. Elaboration And Characterization Of Foam Glass Based On Cullet With Addition Of Soluble Silicates

    SciTech Connect

    Ayadi, A.; Stiti, N.; Benhaoua, F.; Boumchedda, K.; Lerari, Y.

    2011-01-17

    The politics of the energy saving and of the acoustic comfort buildings is at the heart of the research of new compounds permitting to improve the materials performance actually commercialised. With this aim in view, we'll purpose to elaborate a porous material (foam glass) with addition of soluble silicates (up to 40%) of which the principal material is the waste glass in order to recycle it and improving the present laws about the waste products in closed circuit: (Finished products (leftarrow) waste products (leftarrow) finished products). The investigations have shown that grinding waste glass to particle size less than 0.1 mm and adding 1% of Ca CO{sub 3} content provide production of material with the following properties: particle density 0,5 g/cm{sup 3}, strength 17,50 MPa and water adsorption 95%, the temperature for foaming ranges were determined at 850 deg. C. The microstructures are homogenous, with pore sizes up to 2 mm. The addition of soluble silicates (up to 40%) has resulted in the foam glass of very high porosity. The foam glass is counted among the new glass products meeting certain requirements sought comfort in the building industry in particular (thermal and acoustic insulation). The product obtained present of excellent properties thermal ({lambda} = 0,031 W/m deg. C) and acoustic (R = 15 dB).

  20. Encapsulation of TRISO particle fuel in durable soda-lime-silicate glasses

    NASA Astrophysics Data System (ADS)

    Heath, Paul G.; Corkhill, Claire L.; Stennett, Martin C.; Hand, Russell J.; Meyer, Willem C. H. M.; Hyatt, Neil C.

    2013-05-01

    Tri-Structural Isotropic (TRISO) coated particle-fuel is a key component in designs for future high temperature nuclear reactors. This study investigated the suitability of three soda lime silicate glass compositions, for the encapsulation of simulant TRISO particle fuel. A cold press and sinter (CPS) methodology was employed to produce TRISO particle-glass composites. Composites produced were determined to have an aqueous durability, fracture toughness and Vickers' hardness comparable to glasses currently employed for the disposal of high level nuclear wastes. Sintering at 700 °C for 30 min was found to remove all interconnected porosity from the composite bodies and oxidation of the outer pyrolytic carbon layer during sintering was prevented by processing under a 5% H2/N2 atmosphere. However, the outer pyrolytic carbon layer was not effectively wetted by the encapsulating glass matrix. The aqueous durability of the TRISO particle-glass composites was investigated using PCT and MCC-1 tests combined with geochemical modelling. It was found that durability was dependent on silicate and calcium solution saturation. This study provides significant advancements in the preparation of TRISO particle encapsulant waste forms. The potential for the use of non-borosilicate sintered glass composites for TRISO particle encapsulation has been confirmed, although further refinements are required.

  1. Effect of Network Modifying Cations on the Structural Disorder in Multi-Component Silicate Glasses

    NASA Astrophysics Data System (ADS)

    Sung, S.

    2005-12-01

    The structure of complex, multi-component silicate glasses and melts provides insight into the physiochemical properties (e.g. viscosity, diffusivity, and thermodynamic properties) of natural silicate melts. Particularly, quaternary aluminosilicate glasses are important as it covers compositions of slab driven melts at the convergent margin and, thus, yield constraints for the dynamics of magmas in the earth's interior. Despite this importance, the structure of CaO-Na2O-Al2O3-SiO2 (CNAS) glasses has not been well understood because of inherent disorder in glasses and melts (Lee et al., 2005, Am, Min. p 1393). Solid-state 17O triple quantum (3Q) MAS MNR has been effective in yielding unpresented resolutions among oxygen sites in the glasses over conventional 1D MAS NMR, allowing us to determine the structure of multi-component silicate glasses (Lee et al., 2005, Am, Min. p 1393, Stebbins and Xu, 1997, Nature, p 60). Here, we report the first 17O MAS and 3QMAS NMR spectra for CNAS glasses with varying the Ca/Na ([(CaO) x (Na2O) 1.5-x](Al2O3)0.5 (SiO2)6) ratios at static magnetic fields of 14.1 Tesla (600 MHz). 17O MAS spectra show bridging oxygen (BO) peaks and partially resolved non-bridging oxygen (NBO) peaks (Ca-NBO and mixed {Ca, Na}-NBO). NBO in Ca-aluminosilicate glass moves toward lower frequency with increasing the Na/Ca ratios due to the formation of mixed-{Ca, Na}-NBO. This result suggests that the chemical shielding of mixed {Ca, Na}-NBO peak increases with increasing Ca contents and there is a mixing between Ca and Na around NBO in the Ca-Na aluminosilicate glasses. 17O 3QMAS NMR spectra exhibit well resolved BO peaks and partially resolved Ca-NBO and mixed-{Ca, Na}-NBO peaks. The fraction of Ca-NBO decrease with increasing Na/Ca ratios while the fraction of BO appears to be invariant with Na/Ca ratios. These results imply that NBO interacts more severely with network modifying cations than BO does. Another inherent disorder in silicate glasses and melts

  2. Pressure effect on the elasticity and structure of Na- silicate glasses

    NASA Astrophysics Data System (ADS)

    Yu, T.; Sakamaki, T.; Kono, Y.; Jing, Z.; Watson, H. C.; Wang, Y.; Shen, G.

    2013-12-01

    The ratio of non-bridging oxygen to tetrahedrally coordinated cation (NBO/T) represents the degree of polymerization and is a well-known parameter used for categorizing amorphous silicates. The NBO/T ratios are 0, 1, and 2 for pure silica (SiO2), sodium disilicate (Na2Si2O5), and sodium silicate (Na2SiO3) respectively. Previously, we observed a turn-around in sound velocity-pressure relations at ambient temperature in sodium disilicate glass. Velocity minima were located between 2-3GPa for both the longitudinal wave velocity (Vp) and the transverse wave velocity (Vs), similar to those reported for pure SiO2 glasses (Zha et al., 1994; Yokoyama et al., 2010; Kono et al., 2011). Earlier studies on silica suggested certain structural response to pressure that may play an important role in the change of elasticity (Vukcevich, 1972; Jorgensen, 1978). Although silica and sodium disilicate have different NBO/T values, they show similar pressure-dependent velocity trends up to 5GPa at ambient temperature. Rigidity percolation threshold theory of glasses suggests that the elastic behavior is very different with NBO/T above and below ~1.6 (Phillips & Thorpe, 1985). Synthesized Na-silicate glasses (Na2Si2O5 and Na2SiO3) with compositions across the NBO/T=1.6 threshold were loaded into a Paris-Edinburgh (PE) cell at the HPCAT 16-BM-B beamline, and structure information has been collected up to 5GPa at ambient temperature to study the local glass structure evolution during compression, and to compare the structures between these various amorphous silicates, which represent distinct NBO/T values. Elastic wave travel times of the glass samples at high pressure have been collected using the ultrasonic pulse reflection method at the GSECARS beamlines 13-BM-D and 13-ID-D. The velocity and structure data of the Na- silicate glasses will be presented.

  3. Reductive surface synthesis of gold nanoparticles on silicate glass and their biochemical sensor applicationsa

    PubMed Central

    Li, M.; Kim, D.-P.; Jeong, G.-Y.; Seo, D.-K.; Park, C.-P.

    2012-01-01

    Gold nanoparticles (Au NPs) were directly synthesized on the surface of polyvinylsilazane (PVSZ, -[(vinyl)SiH-NH2]-) without use of extra reductive additives. The reductive Si-H functional groups on the surface of cured PVSZ acted as surface bound reducing agents to form gold metal when contacted with an aqueous Au precursor (HAuCl4) solution, leading to formation of Au NPs adhered to silicate glass surface. The Au NPs-silicate platforms were preliminarily tested to detect Rhodamine B (1 μM) by surface enhanced Raman scattering. Furthermore, gold microelectrode obtained by post-chemical plating was used as an integrated amperometric detection element in the polydimethylsilane-glass hybrid microfluidic chip. PMID:24324531

  4. Reductive surface synthesis of gold nanoparticles on silicate glass and their biochemical sensor applications.

    PubMed

    Li, M; Kim, D-P; Jeong, G-Y; Seo, D-K; Park, C-P

    2012-01-01

    Gold nanoparticles (Au NPs) were directly synthesized on the surface of polyvinylsilazane (PVSZ, -[(vinyl)SiH-NH2]-) without use of extra reductive additives. The reductive Si-H functional groups on the surface of cured PVSZ acted as surface bound reducing agents to form gold metal when contacted with an aqueous Au precursor (HAuCl4) solution, leading to formation of Au NPs adhered to silicate glass surface. The Au NPs-silicate platforms were preliminarily tested to detect Rhodamine B (1 μM) by surface enhanced Raman scattering. Furthermore, gold microelectrode obtained by post-chemical plating was used as an integrated amperometric detection element in the polydimethylsilane-glass hybrid microfluidic chip.

  5. Quantitative analysis of major elements in silicate minerals and glasses by micro-PIXE

    USGS Publications Warehouse

    Campbell, J.L.; Czamanske, G.K.; MacDonald, L.; Teesdale, W.J.

    1997-01-01

    The Guelph micro-PIXE facility has been modified to accommodate a second Si(Li) X-ray detector which records the spectrum due to light major elements (11 ??? Z ??? 20) with no deleterious effects from scattered 3 MeV protons. Spectra have been recorded from 30 well-characterized materials, including a broad range of silicate minerals and both natural and synthetic glasses. Sodium is mobile in some of the glasses, but not in the studied mineral lattices. The mean value of the instrumental constant H for each of the elements Mg, Al, and Si in these materials is systematically 6-8% lower than the H-value measured for the pure metals. Normalization factors are derived which permit the matrix corrections requisite for trace-element measurements in silicates to be based upon pure metal standards for Mg, Al and Si, supplemented by well-established, silicate mineral standards for the elements Na, K and Ca. Rigorous comparisons of electron microprobe and micro-PIXE analyses for the entire, 30-sample suite demonstrate the ability of micro-PIXE to produce accurate analysis for the light major elements in silicates. ?? 1997 Elsevier Science B.V.

  6. Optical properties and structure of beryllium lead silicate glasses

    NASA Astrophysics Data System (ADS)

    Zhidkov, I. S.; Zatsepin, A. F.; Cholakh, S. O.; Kuznetsova, Yu. A.

    2014-10-01

    Luminescence and optical properties and structural features of (BeO)x(PbOṡSiO2)1-x glasses (x = 0 ÷ 0.3) are investigated by means of optical absorption and photoluminescence spectroscopy and X-ray diffraction. The regularities of the formation of the optical absorption edge and static disorder are studied. It is shown that the optical absorption and luminescence are determined by transitions between localized states of lead ions. The impact of beryllium oxide on optical and luminescence properties and electronic structure of bands tails is discussed. The presence of two different concentration ranges with various short-range order structure and band tails nature has been established.

  7. Optical properties and structure of beryllium lead silicate glasses

    SciTech Connect

    Zhidkov, I. S.; Zatsepin, A. F.; Cholakh, S. O.; Kuznetsova, Yu. A.

    2014-10-21

    Luminescence and optical properties and structural features of (BeO){sub x}(PbO⋅SiO{sub 2}){sub 1−x} glasses (x = 0 ÷ 0.3) are investigated by means of optical absorption and photoluminescence spectroscopy and X-ray diffraction. The regularities of the formation of the optical absorption edge and static disorder are studied. It is shown that the optical absorption and luminescence are determined by transitions between localized states of lead ions. The impact of beryllium oxide on optical and luminescence properties and electronic structure of bands tails is discussed. The presence of two different concentration ranges with various short-range order structure and band tails nature has been established.

  8. Femtosecond laser writing of waveguide structures in sodium calcium silicate glasses

    SciTech Connect

    Reichman, W J; Click, C A; Krol, D M

    2004-12-13

    Waveguides were written in soda lime silicate glasses with a composition of xNa{sub 2}O xCaO (1-2x)SiO{sub 2}, where x = 15 and 20, using an amplified femtosecond laser. The waveguides formed around, not inside the exposed regions. This is similar to the waveguide behavior our group first observed in a phosphate glass, Schott IOG-1, and is distinctly different from fused silica in which the waveguides are inside the exposed regions. This data supports the rapid quenching theory, i.e. that the exposed regions cool rapidly, locking in a glass structure with a high fictive temperature, with the dependence of the refractive index on the glass cooling rate determining the qualitative behavior of the waveguides.

  9. Structural relaxation phenomena in silicate glasses modified by irradiation with femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Seuthe, Thomas; Mermillod-Blondin, Alexandre; Grehn, Moritz; Bonse, Jörn; Wondraczek, Lothar; Eberstein, Markus

    2017-03-01

    Structural relaxation phenomena in binary and multicomponent lithium silicate glasses were studied upon irradiation with femtosecond (fs) laser pulses (800 nm central wavelength, 130 fs pulse duration) and subsequent thermal annealing experiments. Depending on the annealing temperature, micro-Raman spectroscopy analyses evidenced different relaxation behaviours, associated to bridging and non-bridging oxygen structures present in the glass network. The results indicate that the mobility of lithium ions is an important factor during the glass modification with fs-laser pulses. Quantitative phase contrast imaging (spatial light interference microscopy) revealed that these fs-laser induced structural modifications are closely related to local changes in the refractive index of the material. The results establish a promising strategy for tailoring fs-laser sensitivity of glasses through structural mobility.

  10. Structural relaxation phenomena in silicate glasses modified by irradiation with femtosecond laser pulses

    PubMed Central

    Seuthe, Thomas; Mermillod-Blondin, Alexandre; Grehn, Moritz; Bonse, Jörn; Wondraczek, Lothar; Eberstein, Markus

    2017-01-01

    Structural relaxation phenomena in binary and multicomponent lithium silicate glasses were studied upon irradiation with femtosecond (fs) laser pulses (800 nm central wavelength, 130 fs pulse duration) and subsequent thermal annealing experiments. Depending on the annealing temperature, micro-Raman spectroscopy analyses evidenced different relaxation behaviours, associated to bridging and non-bridging oxygen structures present in the glass network. The results indicate that the mobility of lithium ions is an important factor during the glass modification with fs-laser pulses. Quantitative phase contrast imaging (spatial light interference microscopy) revealed that these fs-laser induced structural modifications are closely related to local changes in the refractive index of the material. The results establish a promising strategy for tailoring fs-laser sensitivity of glasses through structural mobility. PMID:28266615

  11. Ion-exchange characteristics of sodium-calcium-silicate glass: Calculation from mode spectra

    NASA Astrophysics Data System (ADS)

    Zhurikhina, V. V.; Petrov, M. I.; Sokolov, K. S.; Shustova, O. V.

    2010-10-01

    The characteristics of silver-sodium ion exchange in standard commercial sodium-calcium-silicate glass are investigated using mode spectroscopy. The activation energy of the process, the silver-sodium interdiffusion coefficient, and the dependence of the maximal modulation of the refractive index on the silver nitrate concentration in the experimental salt bath are determined. The data set presented here makes it possible to specify the conditions for the formation of ion-exchange optical structures with preset parameters based on the glasses studied here.

  12. Velocity of a freely rising gas bubble in a soda-lime silicate glass melt

    NASA Technical Reports Server (NTRS)

    Hornyak, E. J.; Weinberg, M. C.

    1984-01-01

    A comparison is conducted between measured velocities for the buoyant rise of single bubbles of varying size and composition, in a soda-lime silicate glass melt, with the steady state velocities predicted by the Stokes and Hadamard-Rybczynski formulas. In all cases, the data are noted to fit the Hadamard-Rybczynski expression for steady state rise speed considerably better than the Stokes formula.

  13. Sub-critical crack growth in silicate glasses: Role of network topology

    SciTech Connect

    Smedskjaer, Morten M.; Bauchy, Mathieu

    2015-10-05

    The presence of water in the surrounding atmosphere can cause sub-critical crack growth (SCCG) in glasses, a phenomenon known as fatigue or stress corrosion. Here, to facilitate the compositional design of more fatigue-resistant glasses, we investigate the composition dependence of SCCG by studying fourteen silicate glasses. The fatigue curves (V-K{sub I}) have been obtained by indentation experiments through measurements of the crack length as a function of post-indentation fatigue duration. Interestingly, we find that the fatigue resistance parameter N is generally improved by increasing the alumina content and is thereby found to exhibit a fairly linear dependence on the measured Vickers hardness H{sub V} for a wide range of N and H{sub V} values. This finding highlights the important role of network topology in governing the SCCG in silicate glasses, since hardness has been shown to scale linearly with the number of atomic constraints. Our results therefore suggest that glasses showing under-constrained flexible networks, which feature floppy internal modes of deformation, are more readily attacked by water molecules, thus promoting stress corrosion and reducing the fatigue resistance.

  14. Sub-critical crack growth in silicate glasses: Role of network topology

    NASA Astrophysics Data System (ADS)

    Smedskjaer, Morten M.; Bauchy, Mathieu

    2015-10-01

    The presence of water in the surrounding atmosphere can cause sub-critical crack growth (SCCG) in glasses, a phenomenon known as fatigue or stress corrosion. Here, to facilitate the compositional design of more fatigue-resistant glasses, we investigate the composition dependence of SCCG by studying fourteen silicate glasses. The fatigue curves (V-KI) have been obtained by indentation experiments through measurements of the crack length as a function of post-indentation fatigue duration. Interestingly, we find that the fatigue resistance parameter N is generally improved by increasing the alumina content and is thereby found to exhibit a fairly linear dependence on the measured Vickers hardness HV for a wide range of N and HV values. This finding highlights the important role of network topology in governing the SCCG in silicate glasses, since hardness has been shown to scale linearly with the number of atomic constraints. Our results therefore suggest that glasses showing under-constrained flexible networks, which feature floppy internal modes of deformation, are more readily attacked by water molecules, thus promoting stress corrosion and reducing the fatigue resistance.

  15. Gallium-containing phospho-silicate glasses: synthesis and in vitro bioactivity.

    PubMed

    Franchini, Mirco; Lusvardi, Gigliola; Malavasi, Gianluca; Menabue, Ledi

    2012-08-01

    A series of Ga-containing phospho-silicate glasses based on Bioglass 45S5, having molar formula 46.2SiO2·24.3Na2O·26.9CaO·2.6P2O5·xGa2O3 (x=1.0, 1.6, 3.5), were prepared by fusion method. The reference Bioglass 45S5 without gallium was also prepared. The synthesized glasses were immersed in simulated body fluid (SBF) for 30 days in order to observe ion release and hydroxyapatite (HA) formation. All Ga-containing glasses maintain the ability of HA formation as indicated by main X-ray diffractometric peaks and/or electronic scanning microscopy results. HA layer was formed after 1 day of SBF soaking in 45S5 glass containing up to 1.6% Ga2O3 content. Moreover, gallium released by the glasses was found to be partially precipitated on the glass surface as gallium phosphate. Further increase in gallium content reduced the ion release in SBF. The maximum of Ga(3+) concentration measured in solution is ~6 ppm determined for 3.5% Ga2O3 content. This amount is about half of the toxic level (14 ppm) of gallium and the glasses release gallium till 30 days of immersion in SBF. Considering the above results, the studied materials can be proposed as bioactive glasses with additional antimicrobial effect of gallium having no toxic outcome.

  16. Iron in Silicate Glasses: Systematic Analysis of Pre-Edge And Xanes Features

    SciTech Connect

    Farges, F.; Rossano, S.; Wilke, M.; Lefrere, Y.; Brown, G.E., Jr.; /SLAC, SSRL

    2006-10-27

    A large number (67) of silicate glasses containing variable amounts of iron oxide were studied by high-resolution XANES spectroscopy at the Fe K-edge to determine an accurate method to derive redox information from pre-edge features. The glass compositions studied mimic geological magmas, ranging from basaltic to rhyolitic, dry and hydrous, with variable quench rates. The studied glasses also include more chemically simple calco-sodic silicate glass compositions. The Fe contents range from 30 wt.% to less than 2000 ppm. For most of the series of composition studied, the pre-edge information varies linearly with redox, even under high-resolution conditions. The average coordination of Fe(II) is often similar to its Fe(III) counterpart except in highly polymerized glasses because of the strong influence exerted by the tetrahedral framework on iron's sites. Natural volcanic glasses (from various volcanoes around the world) show similar variations. The average coordination of Fe(II) is often comprised between 4.5 and 5. Fe(III) shows larger variations in coordination (4 to 6, depending on composition). Bond valence models are proposed to predict the average coordination of Fe based on composition. Molecular dynamics simulations (Born-Mayer-Huggins) potentials were carried out on some compositions to estimate the magnitude of disorder effects (both static and thermal) in the XAFS analysis. XANES calculations based on the MD simulations and FEFF 8.2 show large variations in the local structures around Fe. Also, 5-coordinated Fe(III) is found to be an important moiety in ferrisilicate glasses. For Fe(II), discrepancies between glass and melt are larger and are related to its greater structural relaxation at T{sub g}. Also, a strong destructive interference between network formers and modifiers explain the relatively weak intensity of the next-nearest neighbors contributions in the experimental spectra.

  17. A complete inorganic colour converter based on quantum-dot-embedded silicate glasses for white light-emitting-diodes.

    PubMed

    Han, Karam; Im, Won Bin; Heo, Jong; Chung, Woon Jin

    2016-02-28

    A complete inorganic quantum dot color converter for a white LED is achieved using silicate-based quantum-dot-embedded glasses (QDEGs). The white LED exhibits a high CRI of 90 and highly improved thermal stability up to 200 °C, demonstrating its robustness and practicality. The CdSe/CdS core/shell structure within the silicate glass is expected to enhance the colour converting efficiency.

  18. Sulfur Speciation and Network Structural Changes in Sodium Silicate Glass: Raman Spectroscopic Study

    NASA Astrophysics Data System (ADS)

    Tsujimura, T.; Walter, M. J.; Kawamoto, T.; Kusakabe, M.

    2002-12-01

    Information about the state of sulfur (S) in silicate glasses is important in geo- and material sciences. S dissolves as sulfide in silicate glasses under reduced conditions, whereas it dissolves as sulfate under oxidizing conditions1. However, the effects of sulfur speciation on silicate melt structure have not been quantified. Here, we present a systematic study of the relation between S speciation and network structure in sodium silicate glasses by micro-Raman spectroscopy. Nominal compositions of synthesized glasses were Na2Si2O5+S, Na2Si2O5+Na2S, Na2Si2O5+Na2SO4 and Na_{2}O+SiO_{2}+Na_{2}SO_{4} along the Na/Si=1.0. First, S-free sodium silicate glasses were prepared from reagent grade Na_{2}CO_{3} and SiO_{2} at ambient pressure. S-added glasses were loaded in Pt capsules, and held at 1000°C and 1-2kbar for 1h and were quenched to glasses in IHPV. All glasses were clear and no crystals were observed by optical microscope. Glasses were yellow or colorless, however quenched sulfur (~2\\mum) was observed in glasses, and this was eliminated by CS_{2}. After this treatment, sulfur contents in glasses were measured by ion chromatography. SKα shift was measured by EPMA. Micro Raman spectra were obtained using both 514.5 nm Ar-ion laser and 532 nm YAG laser radiation. In order to obtain quantitative relationships, we fitted the high frequency envelope to Gaussian lines. Based on SKα shift systematics, sulfur dissolved mostly as sulfide (>70%) in native-S added glasses, whereas it dissolved as sulfate in sulfate-added glasses. As for the S-free glass, a strong high frequency peak at 1100cm^{-1} can be attributed to the symmetric Si-O stretching of Q_{3} species within the glass, and a peak at 950 cm^{-1} is caused by Si-O stretching of Q_{2} species. Raman bands in the 500-600cm^{-1} region are associated with bending vibrations of the Si-O-Si linkage, and these frequencies depend on degree of polymerization of the silicate units^{2}. As for the S-bearing glasses

  19. The formation of silver metal nanoparticles by ion implantation in silicate glasses

    NASA Astrophysics Data System (ADS)

    Vytykacova, S.; Svecova, B.; Nekvindova, P.; Spirkova, J.; Mackova, A.; Miksova, R.; Böttger, R.

    2016-03-01

    It has been shown that glasses containing silver metal nanoparticles are promising photonics materials for the fabrication of all-optical components. The resulting optical properties of the nanocomposite glasses depend on the composition and structure of the glass, as well as on the type of metal ion implanted and the experimental procedures involved. The main aim of this article was to study the influence of the conditions of the ion implantation and the composition of the glass on the formation of metal nanoparticles in such glasses. Four various types of silicate glasses were implanted with Ag+ ions with different energy (330 keV, 1.2 MeV and 1.7 MeV), with the fluence being kept constant (1 × 1016 ions cm-2). The as-implanted samples were annealed at 600 °C for 1 h. The samples were characterised in terms of: the nucleation of metal nanoparticles (linear optical absorption), the migration of silver through the glass matrix during the implantation and post-implantation annealing (Rutherford backscattering spectroscopy), and the oxidation state of silver (photoluminescence in the visible region).

  20. The effect of viscosity on nanocrystallization of strontium fluoride from a silicate glass

    NASA Astrophysics Data System (ADS)

    Bocker, Christian; Wiemert, Janine; Rüssel, Christian

    2014-04-01

    This paper describes the importance of the viscosity development in the glass-ceramics process with respect to the mechanism of nano crystallization in oxyfluoride glasses. In the glass system under investigation nano crystalline SrF2 is formed from a silicate glass Na2O/K2O/SrF2/Al2O3/SiO2. The occurring crystallization mechanism is clarified by the variation of the SrF2 concentration and the resulting structures. As expected, the mechanism shows similarities to other recently described oxyfluoride systems. The feature of the present system is that during cooling of the melt a liquid/liquid phase separation occurs which is not the case in similar systems containing BaF2. A droplet phase enriched in strontium and fluoride is formed which is embedded in a silicate rich matrix phase. During thermal annealing, nano crystalline cubic SrF2 is precipitated inside the droplet phase. As a result, the viscosity of the residual glassy phase increases during the course of the crystallization. The crystal sizes do not exceed 8 nm, neither if the annealing time nor if the temperature is increased.

  1. High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of mixed-alkali metals uranyl silicates

    NASA Astrophysics Data System (ADS)

    Chen, Yi-Hsin; Liu, Hsin-Kuan; Chang, Wen-Jung; Tzou, Der-Lii; Lii, Kwang-Hwa

    2016-04-01

    Three mixed-alkali metals uranyl silicates, Na3K3[(UO2)3(Si2O7)2]·2H2O (1), Na3Rb3[(UO2)3(Si2O7)2] (2), and Na6Rb4[(UO2)4Si12O33] (3), have been synthesized by high-temperature, high-pressure hydrothermal reactions at 550 °C and 1440 bar, and characterized by single-crystal X-ray diffraction, photoluminescence, and thermogravimetric analysis. Compound 1 and 2 are isostructural and contain layers of uranyl disilicate. The smaller cation, Na+, is located in the intralayer channels, whereas the larger cations, K+ and Rb+, and water molecule are located in the interlayer region. The absence of lattice water in 2 can be understood according to the valence-matching principle. The structure is related to that of a previously reported mixed-valence uranium(V,VI) silicate. Compound 3 adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain with the structural formula {uB,41∞}[3Si12O33] formed of Q2, Q3, and Q4 Si. The connectivity of the Si atoms in the Si12O3318- anion can be interpreted on the basis of Zintl-Klemm concept. Crystal data for compound 1: triclinic, P-1, a=5.7981(2) Å, b=7.5875(3) Å, c=12.8068(5) Å, α=103.593(2)°, β=102.879(2)°, γ=90.064(2)°, V=533.00(3) Å3, Z=1, R1=0.0278; compound 2: triclinic, P-1, a=5.7993(3) Å, b=7.5745(3) Å, c=12.9369(6) Å, α=78.265(2)°, β=79.137(2)°, γ=89.936(2)°, V=546.02(4) Å3, Z=1, R1=0.0287; compound 3: monoclinic, C2/m, a=23.748(1) Å, b=7.3301(3) Å, c=15.2556(7) Å, β=129.116(2)°, V=2060.4(2) Å3, Z=2, R1=0.0304.

  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. Luminescence spectra and structure of Er3+ doped alkali borate and fluoroborate glasses

    NASA Astrophysics Data System (ADS)

    Arul Rayappan, I.; Marimuthu, K.

    2013-11-01

    Trivalent erbium (Er3+) ion doped alkali borate and fluoroborate glasses were prepared and their structural and spectroscopic properties have been studied through XRD, FTIR, optical absorption and luminescence spectral measurements. The FTIR spectral studies reveal the presence of BO3, BO4 structural units and the strong OH- bonds in the title glasses. The absorption spectra were used to determine the bonding parameters (β¯,δ) of the prepared glasses. Judd—Ofelt intensity parameters (Ωλ, λ=2, 4 and 6) have been calculated from the optical absorption spectra and are used to predict the important radiative properties like radiative transition probability (A), stimulated emission cross-section (σPE) and branching ratios (βR) for the excited state transitions such as 2H9/2→4I15/2 and 4S3/2→4I15/2 of the Er3+ ions in the prepared glasses. Optical band gap energy (Eopt) values through direct, indirect allowed transitions and the Urbach energy (ΔE) values of the prepared Er3+ glasses have also been determined and compared with similar studies. The spectral characteristics of the Er3+ ions due to compositional changes have been examined and reported in the present work.

  4. 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.

  5. Phase relations and melting of carbonated peridotite between 10 and 20 GPa: a proxy for alkali- and CO2-rich silicate melts in the deep mantle

    NASA Astrophysics Data System (ADS)

    Ghosh, Sujoy; Litasov, Konstantin; Ohtani, Eiji

    2014-02-01

    We determined the melting phase relations, melt compositions, and melting reactions of carbonated peridotite on two carbonate-bearing peridotite compositions (ACP: alkali-rich peridotite + 5.0 wt % CO2 and PERC: fertile peridotite + 2.5 wt % CO2) at 10-20 GPa and 1,500-2,100 °C and constrain isopleths of the CO2 contents in the silicate melts in the deep mantle. At 10-20 GPa, near-solidus (ACP: 1,400-1,630 °C) carbonatitic melts with < 10 wt % SiO2 and > 40 wt % CO2 gradually change to carbonated silicate melts with > 25 wt % SiO2 and < 25 wt % CO2 between 1,480 and 1,670 °C in the presence of residual majorite garnet, olivine/wadsleyite, and clinoenstatite/clinopyroxene. With increasing degrees of melting, the melt composition changes to an alkali- and CO2-rich silicate melt (Mg# = 83.7-91.6; ~ 26-36 wt % MgO; ~ 24-43 wt % SiO2; ~ 4-13 wt % CaO; ~ 0.6-3.1 wt % Na2O; and ~ 0.5-3.2 wt % K2O; ~ 6.4-38.4 wt % CO2). The temperature of the first appearance of CO2-rich silicate melt at 10-20 GPa is ~ 440-470 °C lower than the solidus of volatile-free peridotite. Garnet + wadsleyite + clinoenstatite + carbonatitic melt controls initial carbonated silicate melting at a pressure < 15 GPa, whereas garnet + wadsleyite/ringwoodite + carbonatitic melt dominates at pressure > 15 GPa. Similar to hydrous peridotite, majorite garnet is a liquidus phase in carbonated peridotites (ACP and PERC) at 10-20 GPa. The liquidus is likely to be at ~ 2,050 °C or higher at pressures of the present study, which gives a melting interval of more than 670 °C in carbonated peridotite systems. Alkali-rich carbonated silicate melts may thus be produced through partial melting of carbonated peridotite to 20 GPa at near mantle adiabat or even at plume temperature. These alkali- and CO2-rich silicate melts can percolate upward and may react with volatile-rich materials accumulate at the top of transition zone near 410-km depth. If these refertilized domains migrate upward and convect out of the

  6. The effect of electron beam irradiation on silver-sodium ion exchange in silicate glasses

    NASA Astrophysics Data System (ADS)

    Sidorov, Alexander I.; Prosnikov, Mikhail A.

    2016-04-01

    It is shown experimentally that electron irradiation of sodium-silicate glasses makes possible the control of the subsequent ion exchange Ag+ ↔ Na+ process in a salt melt. The reason of this effect is the negatively charged regions formation in a glass volume during electron irradiation. The electric field, produced by these regions in glass volume, results in positive Na+ ions field migration into them. The spatial redistribution of Na+ ions results in the decrease of the ion exchange efficiency, or the ion exchange can be even blocked. This led to the decrease of the luminescence intensity of neutral silver molecular clusters in the irradiated zone, and effect on the silver nanoparticles formation during the subsequent thermal treatment. The observed effects can be used for the control of ion exchange processes during integrated optics devices fabrication, and for the electron-beam recording of optical information.

  7. Extruded channel waveguides in a neodymium-doped lead-silicate glass for integrated optic applications

    NASA Astrophysics Data System (ADS)

    Mairaj, Arshad K.; Feng, Xian; Hewak, Daniel W.

    2003-10-01

    We report on the development of channel waveguides in a lead-silicate glass through the extrusion technique. An extruded glass slab with four imbedded fibers each with core size of 8 by 2.5 μm in the horizontal and vertical directions was manufactured. These neodymium-doped channel waveguides were in single-mode operation at 808 nm and had attenuation of 0.1 dB cm-1 at 1.06 μm. The measured 4F3/2 lifetime of 488 μs and emission cross section of 2.5×10-20 cm2 were in good agreement with reported values. The integration of multiple glass variants into a single compact platform is presented as a manufacturing route for complex integrated optical waveguides.

  8. Vibrational features of phospho-silicate glasses: Periodic B3LYP simulations

    NASA Astrophysics Data System (ADS)

    Corno, Marta; Pedone, Alfonso

    2009-07-01

    B3LYP periodic calculations with double-ζ polarised basis set using C RYSTAL06 code have been run on a bioactive phospho-silicate glass similar in composition to Bioglass ® 45S5 (46.1 SiO 2, 24.4 Na 2O, 26.9 CaO and 2.6 P 2O 5 mol%) and a phosphorous-free soda-lime glass (49.5 SiO 2, 24.2 Na 2O and 26.4 CaO mol%). Initial structures have been obtained through a melt-quench process by classical molecular dynamics techniques and the effect of phosphorous on the glass network structure and dynamics have been assessed by B3LYP vibrational spectra.

  9. Effect of Swift Heavy Ion Irradiation on Lithium Zinc Silicate Glasses: A Photoluminescence Study

    NASA Astrophysics Data System (ADS)

    Jogad, M. S.; Jogad, R. M.; Sudarsan, V.; Krishna, P. S. R.; Kothiyal, G. P.

    2011-07-01

    Lithium zinc silicate glasses with and without copper were prepared by melt-quench method and their luminescence characteristics after swift heavy ion irradiation has been investigated. Based on these studies it is established that both these glasses contain colour centres and the luminescence from such centres get significantly quenched once these samples get irradiated with 100 MeV swift heavy Ag+ ions with a fluence of 1013ions/cm2 at room temperature. Trapping of the charge carriers by the increased defect concentration brought about by irradiation is responsible for the decrease in the luminescence intensity from the irradiated samples. Copper in these glasses mainly exists as Cu+ ions as revealed by the broad emission around 500 nm.

  10. Local Structures around Si, Al and Na in Hydrated Silicate Glasses

    SciTech Connect

    Farges, Francois; Wispelaere, Sidoine de; Rossano, Stephanie; Munos, Manuel; Wilke, Max; Flank, Anne-Marie; Lagarde, Pierre

    2007-02-02

    XANES spectra were collected at the Si-, Al-, and Na K-edge in hydrous silicate glasses to understand the effect of water on the local structure around these cations. Around network forming Si and Al, no drastic changes are observed. Around Na, the dissolution of water creates more ordered environments in Al-bearing glasses and less ordered environment in Al-free glasses. Ab-initio XANES calculations were undertaken to understand the structural origins for these features. Based on these results, a bond valence model was refined that considers not only the present XANES experiments and models but also NMR information. The double percolation model refined explains, among others, the explosive properties of water-bearing hydrous melts, at the origin of a number of cataclysmic eruptions in subduction zones.

  11. Structural and optical study on antimony-silicate glasses doped with thulium ions.

    PubMed

    Dorosz, D; Zmojda, J; Kochanowicz, M; Miluski, P; Jelen, P; Sitarz, M

    2015-01-05

    Structural, spectroscopic and thermal properties of SiO₂-Al₂O₃-Sb₂O₃-Na₂O glass system doped with 0.2 mol% Tm₂O₃ have been presented. Synthesis of antimony-silicate glasses with relatively low phonon energy (600 cm(-1), which implicates a small non-radiative decay rate) was performed by conventional high-temperature melt-quenching methods. The effect of SiO₂/Sb₂O₃ ratio in fabricated Tm(3+) doped glass on thermal, structural and luminescence properties was investigated. On the basis of structural investigations decomposition of absorption bands in the infrared FTIR region was performed, thus determining that antimony ions are the only glass-forming ions, setting up the lattice of fabricated glasses. Luminescence band at the wavelength of 1.8 μm corresponding to (3)F₄→(3)H₆ transition in thulium ions was obtained under 795 nm laser pumping. It was observed that combination of relatively low phonon energy and greater separation of optically active centers in the fabricated glasses influenced in decreasing the luminescence intensity at 1800 nm.

  12. Absorption and emission characteristics of Er3+ ions in alkali chloroborophosphate glasses.

    PubMed

    Moorthy, L R; Rao, T S; Janardhnam, K; Radhapathy, A

    2000-08-01

    Alkali chloroborophosphate glasses containing 1 mol% of Er3+ ions were studied experimentally using the absorption and emission spectroscopy. The energy level scheme for the 4f11 (Er3+) electronic configuration was deduced from the observed band energies of the absorption spectra in terms of a parametrized Hamiltonian using the various free-ion spectroscopic parameters. Oscillator strengths (f) measured from the absorption spectra have been analyzed using the Judd-Ofelt theory to evaluate the three intensity parameters omegalambda (lambda = 2, 4 and 6). Reasonable agreement between the measured and calculated f values has been found. Electric and magnetic dipole transition probabilities, fluorescence branching ratios, integrated emission cross sections and radiative lifetimes were calculated for all the excited states of Er3+ ions. The non-radiative (WNR) relaxation rates from the excited levels to the next lower levels have been calculated and the relationship between the energy gap and non-radiative relaxation rate has been established. These results were used to predict the possible potential laser transitions in Er-doped alkali chloroborophosphate glasses.

  13. Deformation, Stress Relaxation, and Crystallization of Lithium Silicate Glass Fibers Below the Glass Transition Temperature

    NASA Technical Reports Server (NTRS)

    Ray, Chandra S.; Brow, Richard K.; Kim, Cheol W.; Reis, Signo T.

    2004-01-01

    The deformation and crystallization of Li(sub 2)O (center dot) 2SiO2 and Li(sub 2)O (center dot) 1.6SiO2 glass fibers subjected to a bending stress were measured as a function of time over the temperature range -50 to -150 C below the glass transition temperature (Tg). The glass fibers can be permanently deformed at temperatures about 100 C below T (sub)g, and they crystallize significantly at temperatures close to, but below T,, about 150 C lower than the onset temperature for crystallization for these glasses in the no-stress condition. The crystallization was found to occur only on the surface of the glass fibers with no detectable difference in the extent of crystallization in tensile and compressive stress regions. The relaxation mechanism for fiber deformation can be best described by a stretched exponential (Kohlrausch-Williams-Watt (KWW) approximation), rather than a single exponential model.The activation energy for stress relaxation, Es, for the glass fibers ranges between 175 and 195 kJ/mol, which is considerably smaller than the activation energy for viscous flow, E, (about 400 kJ/mol) near T, for these glasses at normal, stress-free condition. It is suspected that a viscosity relaxation mechanism could be responsible for permanent deformation and crystallization of the glass fibers below T,

  14. Time Evolution of Radiation-Induced Luminescence in Terbium-Doped Silicate Glass

    NASA Technical Reports Server (NTRS)

    West, Michael S.; Winfree, William P.

    1996-01-01

    A study was made on two commercially available terbium-doped silicate glasses. There is an increased interest in silicate glasses doped with rare-earth ions for use in high-energy particle detection and radiographic applications. These glasses are of interest due to the fact that they can be formed into small fiber sensors; a property that can be used to increase the spatial resolution of a detection system. Following absorption of radiation, the terbium ions become excited and then emit photons via 4f-4f electronic transitions as they relax back to the ground state. The lifetime of these transitions is on the order of milliseconds. A longer decay component lasting on the order of minutes has also been observed. While radiative transitions in the 4f shell of rare-earth ions are generally well understood by the Judd-Olfelt theory, the pr'esence of a longer luminescence decay component is not. Experimental evidence that the long decay component is due, in part, to the thermal release of trapped charge carriers will be presented. In addition, a theoretical model describing the time evolution of the radiation-induced luminescence will be presented.

  15. Compositional investigation of ∼2 μm luminescence of Ho{sup 3+}-doped lead silicate glass

    SciTech Connect

    Liu, Xueqiang; Huang, Feifei; Gao, Song; Wang, Xin; Hu, Lili; Chen, Danping

    2015-11-15

    Graphical abstract: Ho{sup 3+}-doped lead silicate glass with lowest maximum phonon energy possesses highest ∼2 μm luminescence intensity. - Highlights: • With increment of lead oxide, maximum phonon energy in lead silicate glass decreased. • ∼2 μm luminescent intensity of Ho{sup 3+} increased with increment of lead oxide. • Lowest lead oxide content glass possesses highest quantum efficiency due to low maximum phonon energy. - Abstract: Lead silicate glass samples with varying lead oxide content were prepared in this study, and their luminescent properties were examined and analyzed. It was found that with increasing lead oxide content, the maximum phonon energies of the glass samples decreased, while their spontaneous transition probabilities first increased and then decreased. The influence of the spontaneous transition rate, A{sub 10}, and the multi-phonon relaxation rate, W{sub 10}, on the sample luminescent properties was analyzed using rate equations. As a result, it was found that with increasing lead oxide content, W{sub 10}/A{sub 10} decreased, while the quantum efficiency increased. Thus, the luminescent intensity at ∼2 μm increased in the glass samples with increased lead oxide content. The high luminescent intensity and long lifetime indicate that silicate glasses containing high levels of lead oxide could potentially be used in ∼2 μm lasers.

  16. Insights into Silicate and Oxide Melt Structure from Amorphous, Non-Glass-Forming Materials

    NASA Astrophysics Data System (ADS)

    Stebbins, J. F.

    2015-12-01

    Many silicate and oxide liquids of interest in the Earth sciences and in technology cannot readily be quenched to glasses, either because of low silica contents (and hence low viscosity at the melting point and accompanying liquid 'fragility') or because of liquid-liquid unmixing at high temperature. Although in-situ, high temperature structural tools have been in use for decades and are rapidly developing, many methods are still most informative for glass samples quenched to ambient pressure and temperature, e.g. high-resolution solid-state NMR. Amorphous oxides, including alumina and silicate compositions, have widespread technological applications. These are generally deposited by a variety of high-energy sputtering methods, as films of thicknesses of 10's to 100's of nm. Using Al-27, Si-29, and O-17 NMR, we have recently shown that for such films, very similar short-range structure is seen in materials made by very different kinetic pathways, such as sol-gel synthesis vs. ion-beam sputtering. This path-independent structure suggests that these materials pass through transient equilibrium states during their formation, probably that of deeply supercooled liquids just above glass transition temperatures. In the HfO2-SiO2 and ZrO2-SiO2 systems, for example, samples have well-resolved O-17 NMR spectra, allowing quantitation of O sites with only Hf(Zr) neighbors (so-called "free" oxide ions), with mixed Hf(Zr) and Si neighbors, and Si only. The observed oxygen speciation agrees well with a simple thermodynamic model of one of the most fundamental equilibria in silicate systems, namely the reaction of bridging (Si-O-Si) and "free" (e.g. OHf3 and OHf4) oxide ions to produce "non-bridging" oxygens (e.g. Si-OHf2). This new approach to sampling such structural equilibria in compositions far outside the range of normal glass-forming liquids may provide new insights into more geological compositions as well, as well as in more general models of silicate melt chemistry.

  17. Preparations of PbSe quantum dots in silicate glasses by a melt-annealing technique

    NASA Astrophysics Data System (ADS)

    Ma, D. W.; Cheng, C.; Zhang, Y. N.; Xu, Z. S.

    2014-11-01

    Silicate glass containing PbSe quantum dots (QDs) has important prospective applications in near infra-red optoelectronic devices. In this study, single-stage and double-stage heat-treatment methods were used respectively to prepare PbSe QDs in silicate glasses. Investigation results show that the double-stage heat-treatment is a favorable method to synthesize PbSe QDs with strong photoluminescence (PL) intensity and narrow full weight at half maximum (FWHM) in PL peak. Therefore, the method to prepare PbSe QDs was emphasized on the double-stage heat-treatment. Transmission electron microscopy measurements show that the standard deviations of the average QD sizes from the samples heat-treated at the development temperature of 550 °C fluctuate slightly in the range of 0.6-0.8 nm, while this deviation increases up to 1.2 nm for the sample with the development temperature of 600 °C. In addition, the linear relationship between the QD size and holding time indicates that the crystallization behavior of PbSe QDs in silicate glasses is interface-controlled growth in early stage of crystallization. The growth rates of PbSe QDs are determined to be 0.24 nm/h at 550 °C and 0.72 nm/h at 600 °C. In short, the double-stage heat-treatment at 450 °C for 20 h followed by heat-treatment at 550 °C for 5 h is a preferred process for the crystallization of PbSe QDs in silicate glass. Through this treatment, PbSe QDs with a narrow size dispersion of 5.0 ± 0.6 nm can be obtained, the PL peak from this sample is highest in intensity and narrowest in FWHM among all samples, and the peak is centered on 1575 nm, very close to the most common wavelength of 1550 nm in fiber-optic communication systems.

  18. Effects of thermo-plasmonics on laser-induced backside wet etching of silicate glass

    NASA Astrophysics Data System (ADS)

    Tsvetkov, M. Yu; Yusupov, V. I.; Minaev, N. V.; Timashev, P. S.; Golant, K. M.; Bagratashvili, V. N.

    2016-10-01

    The thermo-plasmonic effect (heat deposition via absorption of laser light by metal nanoparticles) is applied to substantially enhance the effectiveness and controllability of the microstructure formation by laser-induced backside wet etching (LIBWE). Experiments were carried out with silicate glass plates using a pulsed 527 nm wavelength laser and an aqueous solution of AgNO3 as a precursor of the Ag nanoparticles. Mechanisms of such thermo-plasmonic LIBWE (TP-LIBWE) versions are considered. They involve: laser-induced photo-thermal reducing of silver (Ag) and self-assembling of Ag nanoparticles in water and the water/glass interface; fast laser-induced overheating of a water and glass surface through the thermo-plasmonic effect; formation of highly reactive supercritical water that causes glass etching and crater formation; generation of steam-gas bubbles in a liquid. It is significant that the emergence of the Marangoni convection results in bubble retention in the focal point at the interface and the accumulation of nanoparticles on the surface of the laser-induced crater, as this facilitates the movement of the bubbles with captured Ag particles from the fluid volume in the crater region, and accelerates the formation of the area of strong ‘surface absorption’ of laser energy. All these mechanisms provide a highly efficient and reproducible process for laser microstructure formation on the surface of glass using a novel TP-LIBWE technique.

  19. In vitro behavior of silicate glass coatings on Ti6Al4V

    SciTech Connect

    Saiz, Eduardo; Goldman, Marni; Gomez-Vega, Jose M.; Tomsia, Antoni P.; Marshall, Grayson W.; Marshall, Sally J.

    2002-01-09

    The in vitro response in simulated body fluid (SBF) of silicate glass coatings on Ti6Al4V was evaluated. Glasses belonging to the SiO2-CaO-MgO-Na2O-K2O-P2O5 system were used to prepare 50-70 (mu)m thick coatings on Ti6Al4V, employing a simple enameling technique. Glasses with silica content higher than 55 wt percent can be used to prepare coatings that do not crack or delaminate and exhibit good adhesion to the alloy. It has been found that coatings with silica content lower than 60 wt percent are more susceptible to corrosion and precipitate carbonated hydroxyapatite on their surface during in vitro tests. However, these coatings have a higher thermal expansion than the metal and are under tension. After 2 months in SBF cracks grow in the coating that reach the glass/metal interface and initiate delamination. Glasses with silica content higher than 60 wt percent are more resistant to corrosion and have lower thermal expansion. These coatings do not crack but they do not precipitate apatite, even after 2 months in SBF.

  20. Silicate and borate glasses as composite fillers: a bioactivity and biocompatibility study.

    PubMed

    Lopes, P P; Ferreira, B J M Leite; Gomes, P S; Correia, R N; Fernandes, M H; Fernandes, M H V

    2011-06-01

    Composites filled with a silicate glass (CSi) and a new borate glass (CB) were developed and compared in terms of their in vitro behaviour both in acellular and cellular media. Acellular tests were carried out in SBF and the composites were characterized by SEM-EDS, XRD and ICP. Biocompatibility studies were investigated by in vitro cell culture with MG-63 osteoblast-like and human bone marrow cells. The growth of spherical calcium phosphate aggregates was observed in acellular medium on all composite surfaces indicating that these materials became potentially bioactive. The biological assessment resulted in a dissimilar behavior of the composites. The CSi demonstrated an inductive effect on the proliferation of cells. The cells showed a normal morphology and high growth rate when compared to standard culture plates. Contrarily, inhibition of cell proliferation occurred in the CB probably due to its high degradation rate, leading to high B and Mg ionic concentration in the cell culture medium.

  1. Sub-nanoscale nanoimprint fabrication of atomically stepped glassy substrates of silicate glass and acryl polymer

    NASA Astrophysics Data System (ADS)

    Yoshimoto, Mamoru

    2015-11-01

    In the nanoimprint process, the resolution limit of patterning has attracted much attention from both scientific and industrial aspects. In this article, we briefly review the main achievements of our research group on sub-nanoscale nanoimprint fabrication of atomically patterned glassy substrates of oxide glass and polymer. By applying the sapphire (α-Al2O3 single crystal) wafers with self-organized nanopatterns of atomic steps as thermal nanoimprinting molds, we successfully transferred their nanoscale patterns onto the surfaces of glassy substrates such as soda-lime silicate glasses and poly(methyl methacrylate) polymers. The surfaces of nanoimprinted glassy materials exhibited regularly arrayed atomic stairs with 0.2-0.3 nm step height, which were in good agreement with the sub-nanopatterns of sapphire molds. These atomically stepped morphologies on the glassy substrates were found to be stable for about 1 year.

  2. 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.

  3. Calcium polyphosphate as an additive to zinc-silicate glass ionomer cements.

    PubMed

    Valliant, Esther Mae; Gagnier, David; Dickey, Brett Thomas; Boyd, Daniel; Filiaggi, Mark Joseph

    2015-07-01

    Aluminum-free glass ionomer cements (GICs) are under development for orthopedic applications, but are limited by their insufficient handling properties. Here, the addition of calcium polyphosphate (CPP) was investigated as an additive to an experimental zinc-silicate glass ionomer cement. A 50% maximum increase in working time was observed with CPP addition, though this was not clinically significant due to the short working times of the starting zinc-silicate GIC. Surprisingly, CPP also improved the mechanical properties, especially the tensile strength which increased by ∼33% after 30 days in TRIS buffer solution upon CPP addition up to 37.5 wt%. This strengthening may have been due to the formation of ionic crosslinks between the polyphosphate chains and polyacrylic acid. Thus, CPP is a potential additive to future GIC compositions as it has been shown to improve handling and mechanical properties. In addition, CPP may stimulate new bone growth and provide the ability for drug delivery, which are desirable modifications for an orthopedic cement.

  4. Optical band gap and spectroscopic study of lithium alumino silicate glass containing Y3+ ions.

    PubMed

    Shakeri, M S; Rezvani, M

    2011-09-01

    The effect of different amounts of Y2O3 dopant on lithium alumino silicate (LAS) glass has been studied in this work. Glasses having 14.8Li2O-20Al2O3-65.2SiO2 (wt%) composition accompanied with Y2O3 dopant were prepared by normal melting process. In order to calculate the absorption coefficient of samples, transmittance and reflectance spectra of polished samples were measured in the room temperature. Optical properties i.e. Fermi energy level, direct and indirect optical band gaps and Urbach energy were calculated using functionality of extinction coefficient from Fermi-Dirac distribution function, Tauc's plot and the exponential part of absorption coefficient diagram, respectively. It has been clarified that variation in mentioned optical parameters is associated with the changes in physical properties of samples i.e. density or molar mass. On the other hand, increasing of Y3+ ions in the glassy microstructure of samples provides a semiconducting character to LAS glass by reducing the direct and indirect optical band gaps of glass samples from 1.97 to 1.67 and 3.46 to 2.1 (eV), respectively. These changes could be attributed to the role of Y3+ ions as the network former in the track of SiO4 tetrahedrals.

  5. Ni2+-doped new silicate glass-ceramics for broadband near infrared luminescence

    NASA Astrophysics Data System (ADS)

    Zheng, Jian; Cheng, Yin

    2016-12-01

    The new composite transparent spinel silicate glass-ceramics containing Ni2+-doped ZnGa2O4 and solid solution MgxZn1-xGa2O4 nanocrystals were fabricated by in situ controlled crystallization method. After heat treatment, the crystal phase content of ZnGa2O4 increase with increasing heat treatment temperature, and the Mg2+ ions could enter the crystal lattice of ZnGa2O4 to replace the Zn2+ ions and form a new solid solution MgxZn1-xGa2O4. The coordination environment of Ni2+ was changed from tetrahedral in glasses to octahedral sites in glass ceramics. The super-broadband infrared luminescence with full width at half maximum (FWHM) of about 400 nm overing 1.1-1.7 μm wavelength region and fluorescent lifetime of about 480 μs were observed from the glass ceramics containing MgxZn1-xGa2O4 nanocrystals. It is probably due to the variety of solid solution structure making Ni2+ ions enter two different octahedral sites. At the same time, the impact of heat treatment temperature and the concentration of NiO on peak position and intensity were also discussed. The results demonstrate that the method presented may be an effective way to fabricate super-broadband optical amplifiers and tunable lasers.

  6. 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

  7. Investigation on the damage threshold of films coated on various silicate, fluorophosphate and phosphate laser glasses. Final report, January 1, 1979-August 29, 1980

    SciTech Connect

    Nakajima, Y; Izumitani, T

    1980-01-01

    Effects of substrate laser glass on the damage threshold and adhesion of dielectric films has been studied in order to improve the damage threshold. The study is divided into two parts: the first part dealing with four types of laser glass, LSG-91H silicate, LHG-8 phosphate, P-1 phosphate and LHG-10 fluorophosphate; the second part dealing with twenty-six glasses with systematically modified compositions in three glass systems, silicate, phosphate and fluorophosphate.

  8. Three-photon-excited upconversion luminescence of niobium ions doped silicate glass by a femtosecond laser irradiation.

    PubMed

    Zeng, Huidan; Song, Juan; Chen, Danping; Yuan, Shuanglong; Jiang, Xiongwei; Cheng, Ya; Yang, Yunxia; Chen, Guorong

    2008-04-28

    We report on the bluish green upconversion luminescence of niobium ions doped silicate glass by a femtosecond laser irradiation. The dependence of the fluorescence intensity on the pump power density of laser indicates that the conversion of infrared irradiation to visible emission is dominated by three-photon excitation process. We suggest that the charge transfer from O(2-) to Nb(5+) can efficiently contribute to the bluish green emission. The results indicate that transition metal ions without d electrons play an important role in fields of optics when embedded into silicate glass matrix.

  9. Free energy profiles of Al3+ and La3+ cation distribution in silica and soda silicate glasses

    SciTech Connect

    Corrales, Louis R.

    2005-03-01

    The factors that control the distribution of Al3+ and La3+ cations in silica and soda silicate glasses is examined by using molecular dynamics (MD) simulations. In particular, the response of the glass network to the presence of metal oxide is probed using liquid state theory that treats the glass network as a solvent and the metal cation as a solute. MD simulations are used to obtain the mean force of the solvent-solute and solute-solute interactions along a trajectory that is then used to obtain the potential of mean force. The resulting free energy is analyzed along the trajectory to determine the stable configurations of the cation pair. Details of determining the PMF for an Al cation pair in silica and silicate glass is presented. A comparison of these results with those previously calculated for a La cation pair in the same glass systems is given. The results reveal that there are distinct differences on how the network accommodates the two different size cations. It is found that the network wraps itself around the larger La cation very much like a solvent shell, whereas, the smaller Al cation is incorporated into the network backbone. In silica and soda silicate glasses clustering of the La ion pair to form La-O-La linkages is favored, in contrast, the glasses favor a separated state of the Al ion pair.

  10. Silicate Based Glass Formulations for Immobilization of U.S. Defense Wastes Using Cold Crucible Induction Melters

    SciTech Connect

    Smith, Gary L.; Kim, Dong-Sang; Schweiger, Michael J.; Marra, James C.; Lang, Jesse B.; Crum, Jarrod V.; Crawford, Charles L.; Vienna, John D.

    2014-05-22

    The cold crucible induction melter (CCIM) is an alternative technology to the currently deployed liquid-fed, ceramic-lined, Joule-heated melter for immobilizing of U.S. tank waste generated from defense related reprocessing. In order to accurately evaluate the potential benefits of deploying a CCIM, glasses must be developed specifically for that melting technology. Related glass formulation efforts have been conducted since the 1990s including a recent study that is first documented in this report. The purpose of this report is to summarize the silicate base glass formulation efforts for CCIM testing of U.S. tank wastes. Summaries of phosphate based glass formulation and phosphate and silicate based CCIM demonstration tests are reported separately (Day and Ray 2013 and Marra 2013, respectively). Combined these three reports summarize the current state of knowledge related to waste form development and process testing of CCIM technology for U.S. tank wastes.

  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. Photo-acoustic spectroscopy and quantum efficiency of Yb{sup 3+} doped alumino silicate glasses

    SciTech Connect

    Kuhn, Stefan Tiegel, Mirko; Herrmann, Andreas; Rüssel, Christian; Engel, Sebastian; Wenisch, Christoph; Gräf, Stephan; Müller, Frank A.; Körner, Jörg; Seifert, Reinhard; Yue, Fangxin; Klöpfel, Diethardt; Hein, Joachim; Kaluza, Malte C.

    2015-09-14

    In this contribution, we analyze the effect of several preparation methods of Yb{sup 3+} doped alumino silicate glasses on their quantum efficiency by using photo-acoustic measurements in comparison to standard measurement methods including the determination via the fluorescence lifetime and an integrating sphere setup. The preparation methods focused on decreasing the OH concentration by means of fluorine-substitution and/or applying dry melting atmospheres, which led to an increase in the measured fluorescence lifetime. However, it was found that the influence of these methods on radiative properties such as the measured fluorescence lifetime alone does not per se give exact information about the actual quantum efficiency of the sample. The determination of the quantum efficiency by means of fluorescence lifetime shows inaccuracies when refractive index changing elements such as fluorine are incorporated into the glass. Since fluorine not only eliminates OH from the glass but also increases the “intrinsic” radiative fluorescence lifetime, which is needed to calculate the quantum efficiency, it is difficult to separate lifetime quenching from purely radiative effects. The approach used in this contribution offers a possibility to disentangle radiative from non-radiative properties which is not possible by using fluorescence lifetime measurements alone and allows an accurate determination of the quantum efficiency of a given sample. The comparative determination by an integrating sphere setup leads to the well-known problem of reabsorption which embodies itself in the measurement of too low quantum efficiencies, especially for samples with small quantum efficiencies.

  13. Irradiation-induced Ag nanocluster nucleation in silicate glasses: Analogy with photography

    SciTech Connect

    Espiau de Lamaestre, R.; Bea, H.; Bernas, H.; Belloni, J.; Marignier, J. L.

    2007-11-15

    The synthesis of Ag nanoclusters in soda lime silicate glasses and silica was studied by optical absorption and electron spin resonance experiments under both low (gamma ray) and high (MeV ion) deposited energy density irradiation conditions. Both types of irradiation create electrons and holes whose density and thermal evolution--notably via their interaction with defects--are shown to determine the clustering and growth rates of Ag nanocrystals. We thus establish the influence of redox interactions of defects and silver (poly)ions. The mechanisms are similar to the latent image formation in photography: Irradiation-induced photoelectrons are trapped within the glass matrix, notably on dissolved noble metal ions and defects, which are thus neutralized (reverse oxidation reactions are also shown to exist). Annealing promotes metal atom diffusion, which, in turn, leads to cluster nuclei formation. The cluster density depends not only on the irradiation fluence but also--and primarily--on the density of deposited energy and the redox properties of the glass. Ion irradiation (i.e., large deposited energy density) is far more effective in cluster formation, despite its lower neutralization efficiency (from Ag{sup +} to Ag{sup 0}) as compared to gamma photon irradiation.

  14. High modulus rare earth and beryllium containing silicate glass compositions. [for glass reinforcing fibers

    NASA Technical Reports Server (NTRS)

    Bacon, J. F. (Inventor)

    1976-01-01

    Glass compositions having a Young's modulus of at least 16 million psi and a specific modulus of at least 110 million inches consisting essentially of approximately, by weight, 20 to 43% SiO2, 8 to 21% Al2O3, 4 to 10% BeO, 27 to 58% of at least one oxide selected from a first group consisting of Y2O3, La2O3, Nd2O3, Ce2O3, Ce2O3, and the mixed rare earth oxides, and 3 to 12% of at least one oxide selected from a second group consisting of MgO, ZrO2, ZnO and CaO are described. The molar ratio of BeO to the total content of the first group oxides is from 1.0 to 3.0.

  15. Spectroscopic properties and energy transfer in Er-Tm co-doped bismuth silicate glass

    NASA Astrophysics Data System (ADS)

    Wang, Xin; Li, Zhilan; Li, Kefeng; Zhang, Lei; Cheng, Jimeng; Hu, Lili

    2013-10-01

    In this paper, we investigate the spectroscopic properties of and energy transfer processes in Er-Tm co-doped bismuth silicate glass. The Judd-Ofelt parameters of Er3+ and Tm3+ are calculated, and the similar values indicate that the local environments of these two kinds of rare earth ions are almost the same. When the samples are pumped at 980 nm, the emission intensity ratio of Tm:3F4 → 3H6 to Er:4I13/2 → 4I15/2 increases with increased Er3+ and Tm3+ contents, indicating energy transfer from Er:4I13/2 to Tm:3F4. When the samples are pumped at 800 nm, the emission intensity ratio of Er:4I13/2 → 4I15/2 to Tm:3H4 → 3F4 increases with increased Tm2O3 concentration, indicating energy transfer from Tm:3H4 to Er:4I13/2. The rate equations are given to explain the variations. The microscopic and macroscopic energy transfer parameters are calculated, and the values of energy transfer from Er:4I13/2 to Tm:3F4 are found to be higher than those of the other processes. For the Tm singly-doped glass pumped at 800 nm and Er-Tm co-doped glass pumped at 980 nm, the pumping rate needed to realize population reversion is calculated. The result shows that when the Er2O3 doping level is high, pumping the co-doped glass by a 980 nm laser is an effective way of obtaining a low-threshold ˜2 μm gain.

  16. Batch Reactions of a Soda-Lime Silicate Glass (Report for G Plus Project for Libbey Inc.)

    SciTech Connect

    Kim, Dong-Sang; Matyas, Josef

    2002-08-29

    The purpose of this project is to develop the batch reaction data for a soda-lime-silicate glass needed to improve the batch part of the glass-furnace model being developed for the glass industry. Evolved gas analysis combined with batch expansion measurement and thermal analysis was successfully applied to obtain batch reaction data. The heat-capacity measurement by differential scanning calorimetry (DSC) was suggested as a promising method to derive the heat-of-fusion data inexpensively for many different technical glass batches. More tests on a variety of glass batches and parametric studies of the suggested methods are needed for validation. The experimental methods for batch reaction studies and the methodology for obtaining inexpensive heat-of-fusion data developed in this study can also be applied to various types of other technical glasses.

  17. A Multi-spectroscopic Investigation of Sulphur Speciation in Silicate Glasses and Slags

    SciTech Connect

    Bingham, P.; Connelly, A; Hand, R; Hyatt, N; Northrup, P; Alonso Mori, R; Glatzel, P; Kavcic, M; Zitnik, M; et al.

    2010-01-01

    Sulphur K-edge x-ray absorption near-edge structure (XANES), sulphur K{sub {alpha}} and K{sub {beta}} high resolution x-ray emission spectroscopies (XES), electron paramagnetic resonance (EPR) and optical absorption spectroscopies have been used to study the speciation of sulphur in a range of soda-lime-silica glasses and silicate slags. Several inorganic standards with known sulphur oxidation states and structural environments have also been analysed. Results confirm that the average oxidation state of sulphur in glasses decreases, as expected, in the order (colourless>light olive>dark olive>light amber>dark amber). This behaviour is consistent with decreasing S{sup 6+}/{Sigma}S ratio, which has been quantified by linear combination fitting of XES S K{alpha} spectra, and with analysed sulphur contents which exhibit a characteristic relationship with oxygen partial pressure, pO{sub 2}. A combination of S{sup 6+}, S{sup 5+}, S{sup 4+} and more reduced sulphur species has been detected in olive and amber glasses. The S{sup 4+} and S{sup 5+} species are most evident in olive-coloured glasses produced under moderately reducing conditions that coincide with minimum sulphur solubilities. The reduced form of sulphur, present in all reduced glasses, is interpreted as being present as S{sup 2-} on the basis of XANES, XES, EPR and optical measurements. An alternative interpretation of the data is that there is a continuum of less strongly reduced species, primarily S{sup +} and S{sup 2+}; this interpretation has less merit. In this paper we show that the established relationship that describes sulphur redox only in terms of S{sup 6+} and S{sup 2-}, and which states that only these two species co-exist over a narrow, moderately reducing range of pO{sub 2}, does not fully describe the behaviour of S in the industrial, non-equilibrated glasses studied. Hence this relationship requires slight modification for non-equilibrated systems to explain the existence of intermediate

  18. Infrared fluorescence, energy transfer process and quantitative analysis of thulium-doped niobium silicate-germanate glass

    NASA Astrophysics Data System (ADS)

    Chen, Rong; Tian, Ying; Li, Bingpeng; Wang, Caizhi; Jing, Xufeng; Zhang, Junjie; Xu, Shiqing

    2016-11-01

    Infrared fluorescence, energy transfer process, thermal stability and quantitative analysis of Tm3+ doped novel niobium silicate-germanate glasses have been investigated. The thermal stability changes indicate that the introduction of La2O3 to substitute for Nb2O5 can improve the anti-crystallization of present glass system. Intense 1.8 μm fluorescence has been achieved and the value of emission cross section can reach as high as 12.2 × 10-21 cm2. Besides, the microparameters of energy transfer were analyzed by the extended overlap integral method. Hence, the results indicate that the excellent spectroscopic characteristics of this kind of silicate-germanate glass together with the good thermal properties may become a promising matrix applied for 1.8 μm band near-infrared laser.

  19. Size Scaling of Tensile Failure Stress in a Soda-Lime-Silicate Float Glass

    SciTech Connect

    Wereszczak, Andrew A; Kirkland, Timothy Philip; Ragan, Meredith E; Strong, Kevin T; Lin, Hua-Tay; Patel, P

    2010-01-01

    The (tensile) strength-size scaling of a float soda-lime silicate glass was studied using biaxial flexure and Hertzian ring crack initiation testing. The examined Weibull effective areas spanned ~ 0.4 to 48,000 mm2. Both the air- and tin-sides were tested. The air side was stronger than the tin side as others have observed; however, the differences in their characteristic strengths decreased with decreasing effective area, and their strengths converged for effective areas smaller than ~ 100 mm2. The failure stress at the smallest effective area examined for the tin-side was ~ 500% greater than that at the largest effective area while that difference was ~ 250% for the air- side. A Weibull modulus change at ~ 100 mm2 suggests different strength-limiting flaw types were dominant below and above that effective area. These results reinforce the importance to interpret and use tensile strength of glass in context to how much of its area is being tensile stressed.

  20. Compressibility of hydrated and anhydrous sodium silicate-based liquids and glasses, as analogues for natural silicate melts, by Brillouin scattering spectroscopy

    NASA Astrophysics Data System (ADS)

    Tkachev, Sergey Nikolayevich

    A mathematical formalism was tested on compressibility studies of water, before applying it to the high pressure-temperature compressibility studies of hydrated and anhydrous sodium silicate-based liquids and glasses. The hypersonic sound velocity, refractive index and attenuation coefficient obtained using Brillouin light scattering spectroscopy technique were in agreement with literature data. From the measured sound velocities, the pressure dependence of the bulk moduli and density of liquid water were calculated, using Vinet equation of state. The formalism was extended to the Brillouin scattering studies of the elastic properties of alkaline-calcium silica hydrogels and float glass, which exhibits a dramatic increase in the pressure dependence of longitudinal velocity and a discontinuity in the compressibility at about 6 GPa. It is demonstrated that an apparent second-order transition to a new amorphous phase can form via the abrupt onset of a new compressional mechanism, which may be triggered by a shift in polymerization of the glass or an onset of a change in coordination of silicon. Brillouin scattering measurements were carried out on an aqueous solution of Na2O-2SiO2 and anhydrous Na2O-2SiO 2 glass and liquid at high P-T conditions. The "modified" platelet scattering geometry has allowed a determination of the longitudinal velocity independently from refractive index, and hence the adiabatic compressibility and density of liquids as a function of pressure and temperature. The observed increase in density of the melt and glass phases formed at high P-T conditions is likely associated with structural effects. The large values of KS' of the liquid phase illustrate that the means of compaction of the liquid differs substantially from that of the glass, and that the liquid is able to access a wider range of compaction mechanisms. The measured bulk modulus of Na2O-2SiO2 aqueous solution is closer to values of silicate melts than to that of end-member water at

  1. Computational modelling of large deformations in layered-silicate/PET nanocomposites near the glass transition

    NASA Astrophysics Data System (ADS)

    Figiel, Łukasz; Dunne, Fionn P. E.; Buckley, C. Paul

    2010-01-01

    Layered-silicate nanoparticles offer a cost-effective reinforcement for thermoplastics. Computational modelling has been employed to study large deformations in layered-silicate/poly(ethylene terephthalate) (PET) nanocomposites near the glass transition, as would be experienced during industrial forming processes such as thermoforming or injection stretch blow moulding. Non-linear numerical modelling was applied, to predict the macroscopic large deformation behaviour, with morphology evolution and deformation occurring at the microscopic level, using the representative volume element (RVE) approach. A physically based elasto-viscoplastic constitutive model, describing the behaviour of the PET matrix within the RVE, was numerically implemented into a finite element solver (ABAQUS) using an UMAT subroutine. The implementation was designed to be robust, for accommodating large rotations and stretches of the matrix local to, and between, the nanoparticles. The nanocomposite morphology was reconstructed at the RVE level using a Monte-Carlo-based algorithm that placed straight, high-aspect ratio particles according to the specified orientation and volume fraction, with the assumption of periodicity. Computational experiments using this methodology enabled prediction of the strain-stiffening behaviour of the nanocomposite, observed experimentally, as functions of strain, strain rate, temperature and particle volume fraction. These results revealed the probable origins of the enhanced strain stiffening observed: (a) evolution of the morphology (through particle re-orientation) and (b) early onset of stress-induced pre-crystallization (and hence lock-up of viscous flow), triggered by the presence of particles. The computational model enabled prediction of the effects of process parameters (strain rate, temperature) on evolution of the morphology, and hence on the end-use properties.

  2. Effect of Zn addition on non-resonant third-order optical nonlinearity of the Cu-doped germano-silicate optical glass fiber.

    PubMed

    Ju, Seongmin; Watekar, Pramod R; Jeong, Seongmook; Kim, Youngwoong; Han, Won-Taek

    2012-01-01

    Cu/Zn-codoped germano-silicate optical glass fiber was manufactured by using the modified chemical vapor deposition (MCVD) process and solution doping process. To investigate the reduction effect of Zn addition on Cu metal formation in the core of the Cu/Zn-codoped germano-silicate optical glass fiber, the optical absorption property and the non-resonant third-order optical nonlinearity were measured. Absorption peaks at 435 nm and 469 nm in the Cu/Zn-codoped germano-silicate optical glass fiber were contributed to Cu metal particles and ZnO semiconductor particles, respectively. The effective non-resonant optical nonlinearity, gamma, of the Cu/Zn-codoped germano-silicate optical glass fiber was measured to be 1.5097 W(-1) x km(-1) by using the continuous-wave self-phase modulation method. The gamma of the Cu/Zn-codoped germano-silicate optical glass fiber was about four times larger than that of the reference germano-silicate optical glass fiber without any dopants. The increase of the effective non-resonant optical nonlinearity, gamma, of the Cu/Zn-codoped germano-silicate optical glass fiber, can be attributed to the enhanced nonlinear polarization due to incorporated ZnO semiconductor particles and Cu metal ions in the glass network. The Cu/Zn-codoped germano-silicate optical glass fiber showed high nonlinearity and low transmission loss at the optical communication wavelength, which makes it suitable for high-speed-high-capacity optical communication systems.

  3. Volumetric properties of magnesium silicate glasses and supercooled liquid at high pressure by X-ray microtomography

    SciTech Connect

    Lesher, Charles E.; Wang, Yanbin; Gaudio, Sarah; Clark, Alisha; Nishiyama, Nori; Rivers, Mark

    2009-06-01

    The volumetric properties of silicate glasses and supercooled liquid are examined at high pressures and temperatures using X-ray computed tomography (CT) and absorption. The high pressure X-ray microtomography (HPXMT) system at the Advanced Photon Source, Argonne National Laboratory (GeoSoilEnvironCARS 13-BM-D beamline) consists of two opposing anvils compressed within an X-ray-transparent containment ring supported by thrust bearings and loaded using a 250-ton hydraulic press. This system permits the pressure cell to rotate under the load, while collecting radiographs through at least 180{sup o} of rotation. The 13-BM-D beamline permits convenient switching between monochromatic radiation required for radiography and polychromatic radiation for pressure determination by energy dispersive diffraction. We report initial results on several refractory magnesium silicate glasses synthesized by levitation laser heating. Volume changes during room temperature compression of Mg-silicate glasses with 33 mol% and 38 mol% SiO2 up to 11.5 GPa give an isothermal bulk moduli of 93--100 GPa for a K' of 1. These values are consistent with ultrasonic measurements of more silica-rich glasses. The volumetric properties of amorphous MgSiO{sub 3} at 2 GPa were examined during annealing up to 1000 C. We consider the consequences of heating through the glass transition and the implications for thermal expansivity of supercooled liquids at high pressure. Our results illustrate the capabilities of HPXMT for studies of refractory glasses and liquids at high pressure and offer strategies for future studies of liquid densities within the melting interval for magmas in planet interiors.

  4. Bone regeneration in rat calvarial defects implanted with fibrous scaffolds composed of a mixture of silicate and borate bioactive glasses.

    PubMed

    Gu, Yifei; Huang, Wenhai; Rahaman, Mohamed N; Day, Delbert E

    2013-11-01

    Previous studies have evaluated the capacity of porous scaffolds composed of a single bioactive glass to regenerate bone. In the present study, scaffolds composed of a mixture of two different bioactive glasses (silicate 13-93 and borate 13-93B3) were created and evaluated for their response to osteogenic MLO-A5 cells in vitro and their capacity to regenerate bone in rat calvarial defects in vivo. The scaffolds, which have similar microstructures (porosity=58-67%) and contain 0, 25, 50 and 100 wt.% 13-93B3 glass, were fabricated by thermally bonding randomly oriented short fibers. The silicate 13-93 scaffolds showed a better capacity to support cell proliferation and alkaline phosphatase activity than the scaffolds containing borate 13-93B3 fibers. The amount of new bone formed in the defects implanted with the 13-93 scaffolds at 12 weeks was 31%, compared to values of 25, 17 and 20%, respectively, for the scaffolds containing 25, 50 and 100% 13-93B3 glass. The amount of new bone formed in the 13-93 scaffolds was significantly higher than in the scaffolds containing 50 and 100% 13-93B3 glass. While the 13-93 fibers were only partially converted to hydroxyapatite at 12 weeks, the 13-93B3 fibers were fully converted and formed a tubular morphology. Scaffolds composed of an optimized mixture of silicate and borate bioactive glasses could provide the requisite architecture to guide bone regeneration combined with a controllable degradation rate that could be beneficial for bone and tissue healing.

  5. Effect of thermal annealing on the spectroscopic parameters of Er3+-doped sodium silicate glass

    NASA Astrophysics Data System (ADS)

    de Morais, Rodrigo F.; Serqueira, Elias Oliveira; Dantas, Noelio Oliveira

    2013-10-01

    This paper presents the optical characteristics of Er3+ ions in sodium silicate glass (SiO2-Na2O), synthesized by the fusion method and later annealed for 0, 30, 60 and 90 min. Thermograms, X-ray diffraction, optical absorption, luminescence spectroscopy measurements were performed in order to determine the thermal and structural of the samples and the radiative characteristics of Er3+ ions under influence of thermal annealing of the samples. Differential thermal analysis provided evidence of a phase change in the system. This phase change was confirmed by X-ray diffraction, which showed the formation and growth of Na2SiO3 crystals for the annealed samples. These crystals affect the neighborhood (from second vicinity) of Er3+ ions. These effects were noted by the J-O parameters (Ω2 and Ω4), which were calculated from the optical absorption spectra. Judd-Ofelt calculations also confirmed that heat treatment induced structural rearrangement of the samples that was dependent on Er2O3 concentration. This resulted in changes in the optical and physical properties of the samples, including stimulated emission cross section and rigidity. Analysis of the spectroscopy parameters after of thermal annealing indicate samples are potential materials for in optical device applications.

  6. Pressure-induced nano-crystallization of silicate garnets from glass

    PubMed Central

    Irifune, T.; Kawakami, K.; Arimoto, T.; Ohfuji, H.; Kunimoto, T.; Shinmei, T.

    2016-01-01

    Transparent ceramics are important for scientific and industrial applications because of the superior optical and mechanical properties. It has been suggested that optical transparency and mechanical strength are substantially enhanced if transparent ceramics with nano-crystals are available. However, synthesis of the highly transparent nano-crystalline ceramics has been difficult using conventional sintering techniques at relatively low pressures. Here we show direct conversion from bulk glass starting material in mutianvil high-pressure apparatus leads to pore-free nano-polycrystalline silicate garnet at pressures above ∼10 GPa in a limited temperature range around 1,400 °C. The synthesized nano-polycrystalline garnet is optically as transparent as the single crystal for almost the entire visible light range and harder than the single crystal by ∼30%. The ultrahigh-pressure conversion technique should provide novel functional ceramics having various crystal structures, including those of high-pressure phases, as well as ideal specimens for some mineral physics applications. PMID:27924866

  7. Pressure-induced nano-crystallization of silicate garnets from glass

    NASA Astrophysics Data System (ADS)

    Irifune, T.; Kawakami, K.; Arimoto, T.; Ohfuji, H.; Kunimoto, T.; Shinmei, T.

    2016-12-01

    Transparent ceramics are important for scientific and industrial applications because of the superior optical and mechanical properties. It has been suggested that optical transparency and mechanical strength are substantially enhanced if transparent ceramics with nano-crystals are available. However, synthesis of the highly transparent nano-crystalline ceramics has been difficult using conventional sintering techniques at relatively low pressures. Here we show direct conversion from bulk glass starting material in mutianvil high-pressure apparatus leads to pore-free nano-polycrystalline silicate garnet at pressures above ~10 GPa in a limited temperature range around 1,400 °C. The synthesized nano-polycrystalline garnet is optically as transparent as the single crystal for almost the entire visible light range and harder than the single crystal by ~30%. The ultrahigh-pressure conversion technique should provide novel functional ceramics having various crystal structures, including those of high-pressure phases, as well as ideal specimens for some mineral physics applications.

  8. Effects of glass fiber modified with calcium silicate hydrate (C-S-H(I)) reinforced cement

    NASA Astrophysics Data System (ADS)

    Xin, M.; Zhang, L.; Ge, S.; Cheng, X.

    2017-03-01

    In this paper, calcium silicate hydrate (C-S-H(I)) and glass fiber modified with C-S-H(I) (SiF) at ambient temperature were synthesized. SiF and untreated fiber (OF) were incorporated into cement paste. Phase composition of C-S-H(I), SiF and OF was characterized by XRD. The surface morphologies were characterized by SEM. Flexural performance of fiber reinforced cement (FRC) at different curing ages was investigated. Results indicated that both SiF and OF could reinforce cement paste. SiF had a more positive effect on improving the flexural performance of FRC than OF. The strength of SiF reinforced cement was 11.48MPa after 28 days curing when fiber volume was 1.0%, 12.55% higher than that of OF reinforced cement. The flexural strength increased with the addition of fiber volume. However, the large dosage of fiber might cause a decrease in flexural strength of FRC.

  9. Diffusion of helium isotopes in silicate glasses and minerals: Implications for petrogenesis and geochronology. Doctoral thesis

    SciTech Connect

    Trull, T.W.

    1989-06-01

    Helium diffusivities in basaltic glasses at seafloor temperatures are about 10 to the -16th power sq cm/s suggesting only very low concentration samples will be compromised, and that U/He geochronology of submarine basalts may be feasible. Helium diffusivities at magmatic temperatures are 10 to the -11th power, to 10 to the -8th power sq cm/s in silicate minerals, too low to regionally homogenize helium in the mantle. Helium exchange rates limit xenolith origin depths and transport times. Faster He diffusion in pyroxene than olivine allows diffusive loss to be evaluated. Diffusivities of {sup 3}He produced by cosmic rays in surface rocks are less than 10 to the -20th power sq cm/s in olivine and quartz, suggesting exposure dating will not be limited by helium loss for ages up to 10,000,000 years. Similar conclusions were found for U/{sup 4}He dating of quartz. Part of the {sup 3}He/{sup 4}He variability (.01 to 9 R{sub a}) of island arc basalts from the western Pacific reflects post-eruptive helium addition. In unaltered samples, Kavachi submarine volcano has different {sup 3}He/{sup 4}He (6.9 + or - .2 R{sub a}) than the Woodlark Spreading Center (8-9 R{sub a}). A contribution from subducted Pacific lithosphere may explain this and 87 Sr/86 Sr variations.

  10. EFFECT OF LASER LIGHT ON MATTER. LASER PLASMAS: Multiphoton coloration of lead silicate glasses by high-power laser radiation

    NASA Astrophysics Data System (ADS)

    Efimov, O. M.; Matveev, Yu A.; Mekryukov, A. M.

    1994-04-01

    A study was made of the mechanism of the formation of colour centres by the exposure of lead silicate glasses to high-power laser radiation. The long-wavelength mobility edge (>5.8 eV) of charge carriers in these glasses was located well above the fundamental absorption edge (3.5 eV), so that coloration was observed only when the glass matrix experienced multiphoton ionisation. The newly formed colour centres make the main contribution to the change in the transmission directly during the action of nanosecond laser pulses. An estimate was obtained of the three-photon absorption coefficient of TF10 glass at the wavelength of 527 nm.

  11. SIMS Calibration of Nitrogen in Silicate Glasses and Applications to Melt Inclusions

    NASA Astrophysics Data System (ADS)

    Regier, M. E.; Hervig, R. L.; Wallace, P. J.; Myers, M.; Wilson, C. J. N.

    2015-12-01

    Previous attempts to constrain N fluxes between the mantle, crust, and atmospheric reservoirs over geologic time have been inhibited due to the difficulty of detecting trace amounts of nitrogen, especially as triply-bonded N2 in oxidized magmas. Secondary ion mass spectrometry (SIMS) can detect nitrogen as N+, and as the molecular ions SiN-, NO-, and CN-. However, there are few matrix-matched, bulk-analyzed standards for N, which makes quantification of its signal challenging. Here, we use the implantation of known amounts of nitrogen into rhyolitic glasses containing a range of H2O, and subsequent depth-profile analysis of these samples to derive N calibration factors1,2. We use a primary beam of O- and detection of N+ ions. Results demonstrate that the useful yield (ions detected per atom sputtered) of N increases with H2O content, whereas the useful yield of the measured matrix ion (30Si) decreases with higher H2O. Quantification is also complicated by variable N background that scales inversely with observed higher sputtering rates in hydrated glasses. The former issue can be resolved by fitting a curve to the H2O vs. calibration factor plot and the latter by varying the primary beam density on low-H2O materials. Together, these approaches allow us to quantify the N content in variably hydrated rhyolitic glasses. Application of these calibrations to quartz-hosted melt inclusions from the Bishop3, 4 and Huckleberry Ridge Tuffs4 reveals un-degassed N contents of melts at depth. We show that N can be used in concert with other volatiles to tease out magmatic processes, such as recharge events and magma mixing. We conclude that unless these inclusions do not represent the bulk concentration of N in the melt, large silicic eruptions have not released enough N to significantly impact the atmospheric reservoir over geologic time. 1Burnett DS et al. (2015) Geostand Geoanalytical Res 39:265-276; 2Wilson RG et al. (1989) Secondary ion mass spectrometry. Wiley (New York

  12. Influence of gallium and alkali halide addition on the optical and thermo mechanical properties of GeSe2-Ga2Se3 glass

    NASA Astrophysics Data System (ADS)

    Volk, Y. V.; Malyarevich, A. M.; Yumashev, K. V.; Matrosov, V. N.; Matrosova, T. A.; Kupchenko, M. I.

    2007-10-01

    A systematic compositional study of a new family of chalcogenide glasses, transparent from the visible range up to 16 μm has been performed. Numerous glass forming regions were explored in the GeSe2-Ga2Se3-MX system (MX = alkali halide) in order to understand the role of alkali halides and the effect of Ga substitution for Sb in the glass structure. To that avail, several ternary diagrams were investigated, and optical and thermo-mechanical measurements were performed. It is shown that the introduction of an alkali halide in the GeSe2-Ga2Se3 glasses increased the band-gap energy Eg by stabilizing electrons from the lone pairs of selenium. However, the glass hardness was lowered due to a decrease in the glass network reticulation. The chemical resistance was studied in a glass containing high CsCl content. Significant corrosion occurred when the glass was exposed to hot water for several hours. There is a great deal of interest in these glasses for use in thermal imaging devices, as they permit the alignment of infrared optical systems with visible red light. Furthermore, the low cost of raw materials and the possibility of shaping these glasses into lenses by molding could extend their utilization from defense to civilian applications.

  13. Influence of gallium and alkali halide addition on the optical and thermo-mechanical properties of GeSe2-Ga2Se3 glass

    NASA Astrophysics Data System (ADS)

    Calvez, L.; Lucas, P.; Rozé, M.; Ma, H. L.; Lucas, J.; Zhang, X. H.

    2007-10-01

    A systematic compositional study of a new family of chalcogenide glasses, transparent from the visible range up to 16 μm has been performed. Numerous glass forming regions were explored in the GeSe2-Ga2Se3-MX system (MX = alkali halide) in order to understand the role of alkali halides and the effect of Ga substitution for Sb in the glass structure. To that avail, several ternary diagrams were investigated, and optical and thermo-mechanical measurements were performed. It is shown that the introduction of an alkali halide in the GeSe2-Ga2Se3 glasses increased the band-gap energy Eg by stabilizing electrons from the lone pairs of selenium. However, the glass hardness was lowered due to a decrease in the glass network reticulation. The chemical resistance was studied in a glass containing high CsCl content. Significant corrosion occurred when the glass was exposed to hot water for several hours. There is a great deal of interest in these glasses for use in thermal imaging devices, as they permit the alignment of infrared optical systems with visible red light. Furthermore, the low cost of raw materials and the possibility of shaping these glasses into lenses by molding could extend their utilization from defense to civilian applications.

  14. Element specificity of ortho-positronium annihilation for alkali-metal loaded SiO2 glasses.

    PubMed

    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 SiO2 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.

  15. Element specificity of ortho-positronium annihilation for alkali-metal loaded SiO2 glasses

    NASA Astrophysics Data System (ADS)

    Sato, K.; Hatta, T.

    2015-03-01

    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 SiO2 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.

  16. 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.

  17. Optical parameters and upconversion fluorescence in Tm3+/Yb3+-doped alkali-barium-bismuth-tellurite glasses.

    PubMed

    Lin, Hai; Liu, Ke; Lin, Lin; Hou, Yanyan; Yang, Dianlai; Ma, Tiecheng; Pun, Edwin Yun Bun; An, Qingda; Yu, Jiayou; Tanabe, Setsuhisa

    2006-11-01

    Tm(3+)/Yb(3+)-doped alkali-barium-bismuth-tellurite (LKBBT) glasses have been fabricated and characterized. Density, refractive index, optical absorption, absorption and emission cross-sections of Yb(3+), Judd-Ofelt parameters and spontaneous transition probabilities of Tm(3+) have been measured and calculated, respectively. Intense blue three-photon upconversion fluorescence and near-infrared two-photon upconversion fluorescence were investigated under the excitation of a 980 nm diode laser at room temperature. Wide infrared transmission window, high refractive index and strong blue three-photon upconversion emission of Tm(3+) indicate that Tm(3+)/Yb(3+) co-doped LKBBT glasses are promising upconversion optical and laser materials.

  18. Infrared spectroscopy and hydrogen isotope geochemistry of hydrous silicate glasses. Progress report, June 1, 1996--May 31, 1999

    SciTech Connect

    Epstein, S.; Stolper, E.

    1998-06-01

    This DOE-funded project (DE-FG03-ER13445, 6/1/96-5/31/99) emphasizes study of the behavior of volatiles in magmatic systems. The project is explicitly focused on the combined application of IR spectroscopy, experimental petrology, and stable isotope geochemistry to understanding the behavior and properties of the volatile components dissolved in silicate melts and glasses, although in recent years, our emphasis has broadened to include non-volatile aspects of stable isotope geochemistry. Results obtained during the current grant and previous grant periods confirm that when applied to study of well-chosen synthetic and natural systems, the combination of these approaches and techniques can yield insights of general petrological and volcanological value and of practical value to DOE. In particular, the results of our DOE-funded work has led to a deeper understanding of the physical chemistry of silicate melts as well as specific constraints on the thermal and chemical evolution of high-level magmatic systems of the sort being evaluated as potential geothermal and magmathermal energy sources. Moreover, our work has also contributed to understanding the behavior of H-, C-, and O-bearing species in amorphous and crystalline silicates, including the kinetics of their interactions; we believe these results will contribute to efforts to use silicates in the development of nuclear waste disposal strategies.

  19. Paleomagnetism and Mineralogy of Unusual Silicate Glasses and Baked Soils on the Surface of the Atacama Desert of Northern Chile: A Major Airburst Impact ~12ka ago?.

    NASA Astrophysics Data System (ADS)

    Roperch, P. J.; Blanco, N.; Valenzuela, M.; Gattacceca, J.; Devouard, B.; Lorand, J. P.; Tomlinson, A. J.; Arriagada, C.; Rochette, P.

    2015-12-01

    Unusual silicate glasses were found in northern Chile in one of the driest place on earth, the Atacama Desert. The scoria-type melted rocks are littered on the ground at several localities distributed along a longitudinal band of about 50km. The silicate glasses have a stable natural remanent magnetization carried by fine-grained magnetite and acquired during cooling. At one locality, fine-grained overbank sediments were heated to form a 10 to 20 cm-thick layer of brick-type samples. Magnetic experiments on oriented samples demonstrate that the baked clays record a thermoremanent magnetization acquired in situ above 600°C down to more than 10cm depth and cooled under a normal polarity geomagnetic field with a paleointensity of 40μT. In some samples of the silicate glass, large grains of iron sulphides (troilite) are found in the glass matrix with numerous droplets of native iron, iron sulphides and iron phosphides indicating high temperature and strong redox conditions during melting. The paleomagnetic record of the baked clays and the unusual mineralogy of the silicate glasses indicate a formation mainly by in situ high temperature radiation. Paleomagnetic experiments and chemical analyses indicate that the silicate glasses are not fulgurite type rocks due to lightning events, nor volcanic glasses or even metallurgical slags related to mining activity. The existence of a well-developped baked clay layer indicates that the silicate glasses are not impact-related ejectas. The field, paleomagnetic and mineralogical observations support evidence for a thermal event likely related to a major airburst. The youngest calibrated 14C age on a charcoal sample closely associated with the glass indicates that the thermal event occurred around 12 to 13 ka BP. The good conservation of the surface effects of this thermal event in the Atacama Desert could provide a good opportunity to further estimate the threats posed by large asteroid airbursts.

  20. Structural environments of incompatible elements in silicate glass/melt systems: II. U IV, U V, and U VI

    NASA Astrophysics Data System (ADS)

    Farges, Franã§Ois; Ponader, Carl W.; Calas, Georges; Brown, Gordon E., Jr.

    1992-12-01

    The structural environments of trace to minor levels (≈2000 ppm to ≈3.0 wt%) of U in several silicate glasses were examined as a function of oxygen fugacity, melt composition, and melt polymerization using X-ray (XANES and EXAFS) and optical absorption spectroscopies. Glass compositions were diopside (CaMgSi 2O 6: DI), anorthite (CaAlSi 2O 8: AN), albite (NaAlSi 3O 8: AB), sodium trisilicate (Na 2Si 3O 7: TS), a peralkaline composition (Na 3.3AlSi 7O 17: PR, approximately halfway between AB and TS), and a calc-alkaline rhyolite composition (RH). A second set of silicate glasses of the same base compositions containing ≈2000 ppm to ≈3.0 wt% U and ≈0.6 to 2.5 wt% F or Cl was also synthesized. In the glasses synthesized under oxidizing conditions (in air), U VI occurs as uranyl groups with two axial oxygens at ≈ 1.77-1.85 ± 0.02 Å and four to five equatorial oxygens at ≈2.21-2.25 ± 0.03 Å. In glasses synthesized under more reducing conditions ( fO2 ≈ 10 -3-10 -7 atm), U V occurs in moderately distorted 6-coordinated polyhedra [ d(U V-O) ≈ 2.19-2.24 ± 0.03 Å], which may co-exist with smaller numbers of U VI species and/or U VI species. Under the most reducing conditions used ( fO2 ≈ 10 -8-10 -12 atm), U IV occurs in less distorted octahedra [ d(U IV-O) ≈ 2.26-2.29 ± 0.02 Å]. No clear evidence for U-F or U-Cl bonds was found for any of the halogen-containing glasses, suggesting that U-halogen "complexes" are not present. In addition, no U-U (second-neighbor) interactions were detected, indicating that no significant clustering of U atoms is present in any of the glasses studied. Bond strength-bond length calculations and constraints placed on local bonding by Pauling's second rule suggest that U IV and U V in 6-coordinated sites in silicate melts will preferentially bond to nonbridging oxygens (NBO's) rather than bridging oxygens (BO's). The unusually low 6-fold coordination of U IV and U V in relatively depolymerized silicate melts (e

  1. Glass as a waste form for the immobilization of plutonium

    SciTech Connect

    Bates, J.K.; Ellison, A.J.G.; Emery, J.W.; Hoh, J.C.

    1995-12-31

    Several alternatives for disposal of surplus plutonium are being considered. One method is incorporating Pu into glass and in this paper we discuss the development and corrosion behavior of an alkali-tin-silicate glass and update results in testing Pu doped Defense Waste Processing Facility (DWPF) reference glasses. The alkali-tin-silicate glass was engineered to accommodate a high Pu loading and to be durable under conditions likely to accelerate glass reaction. The glass dissolves about 7 wt% Pu together with the neutron absorber Gd, and under test conditions expected to accelerate the glass reaction with water, is resistant to corrosion. The Pu and the Gd are released from the glass at nearly the same rate in static corrosion tests in water, and are not segregated into surface alteration phases when the glass is reacted in water vapor. Similar results for the behavior of Pu and Gd are found for the DWPF reference glasses, although the long-term rate of reaction for the reference glasses is more rapid than for the alkali-tin-silicate glass.

  2. Glass Composition-Dependent Silicate Absorption Peaks in FTIR Spectroscopy: Implications for Measuring Sample Thickness and Molecular H2O

    NASA Astrophysics Data System (ADS)

    McIntosh, I. M.; Nichols, A. R.; Schipper, C. I.; Stewart, R. B.

    2015-12-01

    Fourier-transform infrared spectroscopy (FTIR) is often used to measure the H2O and CO2 contents of volcanic glasses. A key advantage of FTIR over other analytical techniques is that it can reveal not only total H2O concentration but also H2O speciation, i.e. how much H2O is present as molecular H2O (H2Om) and how much as hydroxyl groups (OH) bound to the silicate network. This H2O speciation data can be used to investigate cooling rate and glass transition temperature of volcanic glasses, and to interpret H2O contents of pyroclasts affected by partial bubble resorption during cooling or secondary hydration after deposition. FTIR in transmitted light requires sample wafers polished on both sides of known thickness. Thickness is commonly measured using a micrometer but this may damage fragile samples and in samples with non-uniform thickness, e.g. vesicular samples, it is difficult to position at the exact location of FTIR analysis. Furthermore, in FTIR images or maps of such samples it is impractical to determine the thickness across the whole of the analysed area, resulting either in only a selection of the collected data being processed quantitatively and the rest being unused, or results being presented in terms of absorbance, which does not account for variations in thickness.It is known that FTIR spectra contain absorption peaks related to the glass aluminosilicate network at wavenumbers of ~2000, ~1830 and ~1600 cm-1 [1]. These have been shown to be proportional to sample thickness at the analysis location for one obsidian composition with up to 0.66 wt% H2O [2]. We test whether this calibration can be applied more widely by analysing a range of synthetic and natural glasses (andesitic to rhyolitic) to examine how the position and relative intensities of the different silicate absorption peaks vary with composition and H2O content. Our data show that even minor differences in composition necessitate a unique calibration. Furthermore, importantly we show how

  3. Dy3+ ions doped single and mixed alkali fluoro tungsten tellurite glasses for LASER and white LED applications

    NASA Astrophysics Data System (ADS)

    Annapurna Devi, Ch. B.; Mahamuda, Sk.; Venkateswarlu, M.; Swapna, K.; Srinivasa Rao, A.; Vijaya Prakash, G.

    2016-12-01

    A new-fangled series of Dy3+ ions doped Single and Mixed Alkali Fluoro Tungsten Tellurite Glasses have been prepared by using melt quenching technique and their spectroscopic behaviour was investigated by using XRD, optical absorption, photoluminescence and lifetime measurements. The bonding parameter studies reveal the ionic nature of the Dysbnd O bond in the present glasses. From the absorption spectra, the Judd-Ofelt (J-O) intensity parameters have been determined and in turn used to determine various radiative properties for the different emission transitions from the 4F9/2 fluorescent level. The photoluminescence spectra of all the glasses exhibit two intensified peaks in blue and yellow regions corresponding to the transitions 4F9/2 → 6H15/2 (483 nm) and 4F9/2 → 6H13/2 (575 nm) respectively. From the photoluminescence spectra, it is observed that the luminescence intensity is maximum for Dy3+ ion doped potassium combination of tungsten tellurite glass (TeWK:1Dy). The highest emission cross-section and branching ratio values observed for the 4F9/2 → 6H15/2 and 4F9/2 → 6H13/2 transitions suggest the possible laser action in the visible region from these glasses. By correlating the experimental lifetimes (τexp) measured from the decay spectral features with radiative lifetimes (τR), the quantum efficiencies (η) for all the glasses have been evaluated and found to be maximum for potassium combination tungsten tellurite (TeWK:1Dy) glass. The CIE colour chromaticity coordinates (x, y), (u, v), colour correlated temperature (CCT) and Y/B ratio were also estimated from the photoluminescence spectra for different compositions of glasses. The chromaticity colour coordinates evaluated for all the glasses fall within the white light region and white light emission can be tuned by varying the composition of the glass. From all these studies, it was concluded that 1 mol% of Dy3+ ions doped TeWK glass is more suitable for lasing and white-LED applications.

  4. Absorption and photoluminescence properties of Er-doped and Er/Yb codoped soda-silicate laser glasses

    SciTech Connect

    Li, S.F.; Zhang, Q.Y.; Lee, Y.P.

    2004-11-01

    Er-doped and Er/Yb codoped soda-silicate laser glasses with various concentrations of Er and Yb were fabricated. The absorption and the photoluminescence (PL) spectra were measured and analyzed. For the Er- doped soda-slilicate glasses, the optimum Er concentration for the PL intensity at 1536 nm turns out to be 0.5 at. %, and the full width at half maximum (FWHM) of PL spectrum increases from 18 to 26 nm, with the increase of the concentration from 0.1 to 0.8 at. %. The PL intensity of Er/Yb codoped soda-silicate glasses with an Er concentration of 0.5 at. % is enhanced approximately by four times, and the optimum Yb concentration for the PL intensity at 1536 nm is analyzed to be 3.0 at. %. The PL spectrum becomes broader with increasing the Yb concentration, up to a FWHM of 80 nm at 6.0 at. %. Yb. The relation between the absorption and PL spectra, together with the mechanism of PL broadening, has also been addressed.

  5. 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.

  6. Genesis of recent silicic magmatism in the Medicine Lake Highland, California - Evidence from cognate inclusions found at Little Glass Mountain

    NASA Technical Reports Server (NTRS)

    Mertzman, S. A.; Williams, R. J.

    1981-01-01

    Sparse, granular inclusions of early-formed minerals found within the Little Glass Mountain rhyolite flows in northern California are shown to provide a means of characterizing the physical conditions, at depth, beneath the Medicine Lake Highland during the latest phase of volcanic activity. Mineral compositions, in combination with thermodynamic calculations and experiments, suggest crystalization at a pressure of 5,200 bars within a 966-836 C temperature range; implying that mineral segregation and equilibration occurred at a depth of 15-18 km beneath the surface. In addition, mass balance calculations indicate that the Medicine Lake flow is a close approximation to the parental magma for the latest silicic lavas.

  7. Large-mode-area single-mode-output Neodymium-doped silicate glass all-solid photonic crystal fiber.

    PubMed

    Li, Wentao; Chen, Danping; Qinling, Zhou; Hu, Lili

    2015-07-24

    We have demonstrated a 45 μm core diameter Neodymium-doped all-solid silicate glass photonic crystal fiber laser with a single mode laser output. The structure parameters and modes information of the fiber are both demonstrated by theoretical calculations using Finite Difference Time Domain (FDTD) method and experimental measurements. Maximum 0.8 W output power limited by launched pump power has been generated in 1064 nm with laser beam quality factor M(2) 1.18.

  8. Large-mode-area single-mode-output Neodymium-doped silicate glass all-solid photonic crystal fiber

    PubMed Central

    Li, Wentao; Chen, Danping; Qinling, Zhou; Hu, Lili

    2015-01-01

    We have demonstrated a 45 μm core diameter Neodymium-doped all-solid silicate glass photonic crystal fiber laser with a single mode laser output. The structure parameters and modes information of the fiber are both demonstrated by theoretical calculations using Finite Difference Time Domain (FDTD) method and experimental measurements. Maximum 0.8 W output power limited by launched pump power has been generated in 1064 nm with laser beam quality factor M2 1.18. PMID:26205850

  9. Computational interpretation of 23Na MQMAS NMR spectra: A comprehensive investigation of the Na environment in silicate glasses

    NASA Astrophysics Data System (ADS)

    Gambuzzi, Elisa; Charpentier, Thibault; Menziani, Maria Cristina; Pedone, Alfonso

    2014-09-01

    Molecular dynamics, density functional theory calculations and 23Na NMR experiments have been used to inspect the chemical and structural characteristics of the Na environment in soda-lime silicate (CSN) and aluminosilicate (CASN) glasses. The use of an improved 3QMAS pulse sequence has allowed a clear identification of different Na sites. Average coordination numbers have been extracted by fitting the 23Na 3QMAS spectra with the computed NMR parameters. The results show that the 23Na δiso values correlate with the average distances only when the different coordination numbers are explicitly taken into account.

  10. Intense 1.6 μm fluorescence of Nd{sup 3+} doped cadmium bismuth silicate glasses

    SciTech Connect

    Pal, I. Agarwal, A. Sanghi, S.; Bhardwaj, S.; Sanjay

    2014-04-24

    In this work, Judd-Ofelt analysis is applied to rare-earth (RE = Nd{sup 3+}) doped cadmium bismuth silicate (20CdO⋅xSiO{sub 2}⋅(79.5−x)Bi{sub 2}O{sub 3}⋅0.5Nd{sub 2}O{sub 3} (CSBN)) glasses in order to evaluate their potential as well as both glass laser systems and optical materials. The phenomenological Judd-Ofelt parameters (Ω{sub 2}, Ω{sub 4}, Ω{sub 6}) are determined for RE ions with their quality factors and compared with the equivalent parameters for several other hosts. The calculated value of stimulated emission cross-section for {sup 4}F{sub 3/2}→{sup 4}I{sub 11/2} has high and varies 14.72×10{sup −20} to 9.66×10{sup −20} cm{sup 2} with Bi{sub 2}O{sub 3} content in the host glass. The results point out that the glass system is good candidate for the development of photonics devices which are operating near infrared spectral range. Further, the FTIR results reveal that the glasses have BiO{sub 6}, SiO{sub 4} and non-bridging oxygen as local structure.

  11. Multidiffusion mechanisms for noble gases (He, Ne, Ar) in silicate glasses and melts in the transition temperature domain: Implications for glass polymerization

    NASA Astrophysics Data System (ADS)

    Amalberti, Julien; Burnard, Pete; Laporte, Didier; Tissandier, Laurent; Neuville, Daniel R.

    2016-01-01

    Noble gases are ideal probes to study the structure of silicate glasses and melts as the modifications of the silicate network induced by the incorporation of noble gases are negligible. In addition, there are systematic variations in noble gas atomic radii and several noble gas isotopes with which the influence of the network itself on diffusion may be investigated. Noble gases are therefore ideally suited to constrain the time scales of magma degassing and cooling. In order to document noble gas diffusion behavior in silicate glass, we measured the diffusivities of three noble gases (4He, 20Ne and 40Ar) and the isotopic diffusivities of two Ar isotopes (36Ar and 40Ar) in two synthetic basaltic glasses (G1 and G2; 20Ne and 36Ar were only measured in sample G1). These new diffusion results are used to re-interpret time scales of the acquisition of fractionated atmospheric noble gas signatures in pumices. The noble gas bearing glasses were synthesized by exposing the liquids to high noble gas partial pressures at high temperature and pressure (1750-1770 K and 1.2 GPa) in a piston-cylinder apparatus. Diffusivities were measured by step heating the glasses between 423 and 1198 K and measuring the fraction of gas released at each temperature step by noble gas mass spectrometry. In addition we measured the viscosity of G1 between 996 and 1072 K in order to determine the precise glass transition temperature and to estimate network relaxation time scales. The results indicate that, to a first order, that the smaller the size of the diffusing atom, the greater its diffusivity at a given temperature: D(He) > D(Ne) > D(Ar) at constant T. Significantly, the diffusivities of the noble gases in the glasses investigated do not display simple Arrhenian behavior: there are well-defined departures from Arrhenian behavior which occur at lower temperatures for He than for Ne or Ar. We propose that the non-Arrhenian behavior of noble gases can be explained by structural modifications

  12. Silicate glasses and sulfide melts in the ICDP-USGS Eyreville B core, Chesapeake Bay impact structure, Virginia, USA

    USGS Publications Warehouse

    Belkin, H.E.; Horton, J.W.

    2009-01-01

    Optical and electron-beam petrography of melt-rich suevite and melt-rock clasts from selected samples from the Eyreville B core, Chesapeake Bay impact structure, reveal a variety of silicate glasses and coexisting sulfur-rich melts, now quenched to various sulfi de minerals (??iron). The glasses show a wide variety of textures, fl ow banding, compositions, devitrifi cation, and hydration states. Electron-microprobe analyses yield a compositional range of glasses from high SiO2 (>90 wt%) through a range of lower SiO2 (55-75 wt%) with no relationship to depth of sample. Some samples show spherical globules of different composition with sharp menisci, suggesting immiscibility at the time of quenching. Isotropic globules of higher interfacial tension glass (64 wt% SiO2) are in sharp contact with lower-surface-tension, high-silica glass (95 wt% SiO2). Immiscible glass-pair composition relationships show that the immiscibility is not stable and probably represents incomplete mixing. Devitrifi cation varies and some low-silica, high-iron glasses appear to have formed Fe-rich smectite; other glass compositions have formed rapid quench textures of corundum, orthopyroxene, clinopyroxene, magnetite, K-feldspar, plagioclase, chrome-spinel, and hercynite. Hydration (H2O by difference) varies from ~10 wt% to essentially anhydrous; high-SiO2 glasses tend to contain less H2O. Petrographic relationships show decomposition of pyrite and melting of pyrrhotite through the transformation series; pyrite? pyrrhotite? troilite??? iron. Spheres (~1 to ~50 ??m) of quenched immiscible sulfi de melt in silicate glass show a range of compositions and include phases such as pentlandite, chalcopyrite, Ni-As, monosulfi de solid solution, troilite, and rare Ni-Fe. Other sulfi de spheres contain small blebs of pure iron and exhibit a continuum with increasing iron content to spheres that consist of pure iron with small, remnant blebs of Fe-sulfi de. The Ni-rich sulfi de phases can be explained by

  13. 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.

  14. Glass science tutorial lecture {number_sign}6: The melting of silicate glasses, a review of selected topics

    SciTech Connect

    Swarts, E.L.

    1995-03-01

    This report summarizes a two-day lecture given at Westinghouse Hanford Company in March, 1995 and includes the data used in the presentation. Topics included the special needs of a low-level waste vitrification process, glass melting, mechanisms of the formation of foam, glass refining (bubble removal), and homogenization (reduction of chemical heterogeneity to acceptable levels). 96 refs.

  15. Nucleation and Crystallization as Induced by Bending Stress in Lithium Silicate Glass Fibers

    NASA Technical Reports Server (NTRS)

    Reis, Signo T.; Kim, Cheol W.; Brow, Richard K.; Ray, Chandra S.

    2003-01-01

    Glass Fibers of Li2O.2SiO2 (LS2) and Li2O.1.6SiO2 (LS1.6) compositions were heated near, but below, the glass transition temperature for different times while subjected to a constant bending stress of about 1.2 GPa. The nucleation density and the crystallization tendency estimated by differential thermal analysis (DTA) of a glass sample in the vicinity of the maximum of the bending stress increased relative to that of stress-free glass fibers. LS2 glass fibers were found more resistant to nucleation and crystallization than the Ls1.6 glass fibers. These results are discussed in regards to shear thinning effects on glass stability.

  16. 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.

  17. 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.

  18. Oxygen-implanted optical planar waveguides in Er/Yb-codoped silicate glasses for integrated laser generation

    NASA Astrophysics Data System (ADS)

    Liu, Chun-Xiao; Xu, Jun; Xu, Xiao-Li; Wu, Shu; Wei, Wei; Guo, Hai-Tao; Li, Wei-Nan; Peng, Bo

    2014-03-01

    Er3+/Yb3+-codoped silicate glasses are good candidates for the application of laser actions and signal amplification. Optical planar waveguides in Er/Yb-codoped silicate glasses are fabricated by 6.0-MeV oxygen-ion implantation with a dose of 6.0×1014 ions/cm2 at room temperature. The SRIM 2010 code is carried out to simulate the energy losses during the implantation process in order to obtain a better understanding of the waveguide formation. The guiding modes and near-field intensity distributions of the waveguide are characterized by the prism-coupling and end-face coupling methods. The refractive index profile and light propagation mode of the planar waveguide are numerically calculated by the reflectivity calculation method and finite difference beam propagation method. The waveguide has a "well+barrier" refractive index distribution and its optical loss is ˜1.02 dB/cm. The microluminescence and absorption investigation reveal that fluorescent and transmission properties in the waveguide are well preserved with respect to the bulk, suggesting promising potential for waveguide amplifiers and lasers.

  19. Development of a novel aluminum-free glass ionomer cement based on magnesium/strontium-silicate glasses.

    PubMed

    Kim, Dong-Ae; Abo-Mosallam, Hany A; Lee, Hye-Young; Kim, Gyu-Ri; Kim, Hae-Won; Lee, Hae-Hyoung

    2014-09-01

    The effects of strontium substitution for magnesium in a novel aluminum-free multicomponent glass composition for glass ionomer cements (GICs) were investigated. A series of glass compositions were prepared based on SiO2-P2O5-CaO-ZnO-MgO(1-X)-SrOX-CaF2 (X=0, 0.25, 0.5 and 0.75). The mechanical properties of GICs prepared were characterized by compressive strength, flexural strength, flexural modules, and microhardness. Cell proliferation was evaluated indirectly by CCK-8 assay using various dilutions of the cement and rat mesenchyme stem cells. Incorporation of strontium instead of magnesium in the glasses has a significant influence on setting time of the cements and the properties. All mechanical properties of the GICs with SrO substitution at X=0.25 were significantly increased, then gradually decreased with further increase of the amount of strontium substitution in the glass. The GIC at X=0.25, also, showed an improved cell viability at low doses of the cement extracts in comparison with other groups or control without extracts. The results of this study demonstrate that the glass compositions with strontium substitution at low levels can be successfully used to prepare aluminum-free glass ionomer cements for repair and regeneration of hard tissues.

  20. 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.

  1. Novel refractory alkaline earth silicate sealing glasses for planar solid oxide fuel cells

    SciTech Connect

    Chou, Y. S.; Stevenson, Jeffry W.; Singh, Prabhakar

    2007-07-01

    A novel “refractory” Sr-Ca-Y-B-Si sealing glass (glass-ceramic) was developed for solid oxide fuel cells (SOFCs). The objective was to develop sealing glass with desired thermal properties and minimal interfacial reactions with SOFC components, ceramic electrolyte and metallic interconnect. The current glass was different from conventional sealing glass in that the sealing temperatures were targeted higher (>950 degree C) and hence more refractory. Six glasses were formulated and made by conventional glass-making process. Thermal properties were characterized in the glass state and the sintered (crystallized) state. The effect of formulation on thermal properties was discussed. Candidate glasses were also aged for 1000 to 2000 h at elevated temperatures. Thermal expansion measurements showed minimal change after aging. A candidate glass (YSO-1) was used in sealing ceramic electrolyte to a metallic interconnect from 900 degree C to 1050 degree C in air. The interfacial microstructure was characterized and SrCrO4 was identified near the metal interface. Possible reaction mechanism for the chromate formation was discussed.

  2. 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.

  3. Effect of MnO2 doped on physical, structure and optical properties of zinc silicate glasses from waste rice husk ash

    NASA Astrophysics Data System (ADS)

    Al-Nidawi, Ali Jabbar Abed; Matori, Khamirul Amin; Zakaria, Azmi; Mohd Zaid, Mohd Hafiz

    In this study, an investigation was conducted to explore and synthesize silicate (SiO2) glass from waste rice husk ash (RHA). MnO2 doped zinc silicate glasses with chemical formula [(ZnO)55 + (WRHA)45]100-X[MnO2]X, (where X = 0, 1, 3 and 5 wt%) was prepared by conventional melt quenching technique. The glass samples were characterized using energy dispersive X-ray fluorescence (EDXRF), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared (FTIR) spectroscopy, and ultraviolet-visible (UV-Vis) spectroscopy. The results revealed that by increasing the concentration of MnO2, the color of glass samples changed from colorless to brown and the density of glass increased. XRD results showed that a broad halo peak which centered on the low angle (2θ = 30°) indicated the amorphous nature of the glass. FTIR results showed basic structural units of Si-O-Si in non-bridging oxygen, Si-O and Mn-O in the glass network. FESEM result showed a decreasing porosity with an increasing MnO2 content, which was attributed to the Mn ions resort to occupy interstitial sites inside the pores of glass. Besides, the absorption intensity of glass increased and the band gap value decreased with increasing the MnO2 percentage. In this synthesized glass system of MnO2 doped zinc silicate glasses using RHA as a source of silica, the MnO2 affect most of the properties of the glass system under investigation.

  4. Structure, surface reactivity and physico-chemical degradation of fluoride containing phospho-silicate glasses

    SciTech Connect

    Kansal, Ishu; Goel, Ashutosh; Tulyaganov, Dilshat U.; Santos, Luis F.; Ferreira, Jose M.

    2011-03-28

    We report on the structure, apatite-forming ability and physicochemical degradation of glasses along fluorapatite [FA; Ca5(PO4)3F] - diopside (Di; CaMgSi2O6) join. A series of glasses with varying FA/Di ratio have been synthesised by melt-quenching technique. The amorphous glasses could be obtained only for compositions up to 40 wt.% of FA. The detailed structural analysis of glasses has been made by infra-red spectroscopy (FTIR), Raman spectroscopy and magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR). Silicon was predominantly present as Q2 (Si) species while phosphorus was found in orthophosphate type environment in all the investigated glasses. The apatite forming ability of glasses was investigated by immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1 h – 28 days. An extensive precipitation of calcite (CaCO3) after immersion in SBF was found in all the glasses which considerably masked the formation of hydroxyapatite [HA; Ca5(PO4)3OH] as depicted by X-ray diffraction (XRD) and FTIR. The possible mechanism favouring formation of calcite instead of HA has been explained on the basis of experimental results obtained for structure of glasses, leaching profile of glass powders in SBF solution and pH variation in SBF solution. Further, physico-chemical degradation of glasses has been studied in accordance with ISO 10993-14 “Biological evaluation of medical devices – Part 14: Identification and quantification of degradation products from ceramics” in Tris HCl and citric acid buffer. All the FA containing glasses exhibited a weight gain (instead of weight loss) after immersion in citric acid buffer due to the formation of different crystalline products.

  5. 2 μm emission properties and nonresonant energy transfer of Er3+ and Ho3+ codoped silicate glasses

    PubMed Central

    Cao, Ruijie; Lu, Yu; Tian, Ying; Huang, Feifei; Guo, Yanyan; Xu, Shiqing; Zhang, Junjie

    2016-01-01

    2.0 μm emission properties of Er3+/Ho3+ codoped silicate glasses were investigated pumped by 980 nm LD. Absorption spectra were determined. Intense mid-infrared emissions near 2 μm are observed. The spectral components of the 2 μm fluorescence band were analyzed and an equivalent model of four-level system was proposed to describe broadband 2 μm emission. Low OH− absorption coefficient (0.23 cm−1), high fluorescence lifetime (2.95 ms) and large emission cross section (5.61 × 10−21 cm2) corresponding to Ho3+: 5I7→5I8 transition were obtained from the prepared glass. Additionally, energy transfer efficiency from the Er3+: 4I13/2 to the Ho3+: 5I7 level can reach as high as 85.9% at 0.75 mol% Ho2O3 doping concentration. Energy transfer microscopic parameters (CDA) via the host-assisted spectral overlap function were also calculated to elucidate the observed 2 μm emissions in detail. Moreover, the rate equation model between Er3+ and Ho3+ ions was developed to elucidate 2 μm fluorescence behaviors with the change of Ho3+ concentration. All results reveal that Er3+/Ho3+ codoped silicate glass is a promising material for improving the Ho3+ 2.0 μm fiber laser performance. PMID:27901047

  6. 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.

  7. Physical, structural and optical characterization of silicate modified bismuth-borate-tellurite glasses

    NASA Astrophysics Data System (ADS)

    Berwal, Neelam; Dhankhar, Sunil; Sharma, Preeti; Kundu, R. S.; Punia, R.; Kishore, N.

    2017-01-01

    The quaternary glass system xSiO2-(80-x) Bi2O3sbnd 15B2O3sbnd 5TeO2 has been prepared by melt-quench technique. The amorphous nature of glass samples has been ascertained by X-ray diffraction patterns. The variations in density, molar volume and crystalline volume with glass compositions have been discussed. A non-linear change has been observed in glass transition temperature and optical band gap energy. Raman and FTIR spectral studies suggest that glass network is mainly built up of BO3, BO4, SiO4, and TeO3 structural units, whereas BiO3 exists as both network modifying [BiO6] octahedral as well as network forming [BiO3] pyramidal structural units. The values of optical band gap energy have been estimated from fitting of both Mott and Davis's model and Hydrogenic excitonic model (HEM) with experimental data of absorption spectra. The HEM model shows good agreement with experimentally observed absorption spectra, which indicates the exciton formation in studied glass system. The non-linear compositional change in optical band gap energy is related with the structural changes occurring in present glass samples. The Urbach energy has also been estimated. The range of metallization criterion suggests that prepared glasses may be considered as new nonlinear optical materials.

  8. Observation of a stuffed unmodified network in beryllium silicate glasses with multinuclear NMR spectroscopy

    SciTech Connect

    Sen, Sabyasachi; Yu Ping

    2005-10-01

    The structure of BeO-SiO{sub 2} glasses with up to 20 mol % BeO has been studied with {sup 9}Be and {sup 29}Si NMR spectroscopic techniques. The NMR results are consistent with a glass structure consisting of nanoclusters of corner-shared BeO{sub 4} tetrahedra that occupy the interstices of an unmodified and highly strained corner-shared SiO{sub 4} network. The complete absence of nonbridging oxygens in these glasses contradicts the conventional wisdom of oxide glass structures based on the modified random-network-type models. This structure type may have important implications in understanding and designing glasses with unusual properties.

  9. Multicolour laser recording of optical information in silicate glasses with europium, silver and cerium ions

    NASA Astrophysics Data System (ADS)

    Klyukin, D. A.; Khmelev, A. Yu.; Pshenova, A. S.; Sidorov, A. I.; Fedorov, Yu. K.

    2016-10-01

    We have shown experimentally that the effect of cw UV radiation and pulsed UV radiation from a nanosecond laser as well as thermal treatment of glasses with europium, silver and cerium ions (photosensitizer) allow the local formation of the areas in glass, having different luminescence colour or the areas of different colouration. These effects are caused by a change in the charge state of molecular clusters and the formation of silver nanoparticles possessing plasmon resonance in glass. This allows recording of multicolour optical information by means of a focused beam from a UV laser, both near the glass surface and within its volume. We have revealed the influence of chlorine on the formation and properties of silver nanoparticles in glass in the course of thermal treatment following the laser impact.

  10. Effect of natural and synthetic iron corrosion products on silicate glass alteration processes

    NASA Astrophysics Data System (ADS)

    Dillmann, Philippe; Gin, Stéphane; Neff, Delphine; Gentaz, Lucile; Rebiscoul, Diane

    2016-01-01

    Glass long term alteration in the context of high-level radioactive waste (HLW) storage is influenced by near-field materials and environmental context. As previous studies have shown, the extent of glass alteration is strongly related to the presence of iron in the system, mainly provided by the steel overpack around surrounding the HLW glass package. A key to understanding what will happen to the glass-borne elements in the geological disposal lies in the relationship between the iron-bearing phases and the glass alteration products formed. In this study, we focus on the influence of the formation conditions (synthetized or in-situ) and the age of different iron corrosion products on SON68 glass alteration. Corrosion products obtained from archaeological iron artifacts are considered here to be true analogues of the corrosion products in a waste disposal system due to the similarities in formation conditions and physical properties. These representative corrosion products (RCP) are used in the experiment along with synthetized iron anoxic corrosion products and pristine metallic iron. The model-cracks of SON68 glass were altered in cell reactors, with one of the different iron-sources inserted in the crack each time. The study was successful in reproducing most of the processes observed in the long term archaeological system. Between the different systems, alteration variations were noted both in nature and intensity, confirming the influence of the iron-source on glass alteration. Results seem to point to a lesser effect of long term iron corrosion products (RCP) on the glass alteration than that of the more recent products (SCP), both in terms of general glass alteration and of iron transport.

  11. Efficient 2 μm emission in Nd3+/Ho3+ co-doped silicate-germanate glass pumped by common 808 nm LD

    NASA Astrophysics Data System (ADS)

    Chen, Rong; Tian, Ying; Li, Bingpeng; Huang, Feifei; Wang, Caizhi; Jing, Xufeng; Zhang, Junjie; Xu, Shiqing

    2017-03-01

    Nd3+/Ho3+ co-doped silicate-germanate glass has been synthesized by high temperature melt-quenching method. Near infrared emission centered at 2 μm has been successfully obtained by incorporating Nd3+ and Ho3+ in present glass. The Judd-Ofelt intensity parameters Ωt (t=2, 4, 6), and radiative properties of Ho3+ were calculated and discussed by using the Judd-Ofelt theory. The energy transfer processes and luminescence properties of Nd3+/Ho3+ co-doped glasses were analyzed pumped by a conventional 808 nm laser diode. Desirable spectroscopic characteristics indicates that Nd3+/Ho3+ co-doped silicate-germanate glass might be a good alternative matrix for 2 μm band mid-infrared laser.

  12. Broadband 1.53 μm emission property in Er3+ doped germa-silicate glass for potential optical amplifier

    NASA Astrophysics Data System (ADS)

    Wei, Tao; Chen, Fangze; Tian, Ying; Xu, Shiqing

    2014-03-01

    In this paper, a new type of germa-silicate glass was developed. A detailed investigation of thermal stability, absorption spectrum and 1.53 μm emission spectrum was carried out. Based on the absorption spectrum and Judd-Ofelt theory, the Judd-Ofelt parameters and radiative properties were calculated and compared to other glasses. The thermal stability of prepared glass can reach as high as 155 °C. Er3+ doped germa-silicate glass possessing high full-width at half-maximum (FWHM) (77 nm) and large stimulated emission cross-section (9.55×10-21 cm2) shows its potential application in broadband optical amplifier.

  13. Novel alkaline earth silicate sealing glass for SOFC, Part I: the effect of nickel oxide on the thermal and mechanical properties

    SciTech Connect

    Chou, Y. S.; Stevenson, Jeffry W.; Gow, Robert N.

    2007-06-01

    This is a two-part study of a novel Sr-Ca-Ni-Y-B silicate sealing glass for solid oxide fuel cells (SOFC). In this paper (Part I), the effect of NiO on glass forming, thermal, and mechanical properties was studied with two different approaches: glass making and composite glass. In the following paper (Part II), sealing and interfacial microstructure of candidate composite glass with 10v percent NiO will be addressed. In Part I, higher NiO content in the glass resulted in precipitation during the glass making process, and the sintered powder compacts of these glasses showed extensive macro- and micro-cracks. Coefficient of thermal expansion (CTE) showed large decrease for glass with higher NiO contents. On the other hand, glass-based composites showed no fracture even with NiO content as high as 15 percent. The CTE of the composite glass, which increased with increasing NiO content (consistent with the rule of mixtures prediction), could be adjusted to match the CTE of SOFC components. Phase characterization by XRD identified phases of YBO3 and NiO in the glass, which were likely responsible for the poor mechanical and thermal properties for the glass making approach.

  14. Dissolution of glass wool, rock wool and alkaline earth silicate wool: morphological and chemical changes in fibers.

    PubMed

    Campopiano, Antonella; Cannizzaro, Annapaola; Angelosanto, Federica; Astolfi, Maria Luisa; Ramires, Deborah; Olori, Angelo; Canepari, Silvia; Iavicoli, Sergio

    2014-10-01

    The behavior of alkaline earth silicate (AES) wool and of other biosoluble wools in saline solution simulating physiological fluids was compared with that of a traditional wool belonging to synthetic vitreous fibers. Morphological and size changes of fibers were studied by scanning electron microscopy (SEM). The elements extracted from fibers were analyzed by inductively coupled plasma atomic emission spectrometry. SEM analysis showed a larger reduction of length-weighted geometric mean fiber diameter at 4.5 pH than at 7.4 pH. At the 7.4 pH, AES wool showed a higher dissolution rate and a dissolution time less than a few days. Their dissolution was highly non-congruent with rapid leaching of calcium. Unlike rock wool, glass wool dissolved more rapidly at physiological pH than at acid pH. Dissolution of AES and biosoluble rock wool is accompanied by a noticeable change in morphology while by no change for glass wool. Biosoluble rock wool developed a leached surface with porous honeycomb structure. SEM analysis showed the dissolution for glass wool is mainly due to breakage transverse of fiber at pH 7.4. AES dissolution constant (Kdis) was the highest at pH 7.4, while at pH 4.5 only biosoluble rockwool 1 showed a higher Kdis.

  15. Novel adaptations to zinc-silicate glass polyalkenoate cements: the unexpected influences of germanium based glasses on handling characteristics and mechanical properties.

    PubMed

    Dickey, B T; Kehoe, S; Boyd, D

    2013-07-01

    Aluminum-free glass polyalkenoate cements (GPC) have been hindered for use as injectable bone cements by their inability to balance handling characteristics with mechanical integrity. Currently, zinc-based, aluminum-free GPCs demonstrate compression strengths in excess of 60MPa, but set in c. 1-2 min. Previous efforts to extend the setting reaction have remained clinically insufficient and are typically accompanied by a significant drop in strength. This work synthesized novel glasses based on a zinc silicate composition with the inclusion of GeO2, ZrO2, and Na2O, and evaluated the setting reaction and mechanical properties of the resultant GPCs. Germanium based GPCs were found to have working times between 5 and 10 min, setting times between 14 and 36 min, and compression strengths in excess of 30 MPa for the first 30 days. The results of this investigation have shown that the inclusion of GeO2, ZrO2, and Na2O into the glass network have produced, for the first time, an aluminum-free GPC that is clinically viable as injectable bone cements with regards to handling characteristics and mechanical properties.

  16. Parasitic amorphous on single-domain crystal: Structural observations of silicate glass-ceramics

    NASA Astrophysics Data System (ADS)

    Takahashi, Yoshihiro; Yamazaki, Yoshiki; Ihara, Rie; Fujiwara, Takumi

    2013-01-01

    Glass-ceramics (GCs) are materials obtained from the crystallisation of functional phases in glass, and have a structure that the crystallised phase embedded in the glass matrix. Glass-forming oxides are commonly added to the functional phases to improve the stability of precursor glass; however, the issue of glass-ceramics permitting the presence of residual phases resulting from addition is required to be clarified. To elucidate this issue, we prepared `perfectly surface-crystallised' GC consisting of fresnoite-type Sr2TiSi2O8 from a non-stoichiometric glass and performed texture/morphology observations. Numerous SiO2-rich binodal-like nanospheres (~10 nm) were parasitic on the fresnoite single-crystal domains. The parasitic texture is considered to form via the following process: (i) binodal-type phase separation into stoichiometric fresnoite (crystalline matrix) and SiO2-rich phases (amorphous nanoparticles) and (ii) single-domain formation by surface crystallisation in the matrix. Furthermore, in terms of texture, the resulting GC differs from the GCs reported to date, i.e., inverse GC.

  17. Structural investigations of silicate-phosphate glasses containing MoO3 by FTIR, Raman and 31P MAS NMR spectroscopies

    NASA Astrophysics Data System (ADS)

    Szumera, Magdalena

    2014-09-01

    Molybdenum is a transition metal (refers to the “d” block of the periodic table) whose atom has an incomplete d sub-shell. It is known that in silicate glasses molybdenum may exist under four oxidation states: Mo6+, Mo5+, Mo4+ and Mo3+, simultaneously molybdenum cations, depending on their content in the glass network, may either be a glass forming component, or act as a modifier. The contemporary literature data show studies conducted mostly on the structure of silicate, phosphate, borate and borosilicate glasses containing molybdenum ions, but not silicate-phosphate glasses. Therefore, the author has undertaken detailed studies using FTIR, Raman and 31P MAS NMR techniques in order to examine the effect of MoO3 addition into the structure of silicate-phosphate glasses from SiO2sbnd P2O5sbnd K2Osbnd CaOsbnd MgO system. On the basis of obtained results it was concluded that molybdenum ions in the analysed glasses act as a modifier, which follows from the gradual breakage of oxygen bridges, i.e. Psbnd Osbnd P, Sisbnd Osbnd Si, and Sisbnd Osbnd P, and the following formation of connections such as Mo[MoO4]sbnd Osbnd Si and/or Mo[MoO4]sbnd Osbnd P. In summary, it is concluded that the increase of MoO3 content (up to 4.4 mol.%) in the structure of glasses of SiO2sbnd P2O5sbnd K2Osbnd MgOsbnd CaO system results in weakening of the structure and gradual increase of the degree of silico-oxygen and phosphor-oxygen frameworks depolymerisation.

  18. Structural investigations of silicate-phosphate glasses containing MoO3 by FTIR, Raman and 31P MAS NMR spectroscopies.

    PubMed

    Szumera, M

    2014-09-15

    Molybdenum is a transition metal (refers to the "d" block of the periodic table) whose atom has an incomplete d sub-shell. It is known that in silicate glasses molybdenum may exist under four oxidation states: Mo6+, Mo5+, Mo4+ and Mo3+, simultaneously molybdenum cations, depending on their content in the glass network, may either be a glass forming component, or act as a modifier. The contemporary literature data show studies conducted mostly on the structure of silicate, phosphate, borate and borosilicate glasses containing molybdenum ions, but not silicate-phosphate glasses. Therefore, the author has undertaken detailed studies using FTIR, Raman and 31P MAS NMR techniques in order to examine the effect of MoO3 addition into the structure of silicate-phosphate glasses from SiO2P2O5K2OCaOMgO system. On the basis of obtained results it was concluded that molybdenum ions in the analysed glasses act as a modifier, which follows from the gradual breakage of oxygen bridges, i.e. POP, SiOSi, and SiOP, and the following formation of connections such as Mo[MoO4]OSi and/or Mo[MoO4]OP. In summary, it is concluded that the increase of MoO3 content (up to 4.4 mol.%) in the structure of glasses of SiO2P2O5K2OMgOCaO system results in weakening of the structure and gradual increase of the degree of silico-oxygen and phosphor-oxygen frameworks depolymerisation.

  19. 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.

  20. Spectroscopic characterization of alkali modified zinc-tellurite glasses doped with neodymium.

    PubMed

    Rajeswari, R; Babu, S Surendra; Jayasankar, C K

    2010-09-15

    Neodymium doped zinc-tellurite glasses of composition TeO(2)-ZnO-Na(2)O-Li(2)O have been prepared and characterized for their thermal, structural and optical properties. Differential thermal analysis revealed reasonably good forming tendency of the glass composition. FTIR spectra were used to analyze the functional groups present in the glass. Judd-Ofelt intensity parameters were derived from the absorption spectrum and used to calculate the radiative lifetime, branching ratio and stimulated emission cross-section for (4)F(3/2)-->(4)I(9/2, 11/2, 13/2) transitions. The quantum efficiency of the (4)F(3/2) level is comparable to the typical values obtained for the Nd(2)O(3)-doped glasses. The decay properties for higher concentration of Nd(2)O(3) were analyzed using Inokuti-Hirayama model to investigate the non-radiative relaxation of the (4)F(3/2) emitting level. The experimental values of branching ratio and saturation intensity of (4)F(3/2)-->(4)I(11/2) transition and calculated spectroscopic quality factor indicate the favourable lasing action in these glasses.

  1. Physical, structural and optical characterizations of borate modified bismuth-silicate-tellurite glasses

    NASA Astrophysics Data System (ADS)

    Berwal, Neelam; Kundu, R. S.; Nanda, Kirti; Punia, R.; Kishore, N.

    2015-10-01

    Quaternary bismuthate glasses with compositions xB2O3-(80 - x) Bi2O3-15SiO2-5TeO2 have been prepared by melt-quench technique. X-ray diffraction studies were performed to ascertain the amorphous nature of samples. The density, molar volume and crystalline volume decrease with increase in B2O3 content whereas the glass transition temperature shows the reverse trend. The Raman and FTIR spectra of the studied glasses indicate that B2O3 has been found to exist in the form of BO3 trigonal and BO4 tetrahedral structural units and vibrations corresponding to these structural units increase with increase in B2O3 content. SiO2 is present in the form of SiO4 tetrahedral structural units and TeO2 in the form of TeO3 structural units. Bismuth plays the role of network modifier [BiO6 octahedra] as well as network former [BiO3 pyramids] for all the glass compositions. The optical band gap energy has been calculated from the fitting of both Mott and Davis's model and Hydrogenic excitonic model with the experimentally observed absorption spectra. A good fitting of experimental data with HEM indicates the excitonic formation in the studies glass system. The values of optical band gap energy show nonlinear behavior due to the structural changes that take place in the present glass samples. The Urbach energy calculated using Urbach empirical formula for studied glass samples suggest the possibility of reduction in defect concentrations. The metallization criterion of the presently studied samples suggests that the prepared glasses may be potential candidates for nonlinear optical applications.

  2. Development of drug adsorbates onto soluble inorganic silicate glass surface: example with acetaminophen.

    PubMed

    Hristova, Yoanna; Djambaski, Peter; Samuneva, Biserka; Rangelova, Nadya; Bogdanova, Svetla

    2008-02-01

    A ternary melt-derived inorganic glass system (Igl) of composition corresponding to 62SiO(2), 35Na(2)O, 3Al(2)O(3 )(wt.%) has been formulated and studied as a drug carrier. The [Al(2)O(3)/Na(2)O] ratio is less than one and the aluminium ion is a network former that retards the glass dissolution. The processing conditions lead to a brittle, easily grinding, amorphous product. The Igl structure was proven by IR-spectroscopy, energy-dispersive spectrometry, X-ray diffraction, scanning electron microscopy. A very important fact established is that the Igl corrosion (dissolution) is pH-dependent. Inorganic glass system was transformed into model acetaminophen (APH) adsorbate (APH/Igla 1:1(w/w)) with mild experimental conditions and evaluated as a drug carrier. No interactions between Igl and APH during the processing were proven. Besides, APH settles onto the glass surface as crystalline phase. A lower extent of corrosion, apparent solubility and delayed in vitro APH release from the adsorbate in water and artificial gastric juice in comparison to the samples untreated drug and APH/Iglm physical mixture were established. It is hypothesized that the glass decomposition products, formed into contact with a solvent, initiate interactions with APH at the glass/solution interface. Similar behaviour of the Igl and its drug adsorbates could be expected in gastro-intestinal tract.

  3. Analysis of H2O in silicate glass using attenuated total reflectance (ATR) micro-FTIR spectroscopy

    USGS Publications Warehouse

    Lowenstern, Jacob B.; Pitcher, Bradley W.

    2013-01-01

    We present a calibration for attenuated total reflectance (ATR) micro-FTIR for analysis of H2O in hydrous glass. A Ge ATR accessory was used to measure evanescent wave absorption by H2O within hydrous rhyolite and other standards. Absorbance at 3450 cm−1 (representing total H2O or H2Ot) and 1630 cm−1 (molecular H2O or H2Om) showed high correlation with measured H2O in the glasses as determined by transmission FTIR spectroscopy and manometry. For rhyolite, wt%H2O=245(±9)×A3450-0.22(±0.03) and wt%H2Om=235(±11)×A1630-0.20(±0.03) where A3450 and A1630 represent the ATR absorption at the relevant infrared wavelengths. The calibration permits determination of volatiles in singly polished glass samples with spot size down to ~5 μm (for H2O-rich samples) and detection limits of ~0.1 wt% H2O. Basaltic, basaltic andesite and dacitic glasses of known H2O concentrations fall along a density-adjusted calibration, indicating that ATR is relatively insensitive to glass composition, at least for calc-alkaline glasses. The following equation allows quantification of H2O in silicate glasses that range in composition from basalt to rhyolite: wt%H2O=(ω×A3450/ρ)+b where ω = 550 ± 21, b = −0.19 ± 0.03, ρ = density, in g/cm3, and A3450 is the ATR absorbance at 3450 cm−1. The ATR micro-FTIR technique is less sensitive than transmission FTIR, but requires only a singly polished sample for quantitative results, thus minimizing time for sample preparation. Compared with specular reflectance, it is more sensitive and better suited for imaging of H2O variations in heterogeneous samples such as melt inclusions. One drawback is that the technique can damage fragile samples and we therefore recommend mounting of unknowns in epoxy prior to polishing. Our calibration should hold for any Ge ATR crystals with the same incident angle (31°). Use of a different crystal type or geometry would require measurement of several H2O-bearing standards to provide a crystal

  4. High-efficiency ytterbium-free erbium-doped all-glass double cladding silicate glass fiber for resonantly-pumped fiber lasers.

    PubMed

    Qiang, Zexuan; Geng, Jihong; Luo, Tao; Zhang, Jun; Jiang, Shibin

    2014-02-01

    A highly efficient ytterbium-free erbium-doped silicate glass fiber has been developed for high-power fiber laser applications at an eye-safe wavelength near 1.55 μm. Our preliminary experiments show that high laser efficiency can be obtained from a relatively short length of the gain fiber when resonantly pumped at 1535 nm in both core- and cladding-pumping configurations. With a core-pumping configuration as high as 75%, optical-to-optical efficiency and 4 W output power were obtained at 1560 nm from a 1 m long gain fiber. When using a cladding-pumping configuration, approximately 13 W output power with 67.7% slope efficiency was demonstrated from a piece of 2 m long fiber. The lengths of silicate-based gain fiber are much shorter than their silica-based counterparts used in other experiments, which is significantly important for high-power narrow-band and/or pulsed laser applications.

  5. Investigation of spectroscopic properties, structure and luminescence spectra of Sm3+ doped zinc bismuth silicate glasses

    NASA Astrophysics Data System (ADS)

    Pal, I.; Agarwal, A.; Sanghi, S.; Aggarwal, M. P.

    2013-01-01

    The glasses with compositions 20ZnO·(79.5 - x)Bi2O3·xSiO2·0.5Sm2O3 (10 ⩽ x ⩽ 50, mol%) have been synthesized using normal melt-quench technique. Optical absorption and fluorescence spectra of the glasses were recorded at ambient temperature. Judd-Ofelt (J-O) theory has been successfully applied to characterize the absorption and luminescence spectra of these glasses. From the measured intensities of absorption bands of these glasses, the Judd-Ofelt parameters, Ωλ (λ = 2, 4, 6) have been evaluated. The variation of Ω2 with Bi2O3 content has been attributed to changes in the asymmetry of the ligand field at the rare earth (RE) ion site (due to structural change) and to changes in RE-O covalency, whereas the variation of Ω6 is found to be strongly dependent on nephlauxetic effect. The shift of the hypersensitive band shows that the covalency of the RE-O decreases with decrease in Bi2O3 content in the host glass. Also, using J-O theory various radiative properties like spontaneous emission probability (Arad), radiative life time (τr), fluorescence branching ratio (βr) and stimulated emission cross-section (σ) for various emission bands of these glasses in the visible spectral region have been determined. A close correlation is observed between the Bi2O3 content and the spectroscopic, radiative and structural properties of the prepared glasses. The values of radiative properties indicated that 4G5/2 → 6H7/2 and 4G5/2 → 6H9/2 transitions responsible for orange luminescence might be used in the development of materials for LED's and other optical devices in the visible region.

  6. Kinetics and mechanisms of the conversion of silicate (45S5), borate, and borosilicate glasses to hydroxyapatite in dilute phosphate solutions.

    PubMed

    Huang, Wenhai; Day, Delbert E; Kittiratanapiboon, Kanisa; Rahaman, Mohamed N

    2006-07-01

    Bioactive glasses with controllable conversion rates to hydroxyapatite (HA) may provide a novel class of scaffold materials for bone tissue engineering. The objective of the present work was to comprehensively characterize the conversion of a silicate bioactive glass (45S5), a borate glass, and two intermediate borosilicate glass compositions to HA in a dilute phosphate solution at 37 degrees Celsius. The borate glass and the borosilicate glasses were derived from the 45S5 glass by fully or partially replacing the SiO(2) with B(2)O(3). Higher B(2)O(3) content produced a more rapid conversion of the glass to HA and a lower pH value of the phosphate solution. Whereas the borate glass was fully converted to HA in less than 4 days, the silicate (45S5) and borosilicate compositions were only partially converted even after 70 days, and contained residual SiO(2) in a Na-depleted core. The concentration of Na(+) in the phosphate solution increased with reaction time whereas the PO(4) (3-) concentration decreased, both reaching final limiting values at a rate that increased with the B(2)O(3) content of the glass. However, the Ca(2+) concentration in the solution remained low, below the detection limit of atomic absorption, throughout the reaction. Immersion of the glasses in a mixed solution of K(2)HPO(4) and K(2)CO(3) produced a carbonate-substituted HA but the presence of the K(2)CO(3) had little effect on the kinetics of conversion to HA. The kinetics and mechanisms of the conversion process of the four glasses to HA are compared and used to develop a model for the process.

  7. Hardness and incipient plasticity in silicate glasses: Origin of the mixed modifier effect

    NASA Astrophysics Data System (ADS)

    Kjeldsen, Jonas; Smedskjaer, Morten M.; Mauro, John C.; Yue, Yuanzheng

    2014-02-01

    The scaling of Vickers hardness (Hv) in oxide glasses with varying network modifier/modifier ratio is manifested as either a positive or negative deviation from linearity with a maximum deviation at the ratio of about 1:1. In an earlier study [J. Kjeldsen et al., J. Non-Cryst. Solids 369, 61 (2013)], we observed a minimum of Hv in CaO/MgO sodium aluminosilicate glasses at CaO/MgO = 1:1 and postulated that this minimum is linked to a maximum in plastic flow. However, the origin of this link has not been experimentally verified. In this work, we attempt to do so by exploring the links among Hv, volume recovery ratio (VR) and plastic deformation volume (VP) under indentation, glass transition temperature (Tg), Young's modulus (E), and liquid fragility index (m) in CaO/MgO and CaO/Li2O sodium aluminosilicate glasses. We confirm the negative deviations from linearity and find that the maximum deviation (i.e., the so-called mixed modifier effect) of Hv, Tg, and m is at the modifier ratio of 1:1. These deviations increase in intensity as the total modifier concentration increases. We find a strong correlation between VP and Hv for the CaO/MgO series, implying that the minimum in Hv originates primarily from an increased shear flow in the mixed modifier glasses.

  8. Effects of Aqueous Solutions on the Slow Crack Growth of Soda-Lime-Silicate Glass

    NASA Technical Reports Server (NTRS)

    Hausmann, Bronson D.; Salem, Jonathan A.

    2016-01-01

    The slow crack growth (SCG) parameters of soda-lime-silicate were measured in distilled and saltwater of various concentrations in order to determine if the presence of salt and the contaminate formation of a weak sodium film affects stress corrosion susceptibility. Past research indicates that solvents affect the rate of crack growth; however, the effects of salt have not been studied. The results indicate a small but statistically significant effect on the SCG parameters A and n at high concentrations; however, for typical engineering purposes, the effect can be ignored.

  9. The Effects of Salt Water on the Slow Crack Growth of Soda Lime Silicate Glass

    NASA Technical Reports Server (NTRS)

    Hausmann, Bronson D.; Salem, Jonathan A.

    2016-01-01

    The slow crack growth parameters of soda-lime silicate were measured in distilled and salt water of various concentrations in order to determine if stress corrosion susceptibility is affected by the presence of salt and the contaminate formation of a weak sodium film. Past research indicates that solvents effect the rate of crack growth, however, the effects of salt have not been studied. The results indicate a small but statistically significant effect on the slow crack growth parameters A and n. However, for typical engineering purposes, the effect can be ignored.

  10. 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.

  11. Strontium complexation in aqueous solutions and silicate glasses: Insights from high energy-resolution fluorescence detection X-ray spectroscopy and ab-initio modeling

    NASA Astrophysics Data System (ADS)

    Borchert, Manuela; Wilke, Max; Schmidt, Christian; Kvashnina, Kristina; Jahn, Sandro

    2014-10-01

    Although fluid-melt partitioning of trace elements like Sr, Ba, La, and Y is known to be strongly influenced by the fluid and melt chemical composition, their speciation in silicate-saturated fluids is studied insufficiently at high temperatures and pressures. Here, high energy-resolution fluorescence detection-X-ray absorption spectroscopy (HERFD-XAS) has been applied to investigate the local environment of strontium in crystalline model compounds, silicate glasses, and aqueous solutions. Acquisition of Sr K-edge HERFD-XAS spectra of aqueous solutions of SrCl2 and Sr(OH)2, and three aqueous fluids with dissolved silicate components was done in situ at temperatures to 780 °C and pressures to ∼800 MPa using hydrothermal diamond-anvil cells. Experiments were complemented by theoretical spectroscopy calculations using the finite difference method near edge structure (FDMNES) code. This approach was validated for a number of crystalline model compounds. For the silicate glasses and aqueous solutions (SrCl2 and Sr(OH)2), small clusters were examined. Either symmetric or distorted SrO6 clusters were found to describe Sr complexation in peraluminous or peralkaline glasses. However, small ‘static’ clusters seem not to be fully suited to account for the dynamically changing atomic arrangements in aqueous solutions at high temperature. Therefore, ab-initio molecular dynamics simulations were performed and used as input for modeling of X-ray absorption spectra. Analyses of these simulations indicated [SrCl(H2O)6]+ and Sr(OH)2(H2O)4 as the most likely complexes in the chloride and hydroxide solutions, respectively. Analysis of the spectra of the silicate-rich fluids shows that both melt and fluid composition strongly influence Sr complexation. For the silicate-rich fluids, formation of Sr-Cl complexes occurs at low (Na + K)/Cl and (Si + Al)/(Na + K) ratios in the fluid, whereas Sr hydroxide and possibly silicate complexes (similar to those in the silicate glass) are

  12. Characterization of radiative properties of Nd{sub 2}O{sub 3} doped phosphate and silicate glasses for solid state laser

    SciTech Connect

    Nandi, P. Shukla, R. Goswami, M.; Sudarsan, V.

    2014-04-24

    Nd{sub 2}O{sub 3} doped calcium aluminium phosphate and calcium aluminium silicate glasses prepared to compare their absorption and emission properties. Radiative lifetime of the excited state {sup 4}F{sub 3/2} derived by Judd-Ofelt theory applied to the absorption spectra. Using the photoluminescence spectrometer the steady state emission and relaxation time from excited energy level recorded under green light excitation. Phosphate glass has higher emission cross-section, higher radiative lifetime but less quantum efficiency due to non-radiative quenching through hydroxyl ions compared to silicate glass for Nd{sup 3+}:{sup 4}F{sub 3/2}→{sup 4}I{sub 9/2} emission.

  13. Z-scan study of nonlinear absorption of gold nano-particles prepared by ion implantation in various types of silicate glasses

    NASA Astrophysics Data System (ADS)

    Husinsky, W.; Ajami, A.; Nekvindova, P.; Svecova, B.; Pesicka, J.; Janecek, M.

    2012-05-01

    Metal nano-clusters composite glasses synthesized by ion implantation have been shown as promising nonlinear photonic material. In this paper, we report on the nonlinear absorption measurements of gold nano-particles implanted in four structurally different types of silicate glasses. All targets containing gold nano-particles in a layer 500 nm under the surface of the glass have been prepared by ion implantation with subsequent annealing. The targets were characterized by UV-VIS absorption spectroscopy, transmission electron microscopy (TEM) and by the Z-scan technique. The resulting nano-particles differed in size, range of particle size and shape as well as depth distribution characteristic for glasses with different chemical compositions. With the Z-scan technique, it can be shown that the nano-particles produced in silicate glasses exhibit substantial two-photon absorption (TPA). The TPA coefficient differed depending on size, shape, and depth distribution of the metal nano-clusters and the structure and composition of the glass substrates. The highest TPA coefficient (16.25 cm/GW) was found for the glass BK7 in which the largest non-spherical nano-particles have been observed in the thinnest layer.

  14. ∼2 μm fluorescence radiative dynamics and energy transfer between Er{sup 3+} and Tm{sup 3+} ions in silicate glass

    SciTech Connect

    Li, Ming; Liu, Xueqiang; Guo, Yanyan; Hao, Wei; Hu, Lili; Zhang, Junjie

    2014-03-01

    Graphical abstract: - Highlights: • A Er{sup 3+}/Tm{sup 3+} co-doped silicate glass with good thermal stability (k{sub gl} = 0.402 for STE glass) is prepared. • Efficient ∼2 μm emission is observed under 808 nm and 980 nm laser excitation. • The glass structure and spectroscopic properties are confirmed by optical absorption, IR transmission, Raman and fluorescence studies. • The content of OH groups deceases efficiently after fluorine ions are introduced. • The energy transfer coefficient from Er{sup 3+} to Tm{sup 3+} in STFE glass is 13.39 × 10{sup −40} cm{sup 6}/s. - Abstract: A Er{sup 3+}/Tm{sup 3+} co-doped silicate glass with good thermal stability is prepared by melt-quenching method. An efficient emission of ∼2 μm is observed under different selective laser excitations. The optical absorption and transmission spectra, Raman spectra, and emission spectra are tested to characterize ∼2 μm emission properties of Er{sup 3+}/Tm{sup 3+} co-doped silicate glasses and a reasonable energy transfer mechanism of ∼2 μm emission between Er{sup 3+} and Tm{sup 3+} ions is proposed. Based on the optical absorption spectra, the Judd–Ofelt parameters and radiative properties were calculated. Intense ∼2 μm emission is obtained from Er{sup 3+}/Tm{sup 3+} co-doped silicate glasses due to the efficient energy transfer from Er{sup 3+} to Tm{sup 3+} ions. The energy transfer coefficient from Er{sup 3+} to Tm{sup 3+} ions can reach as high as 13.39 × 10{sup −40} cm{sup 6}/s. In addition, the population of the OH groups is decreased and the ∼2 μm emission is effectively enhanced with fluoride introduction. The emission property, together with good thermal property, indicates that Er{sup 3+}/Tm{sup 3+} co-doped silicate glass is a potential kind of laser glass for efficient ∼2 μm laser.

  15. Optical properties and frequency upconversion fluorescence in a Tm3+ -doped alkali niobium tellurite glass

    NASA Astrophysics Data System (ADS)

    Poirier, Gadiaere; L.; Cassanjes, Fabia C.; de Araújo, Cid B.; Jerez, Vladimir A.; Ribeiro, Sidney J. L.; Messaddeq, Younes; Poulain, Marcel

    2003-03-01

    Optical spectroscopic properties of Tm3+-doped 60TeO2-10GeO2-10K2O-10Li2O-10Nb2O5 glass are reported. The absorption spectra were obtained and radiative parameters were determined using the Judd-Ofelt theory. Characteristics of excited states were studied in two sets of experiments. Excitation at 360 nm originates a relatively narrow band emission at 450 nm attributed to transition 1D2→3F4 of the Tm3+ ion with photon energy larger than the band-gap energy of the glass matrix. Excitation at 655 nm originates a frequency upconverted emission at 450 nm (1D2→3F4) and emission at 790 nm (3H4→3H6). The radiative lifetimes of levels 1D2 and 3H4 were measured and the differences between their experimental values and the theoretical predictions are understood as due to the contribution of energy transfer among Tm3+ ions.

  16. Enhanced broadband near-infrared luminescence from transparent Yb3+/Ni2+ codoped silicate glass ceramics.

    PubMed

    Wu, Botao; Zhou, Shifeng; Ruan, Jian; Qiao, Yanbo; Chen, Danping; Zhu, Congshan; Qiu, Jianrong

    2008-02-04

    The near-infrared emission intensity of Ni(2+) in Yb(3+)/Ni(2+) codoped transparent MgO-Al(2)O(3)-Ga(2)O(3)-SiO(2)-TiO(2) glass ceramics could be enhanced up to 4.4 times via energy transfer from Yb(3+) to Ni(2+) in nanocrystals. The best Yb(2)O(3) concentration was about 1.00 mol%. For the Yb(3+)/Ni(2+) codoped glass ceramic with 1.00 mol% Yb(2)O(3), a broadband near-infrared emission centered at 1265 nm with full width at half maximum of about 300 nm and lifetime of about 220 mus was observed. The energy transfer mechanism was also discussed.

  17. Spectroscopic Properties of Erbium Ions Doped in Bismuth Boro-Silicate Glasses

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Sunil; Shukla, Rajni; Sanghi, Sujata; Agarwal, Ashish; Pal, Inder

    Glasses with composition 20B2O3.(79.5-x)Bi2O3.xSiO2 (10 ≤ x ≤ 40) containing 0.5mol% of Er3+ ions were prepared by melt-quench technique. Optical absorption and fluorescence spectra were recorded at room temperature for all glass samples. Based on the Judd-Offelt theory, spectroscopic properties of Er3+ ions are discussed by changing the host glass compositions. The intensity parameters Ω2, Ω4, and Ω6 are determined by applying least square analysis method. The variation of Ω2 and Ω6 with Bi2O3 content has been attributed to changes in the asymmetry of the ligand field at the rare earth ion site and to the changes in the rare earth oxygen (RE-O) covalency. The variation of Ω4 with Bi2O3 content has been attributed to rigidity of the samples. Using these intensity parameters various radiative properties like spontaneous emission probability, branching ratio, radiative life time and stimulated emission cross-section of various emission lines have been evaluated. An intense green luminescence bands with maximum around 516 nm and 536 nm are assigned to the 2H11/2→ 4I15/2 and 4S3/2→ 4I15/2 transitions respectively has been obtained.

  18. Disorder and the extent of polymerization in calcium silicate and aluminosilicate glasses: O-17 NMR results and quantum chemical molecular orbital calculations

    NASA Astrophysics Data System (ADS)

    Lee, Sung Keun; Stebbins, Jonathan F.

    2006-08-01

    Estimation of the framework connectivity and the atomic structure of depolymerized silicate melts and glasses (NBO/T > 0) remains a difficult question in high-temperature geochemistry relevant to magmatic processes and glass science. Here, we explore the extent of disorder and the nature of polymerization in binary Ca-silicate and ternary Ca-aluminosilicate glasses with varying NBO/T (from 0 to 2.67) using O-17 NMR at two different magnetic fields of 9.4 and 14.1 T in conjunction with quantum chemical calculations. Non-random distributions among framework cations (Si and Al) are demonstrated in the variation of relative populations of oxygen sites with NBO/T. The proportion of non-bridging oxygen (NBO, Ca-O-Si) in the binary and ternary aluminosilicate glasses increases with NBO/T. While the trend is consistent with predictions from composition, the detailed fractions apparently deviate from the predicted values, suggesting further complications in the nature of polymerization. The proportion of each bridging oxygen in the glasses also varies with NBO/T. The fractions of Al-O-Si and Al-O-Al increase with increasing polymerization as CaO is replaced with Al 2O 3, while that of Si-O-Si seems to decrease, implying that activity of silica may decrease from calcium silicate to polymerized aluminosilicates (X=constant). Quantum chemical molecular orbital calculations based on density functional theory show that a silicate chain with Al-NBO (Ca-O-Al) has an energy penalty (calculated cluster energy difference) of about 108 kJ/mol compared with the cluster with Ca-O-Si, consistent with preferential depolymerization of Si-networks, reported in an earlier O-17 NMR study [Allwardt, J., Lee, S.K., Stebbins, J.F., 2003. Bonding preferences of non-bridging oxygens in calcium aluminosilicate glass: Evidence from O-17 MAS and 3QMAS NMR on calcium aluminate glass. Am. Mineral.88, 949-954]. These prominent types of non-randomness in the distributions suggest significant chemical

  19. High-precision determination of iron oxidation state in silicate glasses using XANES

    SciTech Connect

    Cottrell, Elizabeth; Kelley, Katherine A.; Lanzirotti, Antonio; Fischer, Rebecca A.

    2009-11-04

    Fe K-edge X-ray absorption near-edge structure (XANES) and Moessbauer spectra were collected on natural basaltic glasses equilibrated over a range of oxygen fugacity (QFM - 3.5 to QFM + 4.5). The basalt compositions and fO{sub 2} conditions were chosen to bracket the natural range of redox conditions expected for basalts from mid-ocean ridge, ocean island, back-arc basin, and arc settings, in order to develop a high-precision calibration for the determination of Fe{sup 3+}/{Sigma}Fe in natural basalts. The pre-edge centroid energy, corresponding to the 1s {yields} 3d transition, was determined to be the most robust proxy for Fe oxidation state, affording significant advantages compared to the use of other spectral features. A second-order polynomial models the correlation between the centroid and Fe{sup 3+}/{Sigma}Fe, yielding a precision of {+-} 0.0045 in Fe{sup 3+}/{Sigma}Fe for glasses with Fe{sup 3+}/{Sigma}Fe > 8%, which is comparable to the precision of wet chemistry. This high precision relies on a Si (311) monochromator to better define the Fe{sup 2+} and Fe{sup 3+} transitions, accurate and robust modeling of the pre-edge feature, dense fO{sub 2}-coverage and compositional appropriateness of reference glasses, and application of a non-linear drift correction. Through re-analysis of the reference glasses across three synchrotron beam sessions, we show that the quoted precision can be achieved (i.e., analyses are reproducible) across multiple synchrotron beam sessions, even when spectral collection conditions (detector parameters or sample geometry) change. Rhyolitic glasses were also analyzed and yield a higher centroid energy at a given Fe{sup 3+}/{Sigma}Fe than basalts, implying that major variations in melt structure affect the relationship between centroid position and Fe{sup 3+}/{Sigma}Fe, and that separate calibrations are needed for the determination of oxidation state in basalts and rhyolites.

  20. 2 μm emission performance in Tm3+/Er3+ codoped silicate glasses under 800 nm and 980 nm excitation

    NASA Astrophysics Data System (ADS)

    Cao, Ruijie; Lu, Yu; Tian, Ying; Huang, Feifei; Guo, Yanyan; Xu, Shiqing; Zhang, Junjie

    2017-03-01

    In this paper, mid-infrared 2 μm emission properties and energy transfer mechanism were investigated in Er3+/Tm3+ co-doped silicate glasses with optimized extra-low hydroxyl content ∂OH- (0.73 cm-1). The intensity parameters Ωt (t = 2, 4, 6) were calculated from the measured absorption spectra based on the Judd-Ofelt theory. The energy transfer efficiency from the Er3+:4I13/2 level to the Tm3+:3F4 level was calculated and reached up to 91.2% under 980 nm LD pumps and quantum efficiency is 63%. Meanwhile, the 1.85 μm band stimulated absorption and emission cross-sections of Tm3+:3F4 → 3H6 transitions were also obtained and analyzed. In addition, the measured ΔT (evaluate the glass forming ability) is as high as 297 °C, which shows that the silicate glass (SBET) possess good thermal stability. Hence, all of the present investigations indicate that the Er3+/Tm3+ co-doped silicate glasses have potential applications in 2 μm laser materials and may provide beneficial guide for investigation of population behaviors of Tm3+ ions at 2 μm emissions.

  1. The in vivo performance of an alkali-free bioactive glass for bone grafting, FastOs(®) BG, assessed with an ovine model.

    PubMed

    Cortez, Paulo P; Brito, Ana F; Kapoor, Saurabh; Correia, Ana F; Atayde, Luis M; Dias-Pereira, Patrícia; Maurício, Ana Colette; Afonso, Américo; Goel, Ashutosh; Ferreira, José M F

    2017-01-01

    Although bioactive glasses are successfully used as bone substitutes, recent studies have revealed that the high alkali content in these glasses leads to fast in vivo degradation rates that may not match the rate of new bone ingrowth. This prompted us to design and develop novel bioactive glasses that are devoid of alkali but still demonstrate high bioactivity in vitro. This article describes the in vivo performance of an alkali-free bioactive glass with the following composition (Wt %): 13.03 MgO-33.98 CaO-13.37 P2 O5 -38.84 SiO2 -0.77 CaF2 (labelled as FastOs(®) BG). An animal model was used to assess the in vivo performance of FastOs(®) BG, using 45S5 Bioglass(®) as control. The evaluation was performed through implantation of FastOs(®) BG and 45S5 Bioglass(®) , during one month, in femoral bone defects in sheep. Subcutaneous implantation of both glasses was also performed in order to assess tissue response through a standardized method. Histological and scanning electron microscopy assessment of retrieved subcutaneous and bone samples demonstrated that FastOs(®) BG is biocompatible, osteoconductive, that it can be osteointegrated, and that it is more slowly resorbed than 45S5 Bioglass(®) . These features suggest that FastOs(®) BG is a potential candidate for bone grafting. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 30-38, 2017.

  2. Small angle X-ray and neutron scattering on cadmium sulfide nanoparticles in silicate glass

    NASA Astrophysics Data System (ADS)

    Kuznetsova, Yu. V.; Rempel, A. A.; Meyer, M.; Pipich, V.; Gerth, S.; Magerl, A.

    2016-08-01

    Small angle X-ray and neutron scattering on Cd and S doped glass annealed at 600 °C shows after the first 12 h nucleation and growth of spherical CdS nanoparticles with a radius of up to 34±4 Å. After the nucleation is completed after 24 h, further growth in this amorphous environment is governed by oriented particle attachment mechanism as found for a liquid medium. Towards 48 h the particle shape has changed into spheroidal with short and long axis of 40±2 Å and 120±2 Å, respectively.

  3. Photocatalytic effect and Mössbauer study of iron titanium silicate glass prepared by sol-gel method

    NASA Astrophysics Data System (ADS)

    Takahashi, Yusuke; Kubuki, Shiro; Akiyama, Kazuhiko; Sinkó, Katalin; Homonnay, Zoltán; Kuzmann, Ernő; Nishida, Tetsuaki

    2015-06-01

    A relationship between the photocatalytic effect and the local structure of 50Fe2O3ṡ (50- x)SiO2ṡ xTiO2 glass abbreviated as 50FS xTi prepared by sol-gel method was investigated by 57Fe-Mössbauer spectroscopy (FeMS), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FT-IR) and ultraviolet-visible diffuse reflectance spectroscopy (UV-VIS). Mössbauer spectra of 50FS xTi glass before annealing showed a doublet with the isomer shift ( δ) and quadrupole splitting (Δ) of 0.41±0.01 mm s-1 and 0.75±0.02 mm s-1, indicating that Fe3+ formed FeO6 octahedra ( O h). A comparable δ of 0.36±0.02 mm s-1 and the larger Δ of 0.92±0.02 mm s-1 values were confirmed for 50FS xTi after annealed at 400 ∘ C for 3 h. These results indicates that the coordination number of iron polyhedra decreases from 6 to 4 due to annealing. UV-VIS diffuse reflectance spectra of 50FS10Ti yielded two optical band gap energies ( E g's) of 2.05 eV and 3.55 eV. This result implied that 50FS10Ti has two optical band gaps in the visible area and UV area. A bleaching test performed by 10 mL of MB aqueous solution and 40 mg of powder 50FS10Ti glass sample showed that MB absorbance decreased from 3.16 to 0.43 after UV-visible light irradiation for 2 h with the first order rate constant ( k) of . These results prove that titanium containing iron silicate glass with the composition of 50Fe2O3ṡ40SiO2ṡ10TiO2 has the UV and visible light responsive photocatalytic effect.

  4. 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.

  5. Optical absorption and near infrared emission properties of Nd 3+ ions in alkali lead tellurofluoroborate glasses

    NASA Astrophysics Data System (ADS)

    Saleem, S. A.; Jamalaiah, B. C.; Kumar, J. Suresh; Babu, A. Mohan; Moorthy, L. Rama; Jayasimhadri, M.; Jang, Kiwan; Lee, Ho Sueb; Yi, Soung Soo; Jeong, Jung Hyun

    2009-12-01

    Nd 3+ doped H 3BO 3-PbO-TeO 2-RF (R = Li, Na and K) glasses were prepared through melt quenching technique. Optical absorption and near infrared (NIR) fluorescence spectra were recorded at room temperature. The spectral intensities were analyzed in terms of the Judd-Ofelt (J-O) parameters ( Ω λ = 2, 4, 6). The covalency effect of Nd-O bond on the J-O parameters was estimated from the relative absorbance ratio (R) between 4I 9/2 → 4F 7/2 and 4I 9/2 → 4S 3/2 transitions. The effect of Nd-O covalency on the Ω4 and Ω6 intensity parameters as well as on the spontaneous emission probabilities ( AR) was discussed. Lomheim and Shazer hybrid method was applied to determine the fluorescence branching ratios ( βR) of each emission transition from the 4F 3/2 metastable level to its lower lying levels. The evaluated total radiative transition probabilities ( AT), stimulated emission cross-sections ( σe) and gain bandwidth parameters ( σe × Δ λP) were compared with the earlier reports.

  6. 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.

  7. 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.

  8. Two-point bend studies of glass fibers

    NASA Astrophysics Data System (ADS)

    Tang, Zhongzhi

    The principal objective of this research is to advance our understanding of how glass breaks. Glass, a material well known for its brittleness, has been used widely but within a frustrating limit of its strength. Generally, strength is not considered as an intrinsic property of glass, due to the difficulty of avoiding the presence of flaws on the sample surface. The fiber drawing system and two-point bending (TPB) equipment developed at Missouri S&T allow the fabrication of pristine glass fibers and failure strain measurements while minimizing the effects of strength limiting critical flaws. Several conditions affect the failure behavior of glasses, including glass composition, thermal history of melts and environmental conditions during the failure tests. Understanding how these conditions affect failure helps us understand how glass fails. In this dissertation, failure strains for many different silicate and borate glasses were measured under a variety of experimental conditions. Failure stresses for various silicate glasses were calculated using values of the nonlinear elastic moduli reported in the literature. Inert intrinsic strengths for alkali silicate glasses were related to the structure and corresponding bond strengths, and the dependence of the inert strengths on faceplate velocity is discussed. Inert failure strains were also obtained for sodium borate glasses. Up to ˜40% failure strain was measured for vitreous B2O 3. The addition of soda to boron oxide increases the dimensionality and connectivity of the glass structure and hence increases its resistance to deformation, as was observed in elasticity and brittleness measurements reported in the literature. The increase in deformation resistance produces lower failure strains, a behavior also seen for alkali silicate and aluminosilicate glasses where the reduction of non-bridging oxygen increases the structure stiffness and leads to lower inert failure strain. Fatigue effects on silicate glasses were

  9. Radiation-Induced Centers in Lead Silicate Glasses Irradiated by Stationary and Pulsed Electron Beams

    NASA Astrophysics Data System (ADS)

    Zhidkov, I. S.; Zatsepin, A. F.; Konev, S. F.; Cholakh, S. O.

    2015-08-01

    Radiation-induced centers formed in heavy flint glasses irradiated by electron beams are investigated by the methods of optical and EPR spectroscopy. It is revealed that stable and short-living optical absorption centers of close natures are formed under irradiation by fast electrons. A correlation is established between the stable optical absorption bands and the EPR signals interpreted as signals of the (Pb2+)/h+ hole centers. The shortliving color centers are formed due to short-term distortion of the O-Pb bonds, and the stable centers are formed due to the spatial separation, thermalization, and subsequent stabilization of excited electrons and holes in tails of the localized states. Irradiation by electron beams leads to a change in the spectral characteristics of the fundamental absorption edge and, in particular, of the Urbach energy that determines the degree of structural disorder.

  10. Mechanical properties of silicate glasses exposed to a low-Earth orbit

    NASA Technical Reports Server (NTRS)

    Wiedlocher, David E.; Tucker, Dennis S.; Nichols, Ron; Kinser, Donald L.

    1992-01-01

    The effects of a 5.8 year exposure to low earth orbit environment upon the mechanical properties of commercial optical fused silica, low iron soda-lime-silica, Pyrex 7740, Vycor 7913, BK-7, and the glass ceramic Zerodur were examined. Mechanical testing employed the ASTM-F-394 piston on 3-ball method in a liquid nitrogen environment. Samples were exposed on the Long Duration Exposure Facility (LDEF) in two locations. Impacts were observed on all specimens except Vycor. Weibull analysis as well as a standard statistical evaluation were conducted. The Weibull analysis revealed no differences between control samples and the two exposed samples. We thus concluded that radiation components of the Earth orbital environment did not degrade the mechanical strength of the samples examined within the limits of experimental error. The upper bound of strength degradation for meteorite impacted samples based upon statistical analysis and observation was 50 percent.

  11. Nonlinear optical properties of Cu nanoclusters by ion implantation in silicate glass

    NASA Astrophysics Data System (ADS)

    Wang, Y. H.; Wang, Y. M.; Lu, J. D.; Ji, L. L.; Zang, R. G.; Wang, R. W.

    2010-02-01

    Metal nanocluster composite glass prepared by 180 keV Cu ions into silica with dose of 1 × 10 17 ions/cm 2 has been studied. The microstructural properties of the nanoclusters were analysed by optical absorption spectra and transmission electron microscopy (TEM). Third-order nonlinear optical properties of the nanoclusters were measured at 1064 nm and 532 nm excitations using Z-scan technique. The nonlinear refraction index, nonlinear absorption coefficient, and the real and imaginary parts of the third-order nonlinear susceptibility were deduced. The mechanisms responsible for the nonlinear response were discussed. Absolute third-order nonlinear susceptibility χ of this kind of sample was determined to be 2.1 × 10 -7 esu at 532 nm and 1.2 × 10 -7 esu at 1064 nm, respectively.

  12. Passivating boron silicate glasses for co-diffused high-efficiency n-type silicon solar cell application

    SciTech Connect

    Engelhardt, Josh Frey, Alexander; Gloger, Sebastian; Hahn, Giso; Terheiden, Barbara

    2015-07-27

    Doping layers commonly have but one function: supplying the dopants to form a doped region within a substrate. This work presents B doping layers/stacks, which at the same time supply dopant atoms, passivate the B-doped crystalline Si surface sufficiently well (j{sub 0E} < 50 fA/cm{sup 2}), and show optical properties suitable for anti-reflective coating. Furthermore, these boron silicate glasses can act as a barrier against parasitic P in-diffusion during a co-diffusion step. The boron emitters diffused from the inductively coupled plasma plasma-enhanced chemical vapor-deposited B containing SiO{sub x} layers are investigated and optimized concerning passivation quality and contact properties for high-efficiency n-type solar Si cell designs. It is shown that even 10 nm thin SiO{sub x}:B films already allow for suitable emitter sheet resistance for screen-printed contacts. Furthermore, SiO{sub x}:B layers presented here allow for iV{sub OC} values of 675 mV and contact resistivity of 1 mΩcm{sup 2} for commercial Ag instead of Ag/Al pastes on the diffused boron emitter passivated with the SiO{sub x}:B layer supporting the contact formation. All of these properties can be achieved within one single B doping layer/stack.

  13. Low-loss channel optical waveguide fabrication in Nd(3+)-doped silicate glasses by femtosecond laser direct writing.

    PubMed

    Li, Shi-Ling; Han, Peigao; Shi, Meng; Yao, Yicun; Hu, Bing; Wang, Mingwei; Zhu, Xiaonong

    2011-11-21

    Optical waveguides were fabricated in neodymium-doped silicate glass by using a low-repetition-rate (1 kHz) femtosecond laser inscription. Two different types of waveguide structure are fabricated. In the first, guiding occurs in the focal spot. In the second, guiding occurs in the region between the two filaments. The near-field intensity distribution, propagation loss, index profile reconstruction, and calculation of the modal intensity distribution by the beam propagation method of these waveguides are presented. On the basis of near-field intensity distribution of the light guided through the waveguides and the propagation loss measurement, the optimum writing conditions such as the pulse energy and scan velocity were determined. The waveguide written with 2.2 µJ pulse energy and 50 µm/s scan velocity shows strong guidance at 632.8 nm, with an index contrast of 7 × 10(-4) and a propagation loss of ~0.8 dB/cm.

  14. Determination of relative sensitivity factors during secondary ion sputtering of silicate glasses by Au+, Au2+ and Au3+ ions.

    PubMed

    King, Ashley; Henkel, Torsten; Rost, Detlef; Lyon, Ian C

    2010-01-01

    In recent years, Au-cluster ions have been successfully used for organic analysis in secondary ion mass spectrometry. Cluster ions, such as Au(2)(+) and Au(3)(+), can produce secondary ion yield enhancements of up to a factor of 300 for high mass organic molecules with minimal sample damage. In this study, the potential for using Au(+), Au(2)(+) and Au(3)(+) primary ions for the analysis of inorganic samples is investigated by analyzing a range of silicate glass standards. Practical secondary ion yields for both Au(2)(+) and Au(3)(+) ions are enhanced relative to those for Au(+), consistent with their increased sputter rates. No elevation in ionization efficiency was found for the cluster primary ions. Relative sensitivity factors for major and trace elements in the standards showed no improvement in quantification with Au(2)(+) and Au(3)(+) ions over the use of Au(+) ions. Higher achievable primary ion currents for Au(+) ions than for Au(2)(+) and Au(3)(+) allow for more precise analyses of elemental abundances within inorganic samples, making them the preferred choice, in contrast to the choice of Au(2)(+) and Au(3)(+) for the analysis of organic samples. The use of delayed secondary ion extraction can also boost secondary ion signals, although there is a loss of overall sensitivity.

  15. Passivating boron silicate glasses for co-diffused high-efficiency n-type silicon solar cell application

    NASA Astrophysics Data System (ADS)

    Engelhardt, Josh; Frey, Alexander; Gloger, Sebastian; Hahn, Giso; Terheiden, Barbara

    2015-07-01

    Doping layers commonly have but one function: supplying the dopants to form a doped region within a substrate. This work presents B doping layers/stacks, which at the same time supply dopant atoms, passivate the B-doped crystalline Si surface sufficiently well (j0E < 50 fA/cm2), and show optical properties suitable for anti-reflective coating. Furthermore, these boron silicate glasses can act as a barrier against parasitic P in-diffusion during a co-diffusion step. The boron emitters diffused from the inductively coupled plasma plasma-enhanced chemical vapor-deposited B containing SiOx layers are investigated and optimized concerning passivation quality and contact properties for high-efficiency n-type solar Si cell designs. It is shown that even 10 nm thin SiOx:B films already allow for suitable emitter sheet resistance for screen-printed contacts. Furthermore, SiOx:B layers presented here allow for iVOC values of 675 mV and contact resistivity of 1 mΩcm2 for commercial Ag instead of Ag/Al pastes on the diffused boron emitter passivated with the SiOx:B layer supporting the contact formation. All of these properties can be achieved within one single B doping layer/stack.

  16. Silicate glass micro and nanospherules generated in explosive eruptions of ultrabasic magmas: Implications for the origin of pelletal lapilli

    NASA Astrophysics Data System (ADS)

    Carracedo Sánchez, M.; Sarrionandia, F.; Arostegui, J.; Gil Ibarguchi, J. I.

    2015-02-01

    The genesis of spherical ash to lapilli-sized clasts with a central phenocryst or lithic fragment, mantled by a rim of fine-grained juvenile material that includes abundant concentrically arranged prismatic crystals, is interpreted as either: (i) the result of the spinning of a magma bleb with a crystalline kernel in a fluidized system, or (ii) the accretion of small melt droplets to a previously crystallized nucleus in a gas jet. We demonstrate that the rims of pelletal lapilli within tephras of the Cabezo Segura volcano (Calatrava, Spain) are clastic and were formed by the progressive welding of juvenile crystals and silicate glass droplets, and, to a lesser extent, filaments (both melt in origin) around a large crystalline nucleus. Our results support the accretion hypothesis and offer explicit and new images of the melt droplets that were so far considered hypothetical particles. These results indicate also that nanometre-scale juvenile pyroclasts (melt droplets and crystals) can be generated in explosive eruptions of ultrabasic magmas. Those pyroclasts can be subsequently welded together inside a dense gas jet generating pelletal lapilli and ash.

  17. Enhancement and retardation of thermal boron diffusion in silicon from atmospheric pressure chemical vapor deposited boron silicate glass film

    NASA Astrophysics Data System (ADS)

    Kurachi, Ikuo; Yoshioka, Kentaro

    2014-03-01

    Thermal boron diffusion into silicon from boron silicate glass (BSG) prepared by atmospheric pressure CVD (AP-CVD) has been investigated in terms of the BSG boron concentration dependence on diffusion mechanism for N-type solar cell applications. With thermal diffusion at 950 °C in N2 for 20 min, the sheet resistance of the boron-diffused layer decreases with BSG boron concentration up to approximately 4 × 1021 cm-3 at which a boron-rich layer (BRL) is formed at the surface. However, the resistance increases with BSG boron concentration when the BSG boron concentration is higher than 4 × 1021 cm-3. It is also confirmed that the diffusion depth decreases with increasing BSG boron concentration within this BSG concentration region. To clarify this mechanism, the BSG boron concentration dependence on boron diffusivity has also been studied. From extracted diffusivities, the anomalous diffusion can be explained by silicon interstitials formed owing to kick-out by diffused boron atoms and by silicon interstitial generation-degradation due to BRL formation.

  18. Formation of luminescent and nonluminescent silver nanoparticles in silicate glasses by near-infrared femtosecond laser pulses and subsequent thermal treatment: the role of halogenides

    NASA Astrophysics Data System (ADS)

    Klyukin, Dmitry A.; Dubrovin, Victor D.; Pshenova, Alisa S.; Putilin, Sergey E.; Shakhverdov, Teimur A.; Tsypkin, Anton N.; Nikonorov, Nikolay V.; Sidorov, Alexander I.

    2016-06-01

    It is shown experimentally that the near-infrared femtosecond laser irradiation and subsequent thermal treatment of silver-containing silicate glasses result in the formation of luminescent silver molecular clusters (MCs) and silver nanoparticles (NPs). In glasses doped also with halides (mostly Br), the nonluminescent silver NPs are formed because of the presence of halogenide shells on their surfaces, whereas, in glasses with no Br ions, the luminescent silver nanoparticles provides an emission in the 600- to 750-nm range. Two possible mechanisms of luminescence of glass with silver NPs are considered: (i) luminescence of silver NPs without halogenide shell and (ii) the luminescence of silver MCs Agm (m=1 to 4) remaining even after the formation of silver NPs.

  19. Evidence for a tektosilicate structure and dominance of Fe(III) over Fe(II) in silicic volcanic glasses of the Nevada Test Site

    SciTech Connect

    Warren, R.G.

    1983-01-01

    More than 400 individual analyses have been obtained by electron microprobe for silicic glasses in 58 samples of tuff and lava from the Nevada Test Site (NTS). These samples comprise a wide range in chemical and petrographic types, including calc-alkaline and peralkaline rock types, and include most of the volcanic units of the NTS. Locations and brief petrographic descriptions are given for representative samples.

  20. NEW ACTIVE MEDIA AND ELEMENTS OF LASER SYSTEMS: Influence of short-lived color centers on the lifetime of a metastable level of neodymium in silicate glasses

    NASA Astrophysics Data System (ADS)

    Dzhibladze, M. I.; Lazarev, L. E.

    1987-11-01

    It was found that the short-lived color centers formed in neodymium-activated silicate glasses under the action of the violet part of the pump spectrum increased the lifetime of a neodymium metastable level by more than an order of magnitude in needle-shaped waveguide lasers. The highly efficient suppression of superradiance and a strong increase in the gain of the active element were due to stimulated decay of the color centers accompanying absorption of photons emitted by the neodymium.

  1. Effect of pressure on the carbon speciation in silicate glasses and melts: Insights from multi-nuclear solid-state NMR

    NASA Astrophysics Data System (ADS)

    Kim, E. J.; Fei, Y.; Lee, S. K.

    2015-12-01

    The pressure-induced structural changes in carbon-bearing silicate glasses and melts is essential to understand the changes in melt properties in the Earth interior and yield atomistic insights into the deep carbon cycle. Despite the extensive pioneering studies on carbon-bearing silicate glasses, spectroscopic and scattering studies at high pressure above ~4 GPa is limited due to the lack of suitable experimental probes. Here, we report the pressure-induced structural changes around C, Si and Al in albite and Na-trisilicate (Na2O:SiO2=1:3, NS3) glasses with varying pressure up to 8 GPa, using 27Al, 29Si and 13C solid-state high-resolution NMR. 27Al 3QMAS NMR spectra for carbon-bearing albite glasses quenched from melts at high pressure up to 6 GPa show only [4]Al environments. The FWHM of [4]Al in albite glasses increases with increasing pressure, indicating that the overall densification of albite glasses at high pressure is accompanied by an increase in the topological disorder around Al. 29Si MAS NMR spectra for NS3 glasses at high pressure up to 8 GPa show the presence of highly coordinated Si, [5,6]Si, which contributes to an increases in the total configurational disorder in the NS3 glasses with pressure. 13C MAS NMR spectra for carbon-bearing albite glasses show the presence of dominant fraction of CO2, and minor amounts of CO32-, and CO. At least three distinct carbonate species, such as [4]Si(CO3)[4]Si, [4]Si(CO3)[4]Al, and CO32- were observed. Among those species, the increase in the fraction of [4]Si(CO3)[4]Al species is most prevalent. 13C MAS NMR spectra for NS3 glasses show the presence of carbonate species. The peaks position of the carbonate species shifts to lower frequency upon compression, suggesting the pressure-induced structural distortion of CO32- in the glasses above 6 GPa. Spin-lattice (T1) relaxation time for molecular CO2 in carbon-bearing albite glasses increases with increasing pressure. T1 relaxation time for CO2 species at 6 GPa is 3

  2. Structure and disorder in iron-bearing sodium silicate glasses and melts: High-resolution 29Si and 17O solid-state NMR study

    NASA Astrophysics Data System (ADS)

    Kim, H.; Lee, S.

    2012-12-01

    Understanding of the effect of iron content on the structure (Si coordination environment and the degree of polymerization) of iron-bearing silicate melts and glasses is essential for studying their macroscopic properties and diverse geological processes in Earth's interior. Although the recent advances in high-resolution solid-state NMR techniques provide detailed structural information of a diverse iron-free oxide glasses with varying composition (e.g., Lee, P. Natl. Acad. Sci. USA., 2011, 108, 6847; Lee and Sung, Chem. Geol., 2008, 256, 326; Park and Lee, Geochim. Cosmochim. Acta, 2012, 80, 125; Lee et al., Phys. Rev., 103, 095501, 2009), their application to iron-bearing silicate glasses has a limited usefulness in resolving atomic configurations due to the effect of paramagnetic cation (i.e., Fe) on the NMR spectra. Here, we report the first ^{29}Si and ^{17}O NMR spectra for sodium-iron silicate glasses with varying iron content (Na_{2}O-Fe_{2}O_{3}-SiO_{2} glasses, up to 34.60 wt% Fe_{2}O_{3}), revealing previously unknown details of iron-induced changes in structure and disorder. While signal intensity decreases and peak width increases exponentially with increasing iron content [=Fe_{2}O_{3}/(Na_{2}O+Fe_{2}O_{3})], ^{29}Si MAS NMR spectra for sodium-iron silicate glasses present the slight peak shift and an asymmetrical peak broadening toward higher Q^{n} species with increasing iron content. This result implies an increase in the degree of polymerization with increasing iron content. Additionally, ^{29}Si spin-relaxation time (T_{1}) for the glasses decreases with increasing of iron content by several orders of magnitude. ^{17}O 3QMAS NMR spectra for the glasses show well-resolved non-bridging oxygen (NBO, Na-O-Si) and bridging oxygen (BO, Si-O-Si) even at relatively high iron content, providing the first direct experimental estimation of the degree of polymerization. In sodium-iron silicate glasses, the fraction of NBO decreases with increasing iron

  3. 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.

  4. Dynamic processes in a silicate liquid from above melting to below the glass transition.

    PubMed

    Nascimento, Marcio Luis Ferreira; Fokin, Vladimir Mihailovich; Zanotto, Edgar Dutra; Abyzov, Alexander S

    2011-11-21

    We collect and critically analyze extensive literature data, including our own, on three important kinetic processes--viscous flow, crystal nucleation, and growth--in lithium disilicate (Li(2)O·2SiO(2)) over a wide temperature range, from above T(m) to 0.98T(g) where T(g) ≈ 727 K is the calorimetric glass transition temperature and T(m) = 1307 K, which is the melting point. We found that crystal growth mediated by screw dislocations is the most likely growth mechanism in this system. We then calculated the diffusion coefficients controlling crystal growth, D(eff)(U), and completed the analyses by looking at the ionic diffusion coefficients of Li(+1), O(2-), and Si(4+) estimated from experiments and molecular dynamic simulations. These values were then employed to estimate the effective volume diffusion coefficients, D(eff)(V), resulting from their combination within a hypothetical Li(2)Si(2)O(5) "molecule". The similarity of the temperature dependencies of 1/η, where η is shear viscosity, and D(eff)(V) corroborates the validity of the Stokes-Einstein/Eyring equation (SEE) at high temperatures around T(m). Using the equality of D(eff)(V) and D(eff)(η), we estimated the jump distance λ ~ 2.70 Å from the SEE equation and showed that the values of D(eff)(U) have the same temperature dependence but exceed D(eff)(η) by about eightfold. The difference between D(eff)(η) and D(eff)(U) indicates that the former determines the process of mass transport in the bulk whereas the latter relates to the mobility of the structural units on the crystal/liquid interface. We then employed the values of η(T) reduced by eightfold to calculate the growth rates U(T). The resultant U(T) curve is consistent with experimental data until the temperature decreases to a decoupling temperature T(d)(U) ≈ 1.1-1.2T(g), when D(eff)(η) begins decrease with decreasing temperature faster than D(eff)(U). A similar decoupling occurs between D(eff)(η) and D(eff)(τ) (estimated from

  5. High Pressure Response of Siliceous Materials

    DTIC Science & Technology

    2013-02-01

    quartz, Starphire soda lime silicate glass, hydrated Starphire, BOROFLOAT borosilicate glass, an iron-containing soda lime silicate glass, opal (a hydrated... Opal (hydrated amorphous silica). .............................................................................. 10 2.7. ROBAX glass ceramic...spectrum as a function of stress for BOROFLOAT borosilicate glass. .......... 29 4.8. Raman spectrum as a function of stress for opal (hydrated

  6. Present and future of glass-ionomers and calcium-silicate cements as bioactive materials in dentistry: Biophotonics-based interfacial analyses in health and disease

    PubMed Central

    Watson, Timothy F.; Atmeh, Amre R.; Sajini, Shara; Cook, Richard J.; Festy, Frederic

    2014-01-01

    Objective Since their introduction, calcium silicate cements have primarily found use as endodontic sealers, due to long setting times. While similar in chemistry, recent variations such as constituent proportions, purities and manufacturing processes mandate a critical understanding of service behavior differences of the new coronal restorative material variants. Of particular relevance to minimally invasive philosophies is the potential for ion supply, from initial hydration to mature set in dental cements. They may be capable of supporting repair and remineralization of dentin left after decay and cavity preparation, following the concepts of ion exchange from glass ionomers. Methods This paper reviews the underlying chemistry and interactions of glass ionomer and calcium silicate cements, with dental tissues, concentrating on dentin–restoration interface reactions. We additionally demonstrate a new optical technique, based around high resolution deep tissue, two-photon fluorescence and lifetime imaging, which allows monitoring of undisturbed cement–dentin interface samples behavior over time. Results The local bioactivity of the calcium-silicate based materials has been shown to produce mineralization within the subjacent dentin substrate, extending deep within the tissues. This suggests that the local ion-rich alkaline environment may be more favorable to mineral repair and re-construction, compared with the acidic environs of comparable glass ionomer based materials. Significance The advantages of this potential re-mineralization phenomenon for minimally invasive management of carious dentin are self-evident. There is a clear need to improve the bioactivity of restorative dental materials and these calcium silicate cement systems offer exciting possibilities in realizing this goal. PMID:24113131

  7. The effect of Mg concentration in silicate glasses on CO2 solubility and solution mechanism: Implication for natural magmatic systems

    NASA Astrophysics Data System (ADS)

    Morizet, Yann; Paris, Michael; Sifré, David; Di Carlo, Ida; Gaillard, Fabrice

    2017-02-01

    Following an experimental approach conducted between 0.5 and 1.5 GPa, we investigated the change in CO2 solubility as a function of the XMg (MgO/(MgO + CaO)) for a range of silicate glasses. The synthesised CO2-bearing glasses have XMg up to 0.72, stoichiometric NBO/T (degree of polymerization) up to 2.6 corresponding to highly depolymerized compositions analogues to kimberlites. Several samples were synthesised with 17O enrichment to investigate the CO2 dissolution mechanism via the change in O species environments by NMR spectroscopy. The experimental results show that CO2 solubility increases with NBO/T in agreement with previous works. In addition, increasing XMg strongly decreases CO2 solubility: from 18 to 7 wt.% CO2 as XMg ranges from 0 to 0.6 (1.5 GPa and NBO/T ∼2). 17O NMR results demonstrate that CO2 molecules dissolve as CO32- groups showing a signal at +146 ppm for which the intensity is linearly correlated to the wt.% CO2 determined by Raman. The analysis of the oxygen environments as a function of CO2 content for Mg ONBO (+62 ppm) and Ca ONBO (+103 ppm) show that CO2 dissolves preferentially in the vicinity of Ca2+ atoms. The difference in CO2 solubility is explained by the ability for Mg2+ cations to act as a weak network former and to be present in fourfold coordination or by the stronger affinity of CO2 molecules for Ca2+ rather than for Mg2+. We show that the CO2 solubility is negatively correlated to the Melt Ionic Field Strength which reflects the variation in the affinity of CO2 molecules for one cation or another. Strongly depolymerized mantle melts, such as kimberlites, melilitites, nephelinites and basanites will exhibit lower CO2 solubility than currently assumed due to their high MgO content which must imply degassing at greater depth, potentially in the sub-lithospheric mantle.

  8. Silicate, borosilicate, and borate bioactive glass scaffolds with controllable degradation rate for bone tissue engineering applications. I. Preparation and in vitro degradation.

    PubMed

    Fu, Qiang; Rahaman, Mohamed N; Fu, Hailuo; Liu, Xin

    2010-10-01

    Bioactive glass scaffolds with a microstructure similar to that of dry human trabecular bone but with three different compositions were evaluated for potential applications in bone repair. The preparation of the scaffolds and the effect of the glass composition on the degradation and conversion of the scaffolds to a hydroxyapatite (HA)-type material in a simulated body fluid (SBF) are reported here (Part I). The in vitro response of osteogenic cells to the scaffolds and the in vivo evaluation of the scaffolds in a rat subcutaneous implantation model are described in Part II. Scaffolds (porosity = 78-82%; pore size = 100-500 microm) were prepared using a polymer foam replication technique. The glasses consisted of a silicate (13-93) composition, a borosilicate composition (designated 13-93B1), and a borate composition (13-93B3), in which one-third or all of the SiO2 content of 13-93 was replaced by B2O3, respectively. The conversion rate of the scaffolds to HA in the SBF increased markedly with the B2O3 content of the glass. Concurrently, the pH of the SBF also increased with the B2O3 content of the scaffolds. The compressive strengths of the as-prepared scaffolds (5-11 MPa) were in the upper range of values reported for trabecular bone, but they decreased markedly with immersion time in the SBF and with increasing B2O3 content of the glass. The results show that scaffolds with a wide range of bioactivity and degradation rate can be achieved by replacing varying amounts of SiO(2) in silicate bioactive glass with B2O3.

  9. The Partial Molar Volume and Thermal Expansivity of Fe2O3 in Alkali Silicate Liquids: Evidence for the Average Coordination of Fe3+

    NASA Astrophysics Data System (ADS)

    Liu, Q.; Lange, R.

    2003-12-01

    Ferric iron is an important component in magmatic liquids, especially in those formed at subduction zones. Although it has long been known that Fe3+ occurs in four-, five- and six-fold coordination in crystalline compounds, only recently have all three Fe3+ coordination sites been confirmed in silicate glasses utilizing XANES spectroscopy at the Fe K-edge (Farges et al., 2003). Because the density of a magmatic liquid is largely determined by the geometrical packing of its network-forming cations (e.g., Si4+, Al3+, Ti4+, and Fe3+), the capacity of Fe3+ to undergo composition-induced coordination change affects the partial molar volume of the Fe2O3 component, which must be known to calculate how the ferric-ferrous ratio in magmatic liquids changes with pressure. Previous work has shown that the partial molar volume of Fe2O3 (VFe2O3) varies between calcic vs. sodic silicate melts (Mo et al., 1982; Dingwell and Brearley, 1988; Dingwell et al., 1988). The purpose of this study is to extend the data set in order to search for systematic variations in VFe2O3 with melt composition. High temperature (867-1534° C) density measurements were performed on eleven liquids in the Na2O-Fe2O3-FeO-SiO2 (NFS) system and five liquids in the K2O-Fe2O3-FeO-SiO2 (KFS) system using Pt double-bob Archimedean method. The ferric-ferrous ratio in the sodic and potassic liquids at each temperature of density measurement were calculated from the experimentally calibrated models of Lange and Carmichael (1989) and Tangeman et al. (2001) respectively. Compositions range (in mol%) from 4-18 Fe2O3, 0-3 FeO, 12-39 Na2O, 25-37 K2O, and 43-78 SiO2. Our density data are consistent with those of Dingwell et al. (1988) on similar sodic liquids. Our results indicate that for all five KFS liquids and for eight of eleven NFS liquids, the partial molar volume of the Fe2O3 component is a constant (41.57 ñ 0.14 cm3/mol) and exhibits zero thermal expansivity (similar to that for the SiO2 component). This value

  10. The influence of the conditions of ion exchange in CuSO4:Na2SO4 melt on the optical properties of surface layers of silicate glass

    NASA Astrophysics Data System (ADS)

    Demichev, I. A.; Sidorov, A. I.; Nikonorov, N. V.

    2015-08-01

    The influence of the temperature and duration of ion exchange in BK7 silicate glass in CuSO4:Na2SO4 melt on the optical properties of the glass surface layers has been investigated. It is shown that ion exchange occurs from the melt according to the Cu2+ ↔ 2Na+ scheme. Cu2+ ions penetrate the sample to a depth of about 1 µm. Reduction of Cu2+ ions near the glass surface gives rise to the Cu+ ↔ Na+ ion exchange in the glass. Measurements of refractive index profiles in the glass sample subjected to ion exchange have revealed the formation of two waveguides in the sample: near the surface and at a depth of more than 3 µm; the second waveguide is formed by Cu+ ions. It is shown that relatively low temperatures and short durations of ion exchange lead to the formation of copper molecular clusters Cu n in glass. An increase of ion exchange temperature and duration leads to decomposition of molecular clusters with formation of Cu2+ ions.

  11. Effect of aluminum on the formation of silver metal quantum dots in sol-gel derived alumino-silicate glass film.

    PubMed

    Kim, Bok Hyeon; Son, Dong Hoon; Ju, Seongmin; Jeong, Chaehwan; Boo, Seongjae; Kim, Cheol Jin; Hanl, Won-Taek

    2006-11-01

    The effect of aluminum incorporation on silver metal quantum dots formation in the alumino-silicate glass film processed by sol-gel process was investigated. The sol-gel derived glass was coated onto the silica glass plate by spin coating with the mixture solution of tetraethyl orthosilicate (TEOS), C2H5OH, H2O, AgNO3, Al(NO3)3. 39H2O, and HNO3 with the molar ratios of Ag/Si = 0.12 and Al/Si varying from 0 to 0.12. The formation of the silver metal quantum dots was confirmed by the measurements of the UV/VIS optical spectra, the X-ray diffraction patterns, and the transmission electron microscope images. While the radius of silver metal quantum dots increased with the increase of aluminum concentration, the concentration of the silver metal quantum dots decreased. The formation of the silver metal quantum dots was found strongly suppressed by incorporation of aluminum ions in the glass. The change in the glass structure due to the aluminum incorporation was investigated by the analysis of the Raman spectra. The silver ions in the glass contributed to form stable (Al:Ag)O4 tetrahedra by pairing with aluminum ions and thus clustering of silver metal quantum dots was hindered.

  12. Reconstructing Final H2O Contents of Hydrated Rhyolitic Glasses: Insights into H2O Degassing and Eruptive Style of Silicic Submarine Volcanoes

    NASA Astrophysics Data System (ADS)

    McIntosh, I. M.; Nichols, A. R.; Tani, K.; Llewellin, E. W.

    2015-12-01

    H2O degassing influences the evolution of magma viscosity and vesicularity during ascent through the crust, and ultimately the eruptive style. Investigating H2O degassing requires data on both initial and final H2O contents. Initial H2O contents are revealed by melt inclusion data, while final H2O contents are found from dissolved H2O contents of volcanic glass. However volcanic glasses, particularly of silicic composition, are susceptible to secondary hydration i.e. the addition of H2O from the surrounding environment at ambient temperature during the time following pyroclast deposition. Obtaining meaningful final H2O data therefore requires distinguishing between the original final dissolved H2O content and the H2O added subsequently during hydration. Since H2O added during hydration is added as molecular H2O (H2Om), and the species interconversion between H2Om and hydroxyl (OH) species is negligible at ambient temperature, the final OH content of the glass remains unaltered during hydration. By using H2O speciation models to find the original H2Om content that would correspond to the measured OH content of the glass, the original total H2O (H2Ot) content of the glass prior to hydration can be reconstructed. These H2O speciation data are obtained using FTIR spectroscopy. In many cases, particularly where vesicular glasses necessitate thin wafers, OH cannot be measured directly and instead is calculated indirectly as OH = H2Ot - H2Om. Here we demonstrate the importance of using a speciation-dependent H2Ot molar absorptivity coefficient to obtain accurate H2Ot and H2O speciation data and outline a methodology for calculating such a coefficient for rhyolite glasses, with application to hydrated silicic pumice from submarine volcanoes in the Japanese Izu-Bonin Arc. Although hydrated pumice from Kurose Nishi and Oomurodashi now contain ~1.0 - 2.5 wt% H2Ot, their pre-hydration final H2O contents were typically ~0.3 - 0.4 wt% H2Ot. Furthermore, we show that pre

  13. Investigation of the local structure of Cu2+ ions doped in alkali lead tetraborate glasses by their electron paramagnetic resonance and optical spectra

    NASA Astrophysics Data System (ADS)

    Wu, Ying; Chen, Zhi

    2014-06-01

    The local structure of the Cu2+ centers in alkali lead tetraborate glasses was theoretically studied based on the optical spectra data and high-order perturbation formulas of the spin Hamiltonian parameters (electron paramagnetic resonance g factors g∥, g⊥ and hyperfine structure constants A∥, A⊥) for a 3d9 ion in a tetragonally elongated octahedron. In these formulas, the relative axial elongation of the ligand O2- octahedron around the Cu2+ due to the Jahn-Teller effect is taken into account by considering the contributions to the g factors from the tetragonal distortion which is characterized by the tetragonal crystal-field parameters Ds and Dt. From the calculations, the ligand O2- octahedral around Cu2+ is determined to suffer about 19.2% relative elongation along the C4 axis of the alkali lead tetraborate glass system, and a negative sign for A∥ and a positive sign for A⊥ for these Cu2+ centers are suggested in the discussion.

  14. Energy transfer characteristics of silicate glass doped with Er3+, Tm3+, and Ho3+ for ˜2 μm emission

    NASA Astrophysics Data System (ADS)

    Li, Ming; Liu, Xueqiang; Guo, Yanyan; Hu, Lili; Zhang, Junjie

    2013-12-01

    A Er3+/Tm3+/Ho3+ tri-doped silicate glass with good thermal stability is prepared by melt-quenching method. Efficient ˜2 μm emission is observed under 808 nm laser excitation. It is found that the 2.0 μm emission of Ho3+ can be enhanced under the excitation at 808 nm by incorporating Er3+ and Tm3+. Based on the measurement of absorption spectra, the Judd-Ofelt intensity parameters, radiation emission probability, and branching ratio are calculated to evaluate the spectroscopic properties simultaneously. The maximum value of emission cross section of Ho3+ is 3.54 × 10-21 cm2 at 2008 nm. Additionally, the phonon assistance and the micro-parameters in the energy transfer process are quantitatively analyzed by using Dexter model. The energy transfer coefficient from Tm3+ to Ho3+ can reach as high as 21.44 × 10-40 cm6/s, respectively. The emission property together with good thermal property indicates that Er3+/Tm3+/Ho3+ tri-doped silicate glass is a potential kind of laser glass for efficient 2 μm laser.

  15. Energy transfer characteristics of silicate glass doped with Er{sup 3+}, Tm{sup 3+}, and Ho{sup 3+} for ∼2 μm emission

    SciTech Connect

    Li, Ming; Liu, Xueqiang; Guo, Yanyan; Hu, Lili; Zhang, Junjie

    2013-12-28

    A Er{sup 3+}/Tm{sup 3+}/Ho{sup 3+} tri-doped silicate glass with good thermal stability is prepared by melt-quenching method. Efficient ∼2 μm emission is observed under 808 nm laser excitation. It is found that the 2.0 μm emission of Ho{sup 3+} can be enhanced under the excitation at 808 nm by incorporating Er{sup 3+} and Tm{sup 3+}. Based on the measurement of absorption spectra, the Judd–Ofelt intensity parameters, radiation emission probability, and branching ratio are calculated to evaluate the spectroscopic properties simultaneously. The maximum value of emission cross section of Ho{sup 3+} is 3.54 × 10{sup −21} cm{sup 2} at 2008 nm. Additionally, the phonon assistance and the micro-parameters in the energy transfer process are quantitatively analyzed by using Dexter model. The energy transfer coefficient from Tm{sup 3+} to Ho{sup 3+} can reach as high as 21.44 × 10{sup −40} cm{sup 6}/s, respectively. The emission property together with good thermal property indicates that Er{sup 3+}/Tm{sup 3+}/Ho{sup 3+} tri-doped silicate glass is a potential kind of laser glass for efficient 2 μm laser.

  16. Silicate, borosilicate, and borate bioactive glass scaffolds with controllable degradation rate for bone tissue engineering applications. II. In vitro and in vivo biological evaluation.

    PubMed

    Fu, Qiang; Rahaman, Mohamed N; Bal, B Sonny; Bonewald, Lynda F; Kuroki, Keiichi; Brown, Roger F

    2010-10-01

    In Part I, the in vitro degradation of bioactivAR52115e glass scaffolds with a microstructure similar to that of human trabecular bone, but with three different compositions, was investigated as a function of immersion time in a simulated body fluid. The glasses consisted of a silicate (13-93) composition, a borosilicate composition (designated 13-93B1), and a borate composition (13-93B3), in which one-third or all of the SiO2 content of 13-93 was replaced by B2O3, respectively. This work is an extension of Part I, to investigate the effect of the glass composition on the in vitro response of osteogenic MLO-A5 cells to these scaffolds, and on the ability of the scaffolds to support tissue infiltration in a rat subcutaneous implantation model. The results of assays for cell viability and alkaline phosphatase activity showed that the slower degrading silicate 13-93 and borosilicate 13-93B1 scaffolds were far better than the borate 13-93B3 scaffolds in supporting cell proliferation and function. However, all three groups of scaffolds showed the ability to support tissue infiltration in vivo after implantation for 6 weeks. The results indicate that the required bioactivity and degradation rate may be achieved by substituting an appropriate amount of SiO2 in 13-93 glass with B2O3, and that these trabecular glass scaffolds could serve as substrates for the repair and regeneration of contained bone defects.

  17. Quartz and feldspar glasses produced by natural and experimental shock.

    NASA Technical Reports Server (NTRS)

    Stoeffler, D.; Hornemann, U.

    1972-01-01

    Refractive index, density, and infrared absorption studies of naturally and experimentally shocked-produced glasses formed from quartz, plagioclase, and alkali-feldspar confirm the existence of two main groups of amorphous forms of the framework silicates: solid-state and liquid-state glasses. These were apparently formed as metastable release products of high-pressure-phases above and below the glass transition temperatures. Solid-state glasses exhibit a series of structural states with increasing disorder caused by increasing shock pressures and temperatures. They gradually merge into the structural state of fused minerals similar to that of synthetic glasses quenched from a melt. Shock-fused alkali feldspars can, however, be distinguished from their laboratory-fused counterparts by infrared absorption and by higher density.

  18. 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.

  19. Spectroscopic properties of Eu3+, Dy3+ and Tb3+ ions in lead silicate glasses obtained by the conventional high-temperature melt-quenching technique

    NASA Astrophysics Data System (ADS)

    Żur, L.; Janek, J.; Sołtys, M.; Pisarska, J.; Pisarski, W. A.

    2013-11-01

    The luminescence properties of selected rare-earth ions in lead silicate glasses have been studied. Europium, dysprosium and terbium ions were chosen as active dopants. Based on excitation and emission measurements as well as luminescence decay analysis, some spectroscopic parameters for these lanthanide ions were determined. In particular, the intensity ratios R/O (Eu3+), Y/B (Dy3+) and G/B (Tb3+) were calculated. Luminescence lifetimes for the 5D0 state of Eu3+ ions, the 4F9/2 state of Dy3+ ions and the 5D4 state of Tb3+ ions were also determined.

  20. An evaluation of the processing conditions, structure, and properties (biaxial flexural strength and antibacterial efficacy) of sintered strontium-zinc-silicate glass ceramics.

    PubMed

    Looney, Mark; Shea, Helen O'; Gunn, Lynda; Crowley, Dolores; Boyd, Daniel

    2013-05-01

    The use of artificial bone grafts has increased in order to satisfy a growing demand for bone replacement materials. Initial mechanical stability of synthetic bone grafts is very advantageous for certain clinical applications. Coupled with the advantage of mechanical strength, a material with inherent antibacterial properties would be very beneficial. A series of strontium-doped zinc silicate (Ca-Sr-Na-Zn-Si) glass ceramics have been characterized in terms of their crystalline structure, biaxial flexural strength and antibacterial efficacy based on the identification of optimum sintering conditions. All three glass ceramics, namely, BT110, BT111, and BT112 were found to be fully crystalline, with BT111 and BT112 comprising of biocompatible crystalline phases. The biaxial flexural strengths of the three glass ceramics ranged from 70 to 149 MPa and were shown to be superior to those of clinically established ceramics in dry conditions and following incubation in simulated physiological conditions. The bacteriostatic effect for each glass ceramic was also established, where BT112 showed an inhibitory effect against three of the most common bacteria found at implantation sites, namely, Enterococcus faecalis, methicillin-resistant Staphylococcus aureus (MRSA), and Pseudomonas aeruginosa. The results of the evaluation suggest that the materials studied offer advantages over current clinical materials and indicate the potential suitability of the glass ceramics as therapeutic bone grafts.

  1. High Pressure Response of Siliceous Materials

    DTIC Science & Technology

    2013-02-01

    iron-containing soda lime silicate glass, opal (a hydrated silicate glass), ROBAX glass ceramic, and others were single crystal (α-quartz) and...10 2.6. Opal (hydrated amorphous silica...Raman spectrum as a function of stress for opal (hydrated silica) glass. ................... 29 4.9. Raman spectrum as a function of stress for

  2. Femtosecond laser-induced modification of potassium-magnesium silicate glasses: An analysis of structural changes by near edge x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Seuthe, T.; Höfner, M.; Reinhardt, F.; Tsai, W. J.; Bonse, J.; Eberstein, M.; Eichler, H. J.; Grehn, M.

    2012-05-01

    The effects of femtosecond laser pulse irradiation on the glass structure of alkaline silicate glasses were investigated by x-ray absorption near edge structure spectroscopy using the beamline of the Physikalisch-Technische Bundesanstalt at the electron synchrotron BESSY II in Berlin (Germany) by analyzing the magnesium K-edge absorption peak for different laser fluences. The application of fluences above the material modification threshold (2.1 J/cm2) leads to a characteristic shift of ˜1.0 eV in the K-edge revealing a reduced (˜3%) mean magnesium bond length to the ligated oxygen ions (Mg-O) along with a reduced average coordination number of the Mg ions.

  3. Compositional dependence of the 1.8 {mu}m emission properties of Tm{sup 3+} ions in silicate glass

    SciTech Connect

    Wang Xin; Fan Sijun; Li Kefeng; Zhang Lei; Wang Shikai; Hu Lili

    2012-11-15

    The compositional dependence of the 1.8 {mu}m emission properties of Tm{sup 3+} ion-doped lead silicate glasses is investigated. Judd-Ofelt parameters are calculated and their variation with different glass modifier ions is obtained. The Judd-Ofelt parameters increase with decreased modifier ionic radius. A large spontaneous emission probability and a large emission cross-section are found to be related with the strength of the modifier ion. Fluorescence spectra are analyzed using rate equations and compared with recorded data. The results are very close, indicating the reliability of this method. Non-radiative probability is deduced by fitting the fluorescence decay curve; it becomes smaller with increased ionic field strength. Energy transfer processes are studied using the extended overlap integral method.

  4. Study of structural and spectroscopic behavior of Sm3+ ions in lead-zinc borate glasses containing alkali metal ions

    NASA Astrophysics Data System (ADS)

    Sasi Kumar, M. V.; Babu, S.; Rajeswara Reddy, B.; Ratnakaram, Y. C.

    2017-02-01

    High luminescence behavior of rare earth inorganic glasses have a variety of uses in the industry. In the past few decades, rare earth ions with characteristic photonics applications are being hosted by heavy metal oxide glasses. Among the rare earth ions Sm3+ ion has features which make it apt for high density optical storage. The authors of the paper have experimented to synthesize Sm3+ doped glasses. In this regard a new series of borate glasses doped with 1 mol% Sm3+ ion are developed by using melt-quenching technique. XRD, FTIR, optical absorption, luminescence techniques are used to study the various characteristics of Sm3+ ion in the present glass matrices. The XRD spectra confirms the amorphous nature of glasses. Further, the researchers have used differential thermal analysis to study the glass transition temperature. The structural groups in the prepared glasses are studied using Fourier transform infrared spectra. From the measurement of its optical absorption, three phenomenological Judd-Ofelt intensity parameters (Ω2, Ω4 and Ω6) have been computed. Based on these Judd-Ofelt intensity parameters, radiative properties such as radiative probabilities (Arad), branching ratios (β), and radiative life time (τR) are calculated. The excitation spectra of Sm3+ doped lithium heavy metal borate glass matrix is recorded under the emission wavelength of 600 nm. The emission spectra are recorded under 404 nm excitation wavelength. From various emission transitions, 4G5/2 → 6H7/2 and 4G5/2 → 6H9/2 bands could be of interest for various applications. The decay profiles of 4G5/2 level exhibit single exponential nature in all the prepared glass matrices. The potassium glass matrix exhibits higher quantum efficiency than the other glass matrices. Finally, by going through these several spectroscopic characterizations, it is concluded that the prepared Sm3+ doped lead-zinc borate glasses might be useful for visible light applications.

  5. Effect of Er{sub 2}O{sub 3} dopant on electrical and optical properties of potassium sodium niobate silicate glass-ceramics

    SciTech Connect

    Yongsiri, Ploypailin; Sirisoonthorn, Somnuk; Pengpat, Kamonpan

    2015-09-15

    Highlights: • The KNN–SiO{sub 2} doped Er{sub 2}O{sub 3} glass-ceramics was prepared by incorporation method. • High dielectric constant (458.41 at 100 kHz) and low loss (0.0005) could be obtained. • TEM and SEM confirmed the existence of KNN crystals embedded in glass matrix. • The Er{sub 2}O{sub 3} dopant causes insignificant effect on modifying E{sub g} value. - Abstract: In this study, transparent glass-ceramics from potassium sodium niobate (KNN)-silicate glass system doped with erbium oxide (Er{sub 2}O{sub 3}) were successfully prepared by incorporation method. KNN was added in glass batches as heterogeneous nucleating agent. The KNN powder was mixed with SiO{sub 2} and Er{sub 2}O{sub 3} dopant with KNN and Er{sub 2}O{sub 3} content varied between 70–80 and 0.5–1.0 mol%, respectively. Each batch was subsequently melted at 1300 °C for 15 min in a platinum crucible using an electric furnace. The quenched glasses were then subjected to heat treatment at various temperatures for 4 h. XRD results showed that the prepared glass ceramics contained crystals of KNN solid solution. In contrary, dielectric constant (ϵ{sub r}) and dielectric loss (tan δ) were found to increase with increasing heat treatment temperature. Additionally, optical properties such as absorbance and energy band gap have been investigated.

  6. Characterization by combined optical and FT infrared spectra of 3d-transition metal ions doped-bismuth silicate glasses and effects of gamma irradiation.

    PubMed

    ElBatal, F H; Abdelghany, A M; ElBatal, H A

    2014-03-25

    Optical and infrared absorption spectral measurements were carried out for binary bismuth silicate glass and other derived prepared samples with the same composition and containing additional 0.2% of one of 3d transition metal oxides. The same combined spectroscopic properties were also measured after subjecting the prepared glasses to a gamma dose of 8 Mrad. The experimental optical spectra reveal strong UV-near visible absorption bands from the base and extended to all TMs-doped samples and these specific extended and strong UV-near visible absorption bands are related to the contributions of absorption from both trace iron (Fe(3+)) ions present as contaminated impurities within the raw materials and from absorption of main constituent trivalent bismuth (Bi(3+)) ions. The strong UV-near visible absorption bands are observed to suppress any further UV bands from TM ions. The studied glasses show obvious resistant to gamma irradiation and only small changes are observed upon gamma irradiation. This observed shielding behavior is related to the presence of high Bi(3+) ions with heavy mass causing the observed stability of the optical absorption. Infrared absorption spectra of the studied glasses reveal characteristic vibrational bands due to both modes from silicate network and the sharing of Bi-O linkages and the presence of TMs in the doping level (0.2%) causes no distinct changes within the number or position of the vibrational modes. The presence of high Bi2O3 content (70 mol%) appears to cause stability of the structural building units towards gamma irradiation as revealed by FTIR measurements.

  7. 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.

  8. Mechanisms and kinetics of short pulse laser-induced destruction of silver-containing nanoparticles in multicomponent silicate photo-thermo-refractive glass.

    PubMed

    Lumeau, Julien; Glebov, Leonid B

    2014-11-01

    Photo-thermo-refractive (PTR) glass is a photosensitive multi-component silicate glass that is commercially used for the recording of volume holographic elements and finds many applications in advanced laser systems. Refractive index decrement in this glass is observed after UV exposure followed by thermal development. This procedure also causes the appearance of Ag-containing particles that can then be optically bleached by using the second harmonic of a Nd:YAG laser. Despite the broad usage of this method, its mechanisms are still unclear. In this paper, a systematic study of the short pulse laser-induced destruction of Ag-containing particles' kinetics versus incident energy per pulse and dosage is presented. We show that no bleaching of Ag-containing particles occurs for an energy density in laser pulses below 0.1  J/cm2 while above 1  J/cm2, the efficiency of bleaching saturates. Efficiency of bleaching depends on the type of particles to be bleached (Ag, AgBr…). Using a simple model of short pulse laser interaction with nanoparticles embedded in glass, the temperature of the Ag-containing particles reached during the laser interaction is shown to be large enough to produce complete dissipation of these particles which is expected to be the main mechanism of short pulse laser-induced destruction of Ag-containing particles.

  9. Optical Properties of K2O-Li2O-WO3-B2O3 Glasses: Evidence of Mixed Alkali Effect

    NASA Astrophysics Data System (ADS)

    Edukondalu, Avula; Sripathi, T.; Kareem Ahmmad, Shaik; Rahman, Syed; Sivakumar, K.

    2017-02-01

    Glass with compositions xK2O-(30 - x)Li2O-10WO3-60B2O3 for 0 ≤ x ≤ 30 mol.% have been prepared using the normal melt quenching technique. The optical reflection and absorption spectra were recorded at room temperature in the wavelength range 300-800 nm. From the absorption edge studies, the values of the optical band gap ( E opt) and Urbach energy (Δ E) have been evaluated. The values of E opt and Δ E vary non-linearly with composition parameter, showing the mixed alkali effect. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple Di-Domenico model.

  10. Density and compressibility of the molten lunar picritic glasses: Implications for the roles of Ti and Fe in the structures of silicate melts

    NASA Astrophysics Data System (ADS)

    Vander Kaaden, Kathleen E.; Agee, Carl B.; McCubbin, Francis M.

    2015-01-01

    The density and compressibility of four synthetic molten lunar picritic glasses was investigated from 0 to 10 GPa and 1748 to 2473 K. The picritic glasses were collected from the lunar surface during the Apollo missions, and they are hypothesized to have rapidly quenched as glass beads during pyroclastic fire fountain eruptions. The specific melt compositions investigated in the present study are the Apollo 15 green glass Type C (A15C, TiO2 = 0.26 wt%), the Apollo 14 yellow glass (A14Y, TiO2 = 4.58 wt%), the Apollo 17 orange glass 74220-type (A17O TiO2 = 9.12 wt%), and the Apollo 14 black glass (A14B, TiO2 = 16.40 wt%). These glasses are reported to represent primary unfractionated melts, making them a prime candidate for experimental studies into lunar basalt density and compressibility during partial melting of the lunar mantle. Sink-float experiments were conducted on the synthetic molten lunar glass compositions using a piston-cylinder apparatus (P < 2 GPa) and a Walker-style multi-anvil device (P > 2.5 GPa) in order to bracket the density of the melts. New sink-float data are reported for A15C, A14Y, and A17O, which are combined with previously published density and compressibility data on A15C, A17O, and A14B. Although the Ti-rich liquids are highly compressible at lower pressures, they become nearly incompressible at much higher pressures when compared to the molten low-Ti glasses. Consequently, the melts with the most TiO2 (A14B) are the least dense at higher pressures, a reversal of what is seen at lower pressures. This change in density and compressibility is attributed to changes in coordination of Ti and Fe in the silicate melt structure. As Ti4+ abundances in the silicate melt increase, predominantly [IV]Ti4+ and [IV]Fe2+ change to [VI]Ti4+ and [VI]Fe2+ in the melt structure. All of the data from the present study were used to calculate a Birch-Murnaghan equation-of-state (BM-EOS) for each melt composition. The BM-EOS model for each composition was

  11. Alteration layer formation of Ca- and Zn-oxide bearing alkali borosilicate glasses for immobilisation of UK high level waste: A vapour hydration study

    NASA Astrophysics Data System (ADS)

    Cassingham, N. J.; Corkhill, C. L.; Stennett, M. C.; Hand, R. J.; Hyatt, N. C.

    2016-10-01

    The UK high level nuclear waste glass modified with CaO/ZnO was investigated using the vapour phase hydration test, performed at 200 °C, with the aim of understanding the impact of the modification on the chemical composition and microstructure of the alteration layer. Experiments were undertaken on non-modified and CaO/ZnO-modified base glass, with or without 25 wt% of simulant Magnox waste calcine. The modification resulted in a dramatic reduction in gel layer thickness and also a reduction in the reaction rate, from 3.4 ± 0.3 g m-2 d-1 without CaO/ZnO modification to 0.9 ± 0.1 g m-2 d-1 with CaO/ZnO. The precipitated phase assemblage for the CaO/ZnO-modified compositions was identified as hydrated Ca- and Zn-bearing silicate phases, which were absent from the non-modified counterpart. These results are in agreement with other recent studies showing the beneficial effects of ZnO additions on glass durability.

  12. 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)

  13. Conversion of melt-derived microfibrous borate (13-93B3) and silicate (45S5) bioactive glass in a simulated body fluid.

    PubMed

    Liu, Xin; Rahaman, Mohamed N; Day, Delbert E

    2013-03-01

    Microfibrous bioactive glasses are showing a considerable capacity to heal soft tissue wounds, but little information is available on the mechanism of healing. In the present study, the conversion of microfibrous borate bioactive glass (diameter = 0.2-5 μm) with the composition designated 13-93B3 (5.5 Na2O, 11.1 K2O, 4.6 MgO, 18.5 CaO, 3.7 P2O5, 56.6 B2O3 wt%) was evaluated in vitro as a function of immersion time in a simulated body fluid (SBF) at 37 °C using structural and chemical techniques. Silicate 45S5glass microfibers (45 SiO2, 24.5 Na2O, 24.5 CaO, 6 P2O5 wt%) were also studied for comparison. Microfibrous 13-93B3 glass degraded almost completely and converted to a calcium phosphate material within 7-14 days in SBF, whereas >85 % of the silica remained in the 45S5 microfibers, forming a silica gel phase. An amorphous calcium phosphate (ACP) product that formed on the 13-93B3 microfibers crystallized at a slower rate to hydroxyapatite (HA) when compared to the ACP that formed on the 45S5 fibers. For immersion times >3 days, the 13-93B3 fibers released a higher concentration of Ca into the SBF than the 45S5 fibers. The fast and more complete degradation, slow crystallization of the ACP product, and higher concentration of dissolved Ca in SBF could contribute to the capacity of the microfibrous borate 13-93B3 glass to heal soft tissue wounds.

  14. Radiative parameters for multi-channel visible and near-infrared emission transitions of Sm3+ in heavy-metal-silicate glasses

    NASA Astrophysics Data System (ADS)

    Yang, Jie; Zhai, Bin; Zhao, Xin; Wang, Zhiqiang; Lin, Hai

    2013-05-01

    Multi-channel visible and near-infrared (NIR) emission transitions originating from 4G5/2 emitting state of Sm3+ in cadmium-aluminum-silicate (CAS) glasses with maximum-phonon-energy of ˜980 cm-1 have been investigated. Based on the measured absorption spectrum, the Judd-Ofelt parameters Ωt (t=2, 4, 6) are derived to be 2.87×10-20, 3.34×10-20 and 1.86×10-20 cm2, respectively. From the evaluated Judd-Ofelt parameters, the radiative parameters such as spontaneous emission probabilities (Arad), branching ratios (β), and radiative lifetime (τrad) are obtained from the 4G5/2 excited level to different lower energy levels. The efficient visible and NIR transition emissions have been observed in the Sm3+ doped CAS glasses, and the maximum stimulated emission cross-sections (σe-max) corresponding to emission peaks are calculated and demonstrated to lay in the same order of magnitude. The quantum efficiency of 4G5/2 level of Sm3+ has been derived to be 60%. Investigations on multi-channel radiative transition emissions originated from 4G5/2 level of Sm3+ in CAS glasses expose its potential applications in tunable laser, medical light source and NIR optoelectronic devices.

  15. Enamel and Dentin Surface Finishing Influence on the Roughness and Microshear Bond Strength of a Lithium Silicate Glass-Ceramic for Laminate Veneers

    PubMed Central

    Gonzaga, Carla Castiglia; Bravo, Ruth Peggy; Pavelski, Thiago Vinícius; Garcia, Paula Pontes; Correr, Gisele Maria; Leonardi, Denise Piotto; da Cunha, Leonardo Fernandes; Furuse, Adilson Yoshio

    2015-01-01

    Objectives. This study evaluated the influence of cavity surface finishing with diamond burs of different grit mounted on high-speed turbine and ultrasound on the roughness and microshear bond strength (MBS) of a lithium silicate glass-ceramic to enamel and dentin. Methods. Enamel and dentin specimens were divided into seven groups, according to the type of surface finishing: 1200-grit sandpaper (control), two different brands of medium-grit and fine-grit diamond burs in a high-speed turbine; medium-grit and fine-grit CVD (chemical vapor deposition) tips in an ultrasonic device. Roughness parameters (n = 5) and MSBS to a glass-ceramic (n = 10) were determined. Data were analyzed using ANOVA and Tukey's test (α = 5%). Results. Control group showed lower mean roughness readings and groups that used medium-grit diamond burs showed the highest mean roughness values. Regarding MSBS, there was no statistical difference when comparing the groups gritted with the same brand of medium- and fine-grit burs and tips. Conclusions. Cavity surface finishing influenced the roughness parameters and MSBS of a glass-ceramic to enamel and dentin. Medium-grit diamond burs in high-speed turbine showed the highest mean roughness values. Fine-grit CVD tips in ultrasound presented the highest MSBS values for both enamel and dentin. PMID:27347507

  16. Enamel and Dentin Surface Finishing Influence on the Roughness and Microshear Bond Strength of a Lithium Silicate Glass-Ceramic for Laminate Veneers.

    PubMed

    Gonzaga, Carla Castiglia; Bravo, Ruth Peggy; Pavelski, Thiago Vinícius; Garcia, Paula Pontes; Correr, Gisele Maria; Leonardi, Denise Piotto; da Cunha, Leonardo Fernandes; Furuse, Adilson Yoshio

    2015-01-01

    Objectives. This study evaluated the influence of cavity surface finishing with diamond burs of different grit mounted on high-speed turbine and ultrasound on the roughness and microshear bond strength (MBS) of a lithium silicate glass-ceramic to enamel and dentin. Methods. Enamel and dentin specimens were divided into seven groups, according to the type of surface finishing: 1200-grit sandpaper (control), two different brands of medium-grit and fine-grit diamond burs in a high-speed turbine; medium-grit and fine-grit CVD (chemical vapor deposition) tips in an ultrasonic device. Roughness parameters (n = 5) and MSBS to a glass-ceramic (n = 10) were determined. Data were analyzed using ANOVA and Tukey's test (α = 5%). Results. Control group showed lower mean roughness readings and groups that used medium-grit diamond burs showed the highest mean roughness values. Regarding MSBS, there was no statistical difference when comparing the groups gritted with the same brand of medium- and fine-grit burs and tips. Conclusions. Cavity surface finishing influenced the roughness parameters and MSBS of a glass-ceramic to enamel and dentin. Medium-grit diamond burs in high-speed turbine showed the highest mean roughness values. Fine-grit CVD tips in ultrasound presented the highest MSBS values for both enamel and dentin.

  17. Sol-gel synthesis and in vitro bioactivity of copper and zinc-doped silicate bioactive glasses and glass-ceramics.

    PubMed

    Bejarano, Julian; Caviedes, Pablo; Palza, Humberto

    2015-03-11

    Metal doping of bioactive glasses based on ternary 60SiO2-36CaO-4P2O5 (58S) and quaternary 60SiO2-25CaO-11Na2O-4P2O5 (NaBG) mol% compositions synthesized using a sol-gel process was analyzed. In particular, the effect of incorporating 1, 5 and 10 mol% of CuO and ZnO (replacing equivalent quantities of CaO) on the texture, in vitro bioactivity, and cytocompatibility of these materials was evaluated. Our results showed that the addition of metal ions can modulate the textural property of the matrix and its crystal structure. Regarding the bioactivity, after soaking in simulated body fluid (SBF) undoped 58S and NaBG glasses developed an apatite surface layer that was reduced in the doped glasses depending on the type of metal and its concentration with Zn displaying the largest inhibitions. Both the ion release from samples and the ion adsorption from the medium depended on the type of matrix with 58S glasses showing the highest values. Pure NaBG glass was more cytocompatible to osteoblast-like cells (SaOS-2) than pure 58S glass as tested by 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) assay. The incorporation of metal ions decreased the cytocompatibility of the glasses depending on their concentration and on the glass matrix doped. Our results show that by changing the glass composition and by adding Cu or Zn, bioactive materials with different textures, bioactivity and cytocompatibility can be synthesized.

  18. L-Edge Xanes Measurements of the Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Righter, K.; Sutton, S.; Newville, M.

    2008-01-01

    Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies are inconsistent on whether W occurs as W(4+) or W(6+). It is assumed that W(4+) is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO2 is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO2 most relevant to core formation, around IW-2.

  19. 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.

  20. Influence of ZnO on optical properties and dc conductivity of vanadyl-doped alkali bismuthate glasses

    NASA Astrophysics Data System (ADS)

    Gahlot, P. S.; Seth, V. P.; Agarwal, A.; Kishore, N.; Gupta, S. K.; Arora, M.; Goyal, D. R.

    2004-04-01

    A new family of glasses based on Bi2O3 was found in the systems x ZnO . (0.30 - x )M2O . 0.70Bi(2)O(3) (M = Li, Na) in the range 0.00 less than or equal to x less than or equal to 0.20 containing 2.0 mol% of V2O5 . Density, molar volume, optical band gap and dc conductivity of these glasses have been investigated. The position of the absorption edge and hence the value of the optical band gap has been reported.

  1. Structure of iron phosphate glasses modified by alkali and alkaline earth additions: neutron and x-ray diffraction studies.

    PubMed

    Bingham, P A; Barney, E R

    2012-05-02

    The structure of iron phosphate glasses modified by additions of K(2)O and BaO, with nominal molar compositions [(1 - x)(0.6P(2)O(5)-0.4Fe(2)O(3))]xMe(y)O, where x = 0-0.4 in increments of 0.1; Me=K or Ba; and y = 1 or 2, has been investigated using neutron diffraction and x-ray diffraction techniques. Fitted coordination numbers for P-O and Fe-O showed a notable change in the P-O(NBO) and P-O(BO) contributions at greater than 20 mol% modifier addition, with barium producing a markedly larger increase in P-O(NBO) contribution than potassium. Fitting of T(N)(r) and T(X)(r) provided average n(BaO) = 9 and n(KO) = 6. Iron occurs in a range of coordination sites in these glasses: ([6])Fe(2+), ([4])Fe(3+), ([5])Fe(3+) and ([6])Fe(3+). The partitioning between these sites gives average n(FeO) = 5.2-5.8, with barium-doped glasses exhibiting higher average n(FeO) than potassium-doped glasses. The stronger depolymerizing effect of Ba(2+) than K(+) on the phosphate network, coupled with its greater ionic charge and higher Me-O, Fe-O and O···O coordination numbers, explain previously observed divergences in physical properties between the barium-doped and the potassium-doped glasses.

  2. Understanding the structure and deformation of titanium-containing silicate glasses from their elastic responses to external stimuli

    NASA Astrophysics Data System (ADS)

    Scannell, Garth

    The responses of structure and properties to composition and temperature have been investigated for glasses in TiO2-SiO2 and Na2O-TiO2-SiO2 systems. Additionally, the response of Na2O-TiO2-SiO2 glasses to plastic deformation has been studied. (x)TiO2-(1-x)SiO2 glasses were prepared through the sol-gel process with compositions 0 ≤ x ≤ 10 mol% and compared to commercial glasses prepared through flame hydrolysis deposition with x = 0, 5.4, and 8.3 mol%. (x) Na2O - (y) TiO 2 - (1-x-y) SiO2 glasses were prepared with x = 10, 15, 20, and 25 mol% and y = 4, 7, and 10 mol% through a melt-quench process. Density and index of refraction of glasses was measured through the Archimedes's method and using a prism coupler, respectively. The glass transition temperature of Na2O-TiO2-SiO2 glasses was measured through differential thermal analysis. The structure and elastic moduli have been studied through Raman spectroscopy and Brillouin light scattering, respectively, at room temperature and in-situ up to 1200 °C for TiO2-SiO2 glasses and up to 800 °C for Na2O-TiO2-SiO2 glasses. Young's modulus was observed to decrease from 72 GPa to 66 GPa with the addition of 8.3 mol% TiO2 in TiO2-SiO2 glasses and to increase from 65 GPa to 73 GPa with the addition of 10 mol% TiO2 in 10 Na2O - (0-10) TiO2-SiO2 glasses. The addition of TiO2 was observed to shift the 460, 490, and 600 cm-1 Raman peaks to lower frequencies in TiO2-SiO2 glasses, suggesting a more open and flexible network, and the 720, 800, and 840 cm -1 Raman peaks to higher frequencies in Na2O-TiO2 -SiO2 glasses, suggesting a lower free volume and stiffer network. The addition of TiO2 has little effect on the temperature response of the elastic moduli in either system, but decreases the thermal expansion and increases the frequency shifts in the 950 and 1100 cm -1 Raman peaks in the TiO2-SiO2 system while the thermal expansion increases with initial additions of TiO2 and then remains constant in the Na2O-TiO2-SiO 2 system

  3. Voids in mixed-cation silicate glasses: Studies by positron annihilation lifetime and Fourier transform infrared spectroscopies.

    PubMed

    Reben, M; Golis, E; Filipecki, J; Sitarz, M; Kotynia, K; Jeleń, P; Grelowska, I

    2014-08-14

    PALS in comparison with FTIR studies have been applied to investigate the structure of different oxide glasses. Three components of the positron lifetime τ (τ1 para- and τ3 ortho-positronium and τ2 intermediate lifetime component) and their intensities were obtained. The results of the calculation of mean values of positron lifetimes for the investigated glasses showed the existence of a long-living component on the positron annihilation lifetime spectra. From the Tao-Eldrup formula we can estimate the size of free volume. On the basis of the measurements we can conclude that the size and fraction of free volume reaches the biggest value for the fused silica glass. The degree of network polymerisation increases void size.

  4. Long-lasting phosphorescence in Sn2+-Cu2+ codoped silicate glass and its high-pressure treatment effect

    NASA Astrophysics Data System (ADS)

    Qiu, Jianbei; Miyauchi, Koichi; Kawamoto, Yoji; Kitamura, Naoyuki; Qiu, Jianrong; Hirao, Kazuyuki

    2002-07-01

    Long-lasting phosphorescence was observed at 510 nm in a Sn2+-Cu2+ codoped Na2O-CaO-SiO2 glass at room temperature under UV illumination of 254 nm. When the glass was compressed under 3, 6, and 9 GPa, the phosphorescence shifted to 465 nm and its decay rate became shorter. The optical absorption spectra of the samples changed after compression, showing that the cupric ions were reduced to the cuprous ions. The high-pressure treatment also resulted in a lower-energy shift in the absorption edge. It was suggested that Sn2+ ions act as hole trapping centers, while oxygen vacancies surrounding by Ca2+ ions as well as active sites in the glass matrix, i.e., as electron trapping centers.

  5. Determination of lead, uranium, thorium, and thallium in silicate glass standard materials by isotope dilution mass spectrometry

    USGS Publications Warehouse

    Barnes, I.L.; Garner, E.L.; Gramlich, J.W.; Moore, L.J.; Murphy, T.J.; Machlan, L.A.; Shields, W.R.; Tatsumoto, M.; Knight, R.J.

    1973-01-01

    A set of four standard glasses has been prepared which have been doped with 61 different elements at the 500-, 50-, 1-, and 0.02-ppm level. The concentrations of lead, uranium, thorium, and thallium have been determined by isotope dilution mass spectrometry at a number of points in each of the glasses. The results obtained from independent determinations in two laboratories demonstrate the homogeneity of the samples and that precision of the order of 0.5% (95% L.E.) may be obtained by the method even at the 20-ppb level for these elements. The chemical and mass spectrometric procedures necessary are presented.

  6. Evidence for extreme fractionation of peralkaline silicic magmas, the Boseti volcanic complex, Main Ethiopian Rift

    NASA Astrophysics Data System (ADS)

    MacDonald, Ray; Bagiński, Bogusław; Ronga, Fiorenzo; Dzierżanowski, Piotr; Lustrino, Michele; Marzoli, Andrea; Melluso, Leone

    2012-03-01

    Matrix glass and melt inclusions in phenocrysts from pantellerite lavas of the Boseti volcanic complex, Ethiopia, record extreme fractionation of peralkaline silicic magma, with Al2O3 contents as low as 2.3 wt.%, FeO* contents up to 17 wt.% and SiO2 contents ~65 wt.%. The new data, and published data for natural and experimental glasses, suggest that the effective minimum composition for peralkaline silicic magmas has ~5 wt.% Al2O3, 13 wt.% FeO* and 66 ± 2 wt.% SiO2. The dominant fractionating assemblage is alkali feldspar + fayalite + hedenbergite + oxides ± quartz. Feldspar - melt relationships indicate that the feldspar is close to the minimum on the albite-orthoclase solid solution loop through the entire crystallization history. There is petrographic, mineralogical and geochemical evidence that magma mixing may have been a common process in the Boseti rhyolites.

  7. Localised doping of Li-silicate glasses by Er 3+ ion exchange to fabricate thin optical layers

    NASA Astrophysics Data System (ADS)

    Salavcova, Linda; Spirkova, Jarmila; Mika, Martin; Mackova, Anna; Oswald, Jiri; Langrova, Anna; Vacik, Jiri

    2007-03-01

    Here we present a new method of fabrication of erbium containing thin optical layers that could be interesting for photonics active structures. These layers were fabricated by a purely thermal ion-exchange process at temperatures above the transformation point of the used glasses to minimise internal strain that arose in the layers during the fabrication process. In order to accelerate migration of rather immobile Er3+ ions, we used substrates with a high content of easily exchangeable Li+ ions. The substrates were prepared either as specially designed Li-glasses or glasses with intentionally created Li-containing surface layers. A number of nuclear analytical methods (i.e., Rutherford backscattering spectroscopy-RBS, and neutron depth profiling-NDP), as well as scanning electron microscopy (SEM-EDAX) were used to confirm presence of erbium in the glass surface and to determine the chemical composition of the fabricated layers. Photoluminescence spectra of the fabricated samples were measured to examine desired emission at the wavelength of 1.5 μm.

  8. Silicate stabilization studies in propylene glycol

    SciTech Connect

    Schwartz, S.A.

    1999-08-01

    In most North American and many European coolant formulations, the corrosion inhibition of heat-rejecting aluminum surfaces is provided by alkali metal silicates. But, their tendency towards polymerization, leading to gelation and/or precipitation, can reduce the effectiveness of a coolant. This paper presents the results of experiments which illustrate formulation-dependent behavior of inorganic silicate in propylene glycol compositions. Specific examples of the effects of glycol matrix, stabilizer type, and hard water on silicate stabilization are provided.

  9. 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.

  10. Scintillating glass fiber-optic neutron sensors

    SciTech Connect

    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 {minus}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 % lithia), we have attributed this aging to aqueous corrosion oat 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.

  11. Pressure determination in HDAC experiments, the behavior of isochoric water-silicate systems at high pressure, and implications for melt (glass) inclusion studies

    NASA Astrophysics Data System (ADS)

    Solferino, Giulio; Anderson, Alan J.

    2015-04-01

    The Hydrothermal Diamond Anvil Cell (HDAC) could be seen as a synthetic fluid inclusion, where the composition of the trapped phase(s) and the type of fluid medium are controlled by the experimentalist. Accurate pressure determination in Hydrothermal Diamond Anvil Cell (HDAC) experiments has proven to be a complex achievement. In this study we employed in-situ visualization of the alpha-beta quartz transformation via laser interferometry for the purpose. This inexpensive and convenient method allowed for an accuracy of less than 30-40 MPa in the pressure range 130-900 MPa, which is relevant for crust and shallower upper mantle investigations. Our experiments with water + haplogranite glass crossed into the undercooled liquid and melt state of the silicate phase, where the pressure medium contains a significant amount of solute. The principal goal of this experimental series was to compare the actual run pressure with that calculated for pure water pressure medium. We found that for runs where the alpha-to-beta transition temperature is ≤ 665 °C run pressure is lower than that computed for pure water. On the contrary, at ~780 °C the pressure in the HDAC is ~100 MPa greater than that estimated using pure water isochore. We employed a simplified model of haplogranite dissolution in water for an isochoric sample chamber to explain the negative sign and the variation of the observed discrepancy between measured and calculated pressure. We suggest that, beyond the change in the intrinsic properties of the fluid phase (e.g., compressibility) with increasing solute concentration, two factors control the P-T path in the HDAC: (1) hydration of the glass prior to the glass transition; and (2) changing volume of the aqueous pressure medium. The latter effects must be considered when investigating hydrothermal isochoric systems where the solid/melt phase is highly soluble in the fluid, such as in the determination of the P-T path during rehomogenization of water-rich melt

  12. Development and effect of different bioactive silicate glass scaffolds: in vitro evaluation for use as a bone drug delivery system.

    PubMed

    Soundrapandian, Chidambaram; Mahato, Arnab; Kundu, Biswanath; Datta, Someswar; Sa, Biswanath; Basu, Debebrata

    2014-12-01

    Local drug delivery systems to bone have attracted appreciable attention due to their efficacy to improve drug delivery, healing and regeneration. In this paper, development and characterization of new formulations of bioactive glass into a porous scaffold has been reported for its suitability to act as a drug delivery system in the management of bone infections, in vitro. Two new glass compositions based on SiO2-Na2O-ZnO-CaO-MgO-P2O5 system (BGZ and MBG) have been developed which after thorough chemical and phase evaluation, studied for acellular static in vitro bioactivity in SBF. Porous scaffolds made of these glasses have been fabricated and characterized thoroughly for bioactivity study, SEM, XRD, in vitro cytotoxicity, MTT assay and wound healing assay using human osteocarcoma cells. Finally, gatifloxacin was loaded into the porous scaffold by vacuum infiltration method and in vitro drug release kinetics have been studied with varying parameters including dissolution medium (PBS and SBF) and with/without impregnation chitosan. Suitable model has also been proposed for the kinetics. 63-66% porous and 5-50μm almost unimodal porous MBG and BGZ bioactive glass scaffolds were capable of releasing drugs successfully for 43 days at concentrations to treat orthopedic infections. In addition, it was also observed that the release of drug followed Peppas-Korsmeyer release pattern based on Fickian diffusion, while 0.5-1% chitosan coating on the scaffolds decreased the burst release and overall release of drug. The results also indicated that MBG based scaffolds were bioactive, biocompatible, noncytotoxic and exhibited excellent wound healing potential while BGZ was mildly cytotoxic with moderate wound healing potential. These results strongly suggest that MBG scaffolds appear to be a suitable bone drug delivery system in orthopedic infections treatment and as bone void fillers, but BGZ should be handled with caution or studied elaborately in detail further to ascertain

  13. Evaluation of shear bond strength of two resin-based composites and glass ionomer cement to pure tricalcium silicate-based cement (Biodentine®)

    PubMed Central

    CANTEKİN, Kenan; AVCİ, Serap

    2014-01-01

    Objectives Tricalcium silicate is the major constituent phase in mineral trioxide aggregate (MTA). It is thus postulated that pure tricalcium silicate can replace the Portland cement component of MTA. The aim of this study was to evaluate bond strength of methacrylate-based (MB) composites, silorane-based (SB) composites, and glass ionomer cement (GIC) to Biodentine® and mineral trioxide aggregate (MTA). Material and Methods Acrylic blocks (n=90, 2 mm high, 5 mm diameter central hole) were prepared. In 45 of the samples, the holes were fully filled with Biodentine® and in the other 45 samples, the holes were fully filled with MTA. The Biodentine® and the MTA samples were randomly divided into 3 subgroups of 15 specimens each: Group-1: MB composite; Group-2: SB composite; and Group-3: GIC. For the shear bond strength (SBS) test, each block was secured in a universal testing machine. Results The highest (17.7±6.2 MPa) and the lowest (5.8±3.2 MPa) bond strength values were recorded for the MB composite-Biodentine® and the GIC-MTA, respectively. Although the MB composite showed significantly higher bond strength to Biodentine (17.7±6.2) than it did to MTA (8.9±5.7) (p<0.001), the SB composite (SB and MTA=7.4±3.3; SB and Biodentine®=8.0±3,6) and GIC (GIC and MTA=5.8±3.2; GIC and Biodentine=6.7±2.6) showed similar bond strength performance with MTA compared with Biodentine (p=0.73 and p=0.38, respectively). Conclusions The new pure tricalcium-based pulp capping, repair, and endodontic material showed higher shear bond scores compared to MTA when used with the MB composite. PMID:25141202

  14. Multiple metasomatic events recorded in Kilbourne Hole peridotite xenoliths: the relative contribution of host basalt interaction vs. silicate metasomatic glass

    NASA Astrophysics Data System (ADS)

    Hammond, S. J.; Yoshikawa, M.; Harvey, J.; Burton, K. W.

    2010-12-01

    Stark differences between bulk-rock lithophile trace element budgets and the sum of the contributions from their constituent minerals are common, if not ubiquitous in peridotite xenoliths [1]. In the absence of modal metasomatism this discrepancy is often attributed to the “catch-all”, yet often vague process of cryptic metasomatism. This study presents comprehensive Sr-Nd isotope ratios for variably metasomatized bulk-rock peridotites, host basalts, constituent peridotite mineral phases and interstitial glass from 13 spinel lherzolite and harzburgite xenoliths from the Kilbourne Hole volcanic maar, New Mexico, USA. Similar measurements were also made on hand-picked interstitial glass from one of the most highly metasomatized samples (KH03-16) in an attempt to unravel the effects of multiple metasomatic events. In all Kilbourne Hole peridotites analysed, hand-picked, optically clean clinopyroxenes preserve a more primitive Sr isotope signature than the corresponding bulk-rock; a pattern preserved in all but one sample for Nd isotope measurements. Reaction textures, avoided during hand-picking, around clinopyroxene grains are evident in the most metasomatized samples and accompanied by films of high-SiO2 interstitial glass. The margins of primary minerals appear partially resorbed and trails of glassy melt inclusions similar in appearance to those previously reported from the same locality [2], terminate in these films. Hand-picked glass from KH03-16 reveals the most enriched 87Sr/86Sr of any component recovered from these xenoliths (87Sr/86Sr = 0.708043 ± 0.00009; [Sr] = 81 ppm). Similarly, the 143Nd/144Nd of the glass is amongst the most enriched of the peridotite components (143Nd/144Nd = 0.512893 ± 0.000012; [Nd] = 10 ppm). However, the host basalt (87Sr/86Sr = 0.703953 ± 0.00012; 143Nd/144Nd = 0.512873 ± 0.000013), similar in composition to nearby contemporaneous Potrillo Volcanic Field basalts [3], contains nearly an order of magnitude more Sr and more

  15. Thermal analysis of reactions in soda-lime silicate glass batches containing melting accelerants: II, multicomponent systems

    SciTech Connect

    Hong, Kug Sun; Lee, Sang Won; Speyer, R.F. )

    1993-03-01

    The glass melting reactions in a multicomponent system (sand-soda ash-calcite-dolomite-feldspar) were studied using data from DTA, TGA, and XRD interactively. The first-formed liquid phase occurred at 700C from eutectic melting among CaCO[sub 3], Na[sub 2]CO[sub 3], and MgO. Further liquid phase formed at the CaCO[sub 3]-Na[sub 2]CO[sub 3] eutectic at 785C and a fusion reaction among SiO[sub 2], CaO, and the molten phase at 812C. Reactions between molten soda ash and silica grains to form a sodium disilicate coating also occurred in this temperature range. The effects of reaction accelerant additions (Na[sub 2], SO[sub 4], NaNO[sub 3], NaCl) on batch fusion were analyzed. Sodium chloride was found to be the most effective melting accelerant due to the formation of a NaCl-Na[sub 2]CO[sub 3] eutectic liquid phase at [approximately]636C, which effectively attacked the silica relic. CO[sub 2] gas release terminated [approximately]80C earlier with 1 wt% NaCl additions to the base glass.

  16. Sulfur Isotope Variation in Basaltic Melt Inclusions from Krakatau Revealed by a Newly Developed Secondary Ion Mass Spectrometry Technique for Silicate Glasses

    NASA Astrophysics Data System (ADS)

    Mandeville, C. W.; Shimizu, N.; Kelley, K. A.; Cheek, L.

    2008-12-01

    Sulfur is a ubiquitous element with variable valance states (S2-, S0, S4+, S6+) allowing for its participation in a wide variety of chemical and biogeochemical processes. However, its potential as an isotopic tracer in magmatic processes has not been fully developed and is crucial to understanding of sulfur recycling in subduction zones and between Earth's major reservoirs, mantle, lithosphere and coupled hydrosphere-atmosphere. Previous studies of silicate glasses and melt inclusions have been hampered by lack of an in situ isotopic measurement technique with spatial resolution of 10 to 100 microns. We have developed a new secondary ion mass spectrometry (SIMS) analytical technique for measurement of 34S/32S ratios in silicate glasses utilizing the IMS 1280 at Woods Hole Oceanographic Institution. A beam of 133Cs+ ions with 13 keV energy and current of 1-2 nA is focused onto a 10 micron spot and rastered over 30 × 30 microns. A Normal Incidence Electron Gun was used to compensate excess charge. The rastered beam is then centered to the optical axis of the machine, and a mechanical aperture is placed on the image plane to limit the area of analysis to the central 15 × 15 microns. The energy slit width was adjusted to 50 eV. A mass resolving power of 5500 was sufficient for eliminating mass interferences. A suite of synthetic and natural glasses with δ34SVCDT values spanning from - 5.6‰ to 18.5‰ with SiO2 from 44-72 weight % were measured. Magnitude of the instrumental mass fractionation (α) for 34S/32S ratios is 0.991 and is constant for all the glasses measured despite their compositions. Precision of individual measurements of 34S/32S ratios is 0.4 ‰, or better. Preliminary δ34S measurements of olivine-hosted basaltic melt inclusions in pre- 1883 basaltic scoria from Krakatau volcano Indonesia vary from -5.6 to 7.9‰ with sulfur concentrations from 490 to 2170 ppm, respectively. Host olivines are Fo77-80 and inclusions generally need minor to no post

  17. Characterization of enameled glass excavated from Laem Pho, southern Thailand

    NASA Astrophysics Data System (ADS)

    Dhanmanonda, W.; Won-in, K.; Tancharakorn, S.; Tantanuch, W.; Thongleurm, C.; Kamwanna, T.; Dararutana, P.

    2012-07-01

    Laem Pho in Surat Thani, southern province of Thailand is one of the most important historic site on the eastern shore of the Gulf of Thailand. In this work, the enameled glass fragments which looked-like Islamic glass mainly excavated from this site were analyzed using SEM-EDS, PIXE and μ-XRF, in order to understand the chemical composition by comparing the archaeological data and topology. The structure of the enameled decoration was also studied. The resulting data indicated that high-magnesia alkali-lime silicate glass was produced. The presence of transition metals such as copper, iron and manganese were affected on the glass colorations. Typological classifications, technological observations and comparative studies serve to clarify the development and cultural inter-relationships of various glass objects along the trade and exchange networks in ancient maritime.

  18. Preferential growth orientation of laser-patterned LiNbO{sub 3} crystals in lithium niobium silicate glass

    SciTech Connect

    Komatsu, T.; Koshiba, K.; Honma, T.

    2011-02-15

    Dots and lines consisting of LiNbO{sub 3} crystals are patterned on the surface of 1CuO-40Li{sub 2}O-32Nb{sub 2}O{sub 5}-28SiO{sub 2} (mole ratio) glass by irradiations of continuous-wave Nd:YAG laser (wavelength: {lambda}=1064 nm), diode laser ({lambda}=795 nm), and Yb:YVO{sub 4} fiber laser ({lambda}=1080 nm), and the feature of laser-patterned LiNbO{sub 3} crystal growth is examined from linearly polarized micro-Raman scattering spectrum measurements. LiNbO{sub 3} crystals with the c-axis orientation are formed at the edge parts of the surface and cross-section of dots. The growth direction of an LiNbO{sub 3} along the laser scanning direction is the c-axis. It is proposed that the profile of the temperature distribution in the laser-irradiated region and its change along laser scanning would be one of the most important conditions for the patterning of crystals with a preferential growth orientation. Laser irradiation giving a narrow width is also proposed to be one of the important factors for the patterning of LiNbO{sub 3} crystal lines with homogeneous surface morphologies. -- Graphical abstract: Polarized optical microscope observations for the surface and cross-section of the dot obtained by LD laser ({lambda}=795 nm) irradiations of P=1.4 W and t=20 s in Cu-LNS glass. Schematic model for the orientation of LiNbO{sub 3} crystals at the edge parts of the surface and cross-section of the dot is also shown. Display Omitted Research highlights: > Dots and lines with LiNbO{sub 3} crystals are patterned on the glass surface by laser irradiations. > LiNbO{sub 3} crystals with the c-axis orientation are formed at the edge parts of the surface and cross-section of dots. > The profile of the temperature distribution in the laser-irradiated region is one of the most important conditions for the patterning of highly oriented crystals.

  19. Carbonation of metal silicates for long-term CO2 sequestration

    DOEpatents

    Blencoe, James G; Palmer, Donald A; Anovitz, Lawrence M; Beard, James S

    2014-03-18

    In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

  20. Carbonation of metal silicates for long-term CO.sub.2 sequestration

    DOEpatents

    Blencoe, James G [Harriman, TN; Palmer, Donald A [Oliver Springs, TN; Anovitz, Lawrence M [Knoxville, TN; Beard, James S [Martinsville, VA

    2012-02-14

    In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

  1. Optoelectronic properties and interfacial durability of CNT and ITO on boro-silicate glass and PET substrates with nano- and heterostructural aspects

    NASA Astrophysics Data System (ADS)

    Park, Joung-Man; Wang, Zuo-Jia; Kwon, Dong-Jun; DeVries, Lawrence

    2011-02-01

    Nano- and hetero-structures of carbon nanotube (CNT) and indium tin oxide (ITO) can control significantly piezoelectric and optoelectronic properties in Microelectromechanical Systems (MEMS) as sensing and actuator under cyclic loading. Optimized preparing conditions were obtained for multi-functional purpose of the specimen by obtaining the best dispersion and turbidity in the solution. Optical transmittance and electrical properties were investigated for CNT and ITO dipping and spraying coating on boro-silicate glass and polyethylene terephthalate (PET) substrates by electrical resistance measurement under cyclic loading and wettability test. Uniform dip-coating was performed using Wilhelmy plate method due to its simple and convenience. Spraying coating was applied to the specimen additionally. The change in the electrical resistance and optical properties of coated layer were mainly dependent upon the number of dip-coating, the concentration of CNT and ITO solutions, and the surface treatment condition. Electric properties of coating layers were measured using four-point probe method, and surface resistance was calculated using a dual configuration method. Optical transmittance of CNT and ITO coated PET film was also evaluated using UV spectrum. Surface energy and their hydrophilic and hydrophobic properties of CNT and ITO coated substrates were investigated by wettability test via static and dynamic contact angle measurements. As the elapsing time of cyclic loading passed, the stability of surface resistance and thus comparative interfacial adhesion between coated layer and substrates was evaluated to compare the thermodynamic work of adhesion, Wa. As dip-coating number increased, surface resistance of coated CNT decreased, whereas the transmittance decreased step-by-step due to the thicker CNT and ITO networked layer. Nano- and heterostructural effects of CNT and ITO solution on the optical and electrical effects have been studied continuously.

  2. Effect of iron content on the structure and disorder of iron-bearing sodium silicate glasses: A high-resolution 29Si and 17O solid-state NMR study

    NASA Astrophysics Data System (ADS)

    Kim, Hyo-Im; Sur, Jung Chul; Lee, Sung Keun

    2016-01-01

    Despite its geochemical importance and implications for the properties of natural magmatic melts, understanding the detailed structure of iron-bearing silicate glasses remains among the outstanding problems in geochemistry. This is mainly because solid-state NMR techniques, one of the most versatile experimental methods to probe the structure of oxide glasses, cannot be fully utilized for exploring the structural details of iron-bearing glasses as the unpaired electrons in Fe induce strong local magnetic fields that mask the original spectroscopic features (i.e., paramagnetic effect). Here, we report high-resolution 29Si and 17O solid-state NMR spectra of iron-bearing sodium silicate glasses (Na2O-Fe2O3-SiO2, Fe3+/ΣFe = 0.89 ± 0.04, thus containing both ferric and ferrous iron) with varying XFe2O3 [=Fe2O3/(Na2O + Fe2O3)], containing up to 22.9 wt% Fe2O3. This compositional series involves Fe-Na substitution at constant SiO2 contents of 66.7 mol% in the glasses. For both nuclides, the NMR spectra exhibit a decrease in the signal intensities and an increase in the peak widths with increasing iron concentration partly because of the paramagnetic effect. Despite the intrinsic difficulties that result from the pronounced paramagnetic effect, the 29Si and 17O NMR results yield structural details regarding the effect of iron content on Q speciation, spatial distribution of iron, and the extent of polymerization in the iron-bearing silicate glasses. The 29Si NMR spectra show an apparent increase in highly polymerized Q species with increasing XFe2O3 , suggesting an increase in the degree of melt polymerization. The 17O 3QMAS NMR spectra exhibit well-resolved non-bridging oxygen (NBO, Na-O-Si) and bridging oxygen (BO, Si-O-Si) peaks with varying iron concentration. By replacing Na2O with Fe2O3 (and thus with increasing iron content), the fraction of Na-O-Si decreases. Quantitative consideration of this effect confirms that the degree of polymerization is likely to

  3. 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.

  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. Laser scanning confocal microscopy for in situ monitoring of alkali-silica reaction.

    PubMed

    Collins, C L; Ideker, J H; Kurtis, K E

    2004-02-01

    Alkali-silica reaction (ASR) occurs in concrete between reactive siliceous components in the aggregate and the strongly alkaline pore solution, resulting in the formation of a potentially expansive gel product. Lithium additives have been shown to reduce expansion associated with ASR, but the mechanism(s) by which lithium reduces expansion have not been understood. Therefore, development of an in situ method to observe reactions associated with ASR is highly desirable, as it will allow for non-destructive observation of the reaction product formation and damage evolution over time, as the reaction progresses. A technique to image into mortar through glass aggregate by laser scanning confocal microscopy (LSCM), producing three-dimensional representations of the sample was developed. This LSCM technique was utilized to monitor the progress of alkali-silica reaction in mortar samples prepared with alkali-reactive glass aggregate both in the presence and in the absence of lithium additives: LiNO3, LiCl or LiOH. The method proved to be effective in qualitatively monitoring crack formation and growth and product formation, within cracks and at the paste/aggregate interface. In particular, dendritic products were observed at the paste/aggregate interface only in those samples containing lithium, suggesting that these products may play a role in ASR mitigation.

  6. 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.

  7. Ion-implantation-induced stress in glasses: Variation of damage mode efficiency with changes in glass structure

    NASA Astrophysics Data System (ADS)

    Arnold, G. W.

    1988-05-01

    Ion implantation induces lateral stress in glass due to the volume dilatation in the implanted near-surface region. Cantilever-beam experiments allow these quantities to be measured as a function of fluence. For fused silica the stress data for various incident ions are found to scale with atomic collision energy deposition. In sharp contrast, Pyrex (alkali-borosilicate) glass, (1 - x)(Na, K) 2O· xB 2O 3·3SiO 2 glass, and a sodalime (microscope slide) glass, yield stress values which scale with energy deposition into electronic processes. More significantly, this mode of damage production is dominant for the nuclear waste glasses PNL 76-68 and SRP. The void space in fused silica allows room for displaced Si and/or O. For the complex alkali-containing silicates, the interstitial volume is restricted. In the latter case, the probability increases that permanent defects can be formed by ionization-induced bond-breaking and network relaxation. These data imply that alpha-particle ionization energy deposition may be an important factor in nuclear waste glass radiation damage production, but the magnitude of this contribution has not yet been evaluated.

  8. Physical and optical properties of Co{sup 2+}, Ni{sup 2+} doped 20ZnO + xLi{sub 2}O + (30 − x)K{sub 2}O + 50B{sub 2}O{sub 3} (5 ≤ x ≤ 25) glasses: Observation of mixed alkali effect

    SciTech Connect

    Krishna Kumari, G.; Muntaz Begum, Sk.; Rama Krishna, Ch.; Sathish, D.V.; Murthy, P.N.; Rao, P.S.; Ravikumar, R.V.S.S.N.

    2012-09-15

    Graphical abstract: Composition dependence of density and Urbach energy of Co{sup 2+} and Ni{sup 2+} doped ZLKB glasses: (a) Co{sup 2+} doped glasses and (b) Ni{sup 2+} doped glasses. Both are exhibited mixed alkali effect. Highlights: ► Mixed alkali effect is observed. ► Band gap studies indicate that the glasses are structural stable. ► The glasses are observed to be partially covalent in nature. -- Abstract: Co{sup 2+} and Ni{sup 2+} ions doped 20ZnO + xLi{sub 2}O + (30 − x) K{sub 2}O + 50B{sub 2}O{sub 3} (5 ≤ x ≤ 25) mol% glasses are prepared using melt quenching technique. Structural changes of the prepared glasses by addition of transition metal oxides, CoO and NiO are investigated by UV–vis–NIR, FT-IR spectroscopy and XRD. The XRD pattern indicates the amorphous nature of prepared glasses. FT-IR measurements of the all glasses revealed that the network structure of the glasses are mainly based on BO{sub 3} and BO{sub 4} units placed in different structural groups in which the BO{sub 3} units being dominant. The optical absorption spectra suggest the site symmetry of Co{sup 2+} and Ni{sup 2+} ions in the glasses are near octahedral. Crystal field and inter-electronic repulsion parameters are also evaluated. The optical band gap and Urbach energies exhibited the mixed alkali effect. Various physical parameters such as density, refractive index, optical dielectric constant, polaron radius, electronic polarizability and inter-ionic distance are also determined.

  9. 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.

  10. Ion Exchange in Glass-Ceramics

    NASA Astrophysics Data System (ADS)

    Beall, George; Comte, Monique; Deneka, Matthew; Marques, Paulo; Pradeau, Philippe; Smith, Charlene

    2016-08-01

    In the past few years ion-exchange in glasses has found a renewed interest with a lot of new development and research in industrial and academic labs and the commercialization of materials with outstanding mechanical properties. These glasses are now widely used in many electronic devices including hand-held displays and tablets. The exchange is generally conducted in a bath of molten salt below the transition temperature of the glass. The exchange at the surface of an alkali ion by a bigger one brings compressive stress at the surface. The mechanical properties are dependent on the stress level at the surface and the depth of penetration of the bigger ion. As compared to glasses, glass-ceramics have the interest to display a wide range of aspects (transparent to opaque) and different mechanical properties (especially higher modulus and toughness). There has been little research on ion-exchange in glass-ceramics. In these materials the mechanisms are much more complex than in glasses because of their polyphasic nature: ion-exchange generally takes place mostly in one phase (crystalline phase or residual glass). The mechanism can be similar to what is observed in glasses with the replacement of an ion by another in the structure. But in some cases this ion-exchange leads to microstructural modifications (for example amorphisation or phase change). This article reviews these ion-exchange mechanisms using several transparent and opaque alumino-silicate glass-ceramics as examples. The effect of the ion exchange in the various glass-ceramics will be described, with particular emphasis on flexural strength.

  11. 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

  12. The Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses: Results from W L-Edge Xanes Measurements

    NASA Technical Reports Server (NTRS)

    Danielson, Lisa R.; Righter, K.; Sutton S.; Newville, M.; Le, L.

    2007-01-01

    Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted approx. 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies (figure 1) are inconsistent on whether W occurs as W(4+) or W(6+).

  13. Structure and Chemical Durability of Lead Crystal Glass.

    PubMed

    Angeli, Frédéric; Jollivet, Patrick; Charpentier, Thibault; Fournier, Maxime; Gin, Stéphane

    2016-11-01

    Silicate glasses containing lead, also called lead crystal glasses, are commonly used as food product containers, in particular for alcoholic beverages. Lead's health hazards require major attention, which can first be investigated through the understanding of Pb release mechanisms in solution. The behavior of a commercial crystal glass containing 10.6 mol % of PbO (28.3 wt %) was studied in a reference solution of 4% acetic acid at 22, 40, and 70 °C at early and advanced stages of reaction. High-resolution solid-state (17)O and (29)Si NMR was used to probe the local structure of the pristine and, for the first time, of the altered lead crystal glass. Inserted into the vitreous structure between the network formers as Si-O-Pb bonds, Pb does not form Pb-O-Pb clusters which are expected to be more easily leached. A part of K is located near Pb, forming mixed Si-O-(Pb,K) near the nonbridging oxygens. Pb is always released into the solution following a diffusion-controlled dissolution over various periods of time, at a rate between 1 and 2 orders of magnitude lower than the alkalis (K and Na). The preferential release of alkalis is followed by an in situ repolymerization of the silicate network. Pb is only depleted in the outermost part of the alteration layer. In the remaining part, it stays mainly surrounded by Si in a stable structural configuration similar to that of the pristine glass. A simple model is proposed to estimate the Pb concentration as a function of glass surface, solution volume, temperature, and contact time.

  14. Mafic intrusion remobilising silicic magma under El Hierro, Canary Islands

    NASA Astrophysics Data System (ADS)

    Sigmarsson, O.; Laporte, D.; Marti, J.; Devouard, B.; Cluzel, N.

    2012-04-01

    The 2011 submarine eruption at El Hierro, Canary Islands, has produced volcanic bombs that degas at sea surface, boil seawater and sink when cooled and degassed. At the beginning of the eruption white coloured pumices enveloped in darker coloured spatters floated on land. These composite pumices show evidence of magma mingling with folds and undulations of the darker coloured magma within the white pumice suggesting magma mingling in a viscous regime. The white pumice is highly vesicular and resembles foam. Most of the vesicular structure is made of tightly packed, polygonal bubbles of uniform size (˜ 100 μm), suggesting a single event of homogeneous bubble nucleation. An earlier event of heterogeneous bubble nucleation is indicated by the presence of a few large bubbles developed around tiny quartz crystals. Both the darker and lighter coloured pumices are almost aphyric. A few olivine crystals with perfect euhedral morphology occur within the darker part. Rare olivines of same composition are also found in the white pumice glass but then display somewhat rounded outlines and hopper-type structure. Melt inclusions in olivines of the darker pumice are of the same composition as the enveloping mafic glass, whereas olivines in the mixing boundary layer have melt inclusions of less mafic composition. The whole-rock composition and slightly more evolved glass composition are of basanitc and alkali rhyolitic composition (at the limit of the trachyte field) according to the TAS classification. Such rhyolitic compositions are rare in the Canaries. Analyses of residual volatile concentration in the glasses show that the silicic glass is highly degassed (F: 511 ±222; Cl: 202 ±58; S: below detection limit; values in ppm,1SD, n=10), whereas the basanitic glass still has very high halogene concentrations (F: 1354 ±151; Cl: 1026 ±47; S: 362 ±29; 1SD, n=10). In-situ analysis of trace element compositions of the dark glasses reveal typical basanitic compositions with

  15. Surface stress relaxation of oxide glasses: The effects on mechanical strength

    NASA Astrophysics Data System (ADS)

    Lezzi, Peter Joseph

    A new glass strengthening mechanism based upon surface compressive stress formation by surface stress relaxation of glasses that were held under a tensile stress, at a temperature lower than the glass transition temperature, in low water vapor pressure, has been demonstrated. Although glass fibers are traditionally known to become mechanically weaker when heat-treated at a temperature lower than the glass transition temperature in the presence of water vapor, the strength was found to become greater than the as-received fiber strength when fibers were subjected to a sub-critical tensile stress during heat-treatment. The observed strengthening was attributed to surface compressive residual stress formation through surface stress relaxation during the sub-critical tensile stress application in the atmosphere containing water vapor. Surface stress relaxation of the same glass fibers was shown to take place under conditions identical to those experienced by the strengthened mechanical test specimens by observing permanent bending of the fiber. Furthermore, the magnitude and presence of the residual stresses formed during bending or tensile heat-treatments were confirmed by FTIR, fiber etching, and fiber slicing methods. The method can in principle be used to strengthen any oxide glass and is not subjected to the constraints of traditional strengthening methods such as a minimum thickness for tempering, or a glass containing alkali ions for ion-exchange. Thus far, the method has been successful in strengthening silica glass, E-glass, and soda-lime silicate glass by approximately 20-30%.

  16. Effect of copper-doped silicate 13-93 bioactive glass scaffolds on the response of MC3T3-E1 cells in vitro and on bone regeneration and angiogenesis in rat calvarial defects in vivo.

    PubMed

    Lin, Yinan; Xiao, Wei; Bal, B Sonny; Rahaman, Mohamed N

    2016-10-01

    The release of inorganic ions from biomaterials could provide an alternative approach to the use of growth factors for improving tissue healing. In the present study, the release of copper (Cu) ions from bioactive silicate (13-93) glass scaffolds on the response of cells in vitro and on bone regeneration and angiogenesis in vivo was studied. Scaffolds doped with varying concentrations of Cu (0-2.0wt.% CuO) were created with a grid-like microstructure by robotic deposition. When immersed in simulated body fluid in vitro, the Cu-doped scaffolds released Cu ions into the medium in a dose-dependent manner and converted partially to hydroxyapatite. The proliferation and alkaline phosphatase activity of pre-osteoblastic MC3T3-E1 cells cultured on the scaffolds were not affected by 0.4 and 0.8wt.% CuO in the glass but they were significantly reduced by 2.0wt.% CuO. The percent new bone that infiltrated the scaffolds implanted for 6weeks in rat calvarial defects (46±8%) was not significantly affected by 0.4 or 0.8wt.% CuO in the glass whereas it was significantly inhibited (0.8±0.7%) in the scaffolds doped with 2.0wt.% CuO. The area of new blood vessels in the fibrous tissue that infiltrated the scaffolds increased with CuO content of the glass and was significantly higher for the scaffolds doped with 2.0wt.% CuO. Loading the scaffolds with bone morphogenetic protein-2 (1μg/defect) significantly enhanced bone infiltration and reduced fibrous tissue in the scaffolds. These results showed that doping the 13-93 glass scaffolds with up to 0.8wt.% CuO did not affect their biocompatibility whereas 2.0wt.% CuO was toxic to cells and detrimental to bone regeneration.

  17. 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.

  18. 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.

  19. Glasses in the D'Orbigny Angrite

    NASA Astrophysics Data System (ADS)

    Varela, M. E.; Kurat, G.; Brandstätter, F.; Bonnin-Mosbah, M.; Metrich, N.

    2001-03-01

    The D'Orbigny angrite contains abundant glasses, a phase which has not been previously reported from any other angrite. Glasses fill in part open druses and intersticial spaces between major silicates, or occur as glass inclusions in olivine.

  20. The geochemistry and provenance of Apollo 16 mafic glasses

    NASA Astrophysics Data System (ADS)

    Zeigler, Ryan A.; Korotev, Randy L.; Jolliff, Bradley L.; Haskin, Larry A.; Floss, Christine

    2006-12-01

    The regolith of the Apollo 16 lunar landing site is composed mainly of feldspathic lithologies but mafic lithologies are also present. A large proportion of the mafic material occurs as glass. We determined the major element composition of 280 mafic glasses (>10 wt% FeO) from six different Apollo 16 soil samples. A small proportion (˜5%) of the glasses are of volcanic origin with picritic compositions. Most, however, are of impact origin. Approximately half of the mafic impact glasses are of basaltic composition and half are of noritic composition with high concentrations of incompatible elements. A small fraction have compositions consistent with impact mixtures of mare material and material of the feldspathic highlands. On the basis of major-element chemistry, we identified six mafic glass groups: VLT picritic glass, low-Ti basaltic glass, high-Ti basaltic glass, high-Al basaltic glass, KREEPy glass, and basaltic-andesite glass. These glass groups encompass ˜60% of the total mafic glasses studied. Trace-element analyses by secondary ion mass spectroscopy for representative examples of each glass group (31 total analyses) support the major-element classifications and groupings. The lack of basaltic glass in Apollo 16 ancient regolith breccias, which provide snapshots of the Apollo 16 soil just after the infall of Imbrium ejecta, leads us to infer that most (if not all) of the basaltic glass was emplaced as ejecta from small- or moderate-sized impacts into the maria surrounding the Apollo 16 site after the Imbrium impact. The high-Ti basaltic glasses likely represent a new type of basalt from Mare Tranquillitatis, whereas the low-Ti and high-Al basaltic glasses possibly represent the composition of the basalts in Mare Nectaris. Both the low-Ti and high-Al basaltic glasses are enriched in light-REEs, which hints at the presence of a KREEP-bearing source region beneath Mare Nectaris. The basaltic andesite glasses have compositions that are siliceous, ferroan

  1. Calcium-borosilicate glass-ceramics wasteforms to immobilize rare-earth oxide wastes from pyro-processing

    NASA Astrophysics Data System (ADS)

    Kim, Miae; Heo, Jong

    2015-12-01

    Glass-ceramics containing calcium neodymium(cerium) oxide silicate [Ca2Nd8-xCex(SiO4)6O2] crystals were fabricated for the immobilization of radioactive wastes that contain large portions of rare-earth ions. Controlled crystallization of alkali borosilicate glasses by heating at T ≥ 750 °C for 3 h formed hexagonal Ca-silicate crystals. Maximum lanthanide oxide waste loading was >26.8 wt.%. Ce and Nd ions were highly partitioned inside Ca-silicate crystals compared to the glass matrix; the rare-earth wastes are efficiently immobilized inside the crystalline phases. The concentrations of Ce and Nd ions released in a material characterization center-type 1 test were below the detection limit (0.1 ppb) of inductively coupled plasma mass spectroscopy. Normalized release values performed by a product consistency test were 2.64·10-6 g m-2 for Ce ion and 2.19·10-6 g m-2 for Nd ion. Results suggest that glass-ceramics containing calcium neodymium(cerium) silicate crystals are good candidate wasteforms for immobilization of lanthanide wastes generated by pyro-processing.

  2. Strength of inorganic glass

    SciTech Connect

    Kurkjian, C.R.

    1985-01-01

    This book presents information on the following topics: a look at the history of glass strength; atomistic theory of fracture; surface chemistry in relation to the strength and fracture of silicate glasses; high-speed photographic investigations of the dynamic localized loading of some oxide glasses; a correction for measurements of contact area using Newton's rings; envionmentally enhanced crack growth; fatigue in glass; behavior of flaws in fused silica fibers; fracture toughness of chalcogenide glasses and glass-ceramics; fracture analysis of glass surfaces; and fracture mechanics parameters for glasses - a compilation and correlation.

  3. Activity composition relationships in silicate melts

    SciTech Connect

    Glazner, A.F.

    1990-01-01

    Equipment progress include furnace construction and electron microprobe installation. The following studies are underway: phase equilibria along basalt-rhyolite mixing line (olivine crystallization from natural silicic andensites, distribution of Fe and Mg between olivine and liquid, dist. of Ca and Na between plagioclase and liquid), enthalpy-composition relations in magmas (bulk heat capacity of alkali basalt), density model for magma ascent and contamination, thermobarometry in igneous systems (olivine/plagioclase phenocryst growth in Quat. basalt), high-pressure phase equilibria of alkali basalt, basalt-quartz mixing experiments, phase equilibria of East African basalts, and granitic minerals in mafic magma. (DLC)

  4. Aubrite basalt vitrophyres: High sulfur silicate melts and a snapshot of aubrite formation. [Abstract only

    NASA Technical Reports Server (NTRS)

    Fogel, R. A.

    1994-01-01

    Two aubrite basalt vitrophyre clasts have been found within AMNH thin sections from the Parsa EH3 chondrite and the Khor Temiki aubrite. Polished sections of the Parsa Aubrite Inclusion (PAI) and the Khor Temiki Inclusion (KTI) were studied by optical, electron probe microanalysis (EPMA), and scanning electron microscopy (SEM) techniques with broad-beam and low absorbed EPMA currents used to minimize glass volatile loss. Some data have previously been reported for PAI and KTI may possibly correlate to a previously reported inclusion in Khor Tiimiki. In polished sections, PAI and KTI are approximately equal 4 mm in diameter and contain a large volume of glass. The clasts have similar textural characteristics and are akin to lunar vitrophyre textures. The glasses have high alkali rhyodacitic compositions Al-though PAI is peraluminous, KTI is significantly peralkaline. Additionally, the glasses have elevated sulfur concentrations that are extremely high by geochemical standards. SEM examination for beam overlap of microscopic CaS, FeS, and (Mg, Mn, Fe) S inclusions showed no such contamination. Furthermore, homogeneity of glass S content and low FeO contents help rule out contamination. Materials research data show that under reducing conditions alumino-silicate melts can dissolve up to several weight percent sulfur in the absence of Fe. The high S and alkali contents, the lack of associated high shock features, and the rationalized phase equilibria suggest that PAI and KTI are igneous melting products of an E-chondrite-like source material. Although large-scale impact melting cannot totally be ruled out, the above observations eliminate the possibility of in-situ shock melting.

  5. Broadband infrared light-emitting patterns in optical glass by laser-induced nanostructuring of NiO-doped alkali-gallium germanosilicates.

    PubMed

    Lotarev, S V; Lipatiev, A S; Golubev, N V; Ignat'eva, E S; Malashkevich, G E; Mudryi, A V; Priseko, Y S; Lorenzi, R; Paleari, A; Sigaev, V N

    2013-02-15

    In this Letter, we show functionalization of NiO-doped 7.5Li(2)O·2.5Na(2)O·20Ga(2)O(3)·35SiO(2)·35GeO(2) glass by space-selective nanocrystallization via exposure to the focused beam of a pulsed copper vapor laser (510.6 and 578.2 nm) at temperature close to the glass transition point (570°C). Irradiated areas drastically change their color, caused by electronic transitions of Ni(2+) dopant ions, without any alteration of the optical quality. Importantly, irradiated regions acquire broadband infrared luminescence (centered at about 1400 nm and possessing 400 nm effective bandwidth) typical of Ni(2+) ions in crystalline environment, and by positive change of refractive index (more than 10(-3)). Spectroscopic and diffractometric data of the irradiated regions indeed resemble those previously observed in thermally nanocrystallized glass, with Ni(2+) ions embedded in γ-Ga(2)O(3) nanocrystals. The results demonstrate the possibility of laser writing nanocrystallized multifunction patterns in germanosilicate glasses for the fabrication of active integrated devices.

  6. Silicate diffusion in alkali-carbonatite and hydrous melts at 16.5 and 24 GPa: Implication for the melt transport by dissolution-precipitation in the transition zone and uppermost lower mantle

    NASA Astrophysics Data System (ADS)

    Shatskiy, Anton; Litasov, Konstantin D.; Borzdov, Yuriy M.; Katsura, Tomoo; Yamazaki, Daisuke; Ohtani, Eiji

    2013-12-01

    The diffusivity of dissolved Mg2SiO4 in wadsleyite saturated KMC melt (K2Mg(CO3)2 + 25.7 wt.% MgSiO3) at 16.5 GPa and 1700 °C, MgSiO3 diffusivity in perovskite saturated KMCH (K2Mg(CO3)2 × 2H2O + 31.7 wt.% MgSiO3) and HM (H2O + 75.7 wt.% MgSiO3) melts at 24 GPa and 1500 °C were determined experimentally using a scaled-up version of a Kawai-type multi-anvil apparatus. During a diffusion experiment, silicate saturation was maintained at different levels in the two temperature regions by placing the diffusion cell in the thermal gradient of 20 °C/mm. The diffusivity was computed from the total mass of silicate transported from “hot” to the “cold” region during the course of an experiment. At given conditions silicate diffusivities were estimated to be DKMCMg2SiO4=2×10-9 m/s, DKMCHMgSiO3=4×10-9 m/s, and DHMMgSiO3=5×10-8 m/s. Using obtained diffusivities we estimated possible migration rates of dispersed melt inclusion in the deep mantle by means of dissolution-precipitation considering different driving forces. The rates of melt migration driven by the lateral thermal gradient of 1 °C/km in the mantle plume range from 4 × 10-8 to 8 × 10-7 m/year. This means that during plume ascent time of about 50 Ma, the melt can be moved by 2-40 m. These values clearly demonstrate that the thermal gradient is very weak driving force in terms of melt segregation in the deep mantle. On the other hand, at typical mantle stress of 1 MPa and droplet size of 100 μm the migration rates of the HM, KMCH and KMC melts are estimated to be 22.5, 0.9 and 0.2 m/year, respectively, which are 2-3 orders of magnitude faster than ascent rate of the mantle plume. This implies that all melt droplets on the way of ascending plume would be entrapped by the stressed zone in front of plume and accumulated in the plume head. This mechanism may explain segregation of mantle magmas with the source regions deeper than 150-250 km, such as kimberlites.

  7. Where's the glass? Biomarkers, molecular clocks, and microRNAs suggest a 200-Myr missing Precambrian fossil record of siliceous sponge spicules

    NASA Astrophysics Data System (ADS)

    Sperling, E. A.; Robinson, J.; Pisani, D.; Peterson, K.

    2010-12-01

    The earliest evidence for animal life comes from the fossil record of 24-isopropylcholestane, a sterane found in Cryogenian deposits, and whose precursors are found in modern demosponges, but not choanoflagellates, calcareans, hexactinellids, or eumetazoans. However, many modern demosponges are also characterized by the presence of siliceous spicules, and there are no convincing demosponge spicules in strata older than the Cambrian. This temporal disparity highlights a problem with our understanding of the Precambrian fossil record - either these supposed demosponge-specific biomarkers were derived from the sterols of some other organism and are simply retained in modern demosponges, or spicules do not primitively characterize crown-group demosponges. Resolving this issue requires resolving the phylogenetic placement of another group of sponges, the hexactinellids, which not only make a spicule thought to be homologous to the spicules of demosponges, but also make their first appearance near the Precambrian/Cambrian boundary. Using two independent analytical approaches and data sets - traditional molecular phylogenetic analyses and the presence or absence of specific microRNA genes - we show that demosponges are monophyletic, and that hexactinellids are their sister group (together forming the Silicea). Thus, spicules must have evolved before the last common ancestor of all living siliceans, suggesting the presence of a significant gap in the silicean spicule fossil record. Molecular divergence estimates date the origin of this last common ancestor well within the Cryogenian, consistent with the biomarker record, and strongly suggests that siliceous spicules were present during the Precambrian but were not preserved.

  8. Where's the glass? Biomarkers, molecular clocks, and microRNAs suggest a 200-Myr missing Precambrian fossil record of siliceous sponge spicules.

    PubMed

    Sperling, E A; Robinson, J M; Pisani, D; Peterson, K J

    2010-01-01

    The earliest evidence for animal life comes from the fossil record of 24-isopropylcholestane, a sterane found in Cryogenian deposits, and whose precursors are found in modern demosponges, but not choanoflagellates, calcareans, hexactinellids, or eumetazoans. However, many modern demosponges are also characterized by the presence of siliceous spicules, and there are no convincing demosponge spicules in strata older than the Cambrian. This temporal disparity highlights a problem with our understanding of the Precambrian fossil record--either these supposed demosponge-specific biomarkers were derived from the sterols of some other organism and are simply retained in modern demosponges, or spicules do not primitively characterize crown-group demosponges. Resolving this issue requires resolving the phylogenetic placement of another group of sponges, the hexactinellids, which not only make a spicule thought to be homologous to the spicules of demosponges, but also make their first appearance near the Precambrian/Cambrian boundary. Using two independent analytical approaches and data sets--traditional molecular phylogenetic analyses and the presence or absence of specific microRNA genes--we show that demosponges are monophyletic, and that hexactinellids are their sister group (together forming the Silicea). Thus, spicules must have evolved before the last common ancestor of all living siliceans, suggesting the presence of a significant gap in the silicean spicule fossil record. Molecular divergence estimates date the origin of this last common ancestor well within the Cryogenian, consistent with the biomarker record, and strongly suggests that siliceous spicules were present during the Precambrian but were not preserved.

  9. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates

    NASA Astrophysics Data System (ADS)

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; D'Espinose de Lacaillerie, Jean-Baptiste

    2016-03-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured.

  10. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates

    PubMed Central

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; d'Espinose de Lacaillerie, Jean-Baptiste

    2016-01-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured. PMID:27009966

  11. Origin of hydrous alkali feldspar-silica intergrowth in spherulites from intra-plate A2-type rhyolites at the Jabal Shama, Saudi Arabia

    NASA Astrophysics Data System (ADS)

    Surour, Adel A.; El-Nisr, Said A.; Bakhsh, Rami A.

    2016-03-01

    Miocene rhyolites (19.2 ± 0.9 Ma) at the Jabal Shama in western Saudi Arabia represent an example of rift-related silicic volcanism that took place during the formation of the Red Sea. They mostly consist of tuffaceous varieties with distinct flow banding, and pea-sized spherulites, obsidian and perlitized rhyolite tuffs. Although they have the geochemical signature of A2-type rhyolites, these silicic rocks are not typically alkaline but alkali-calcic to calc-alkaline. They developed in a within-plate regime and possibly derived from a recycled mafic subducted slab in depleted sub-continental mantle beneath the western Arabian plate. The Jabal Shama rhyolites are younger in age than their Miocene counterparts in Yemen and Ethiopia. The Jabal Shama spherulites consist of hydrous alkali feldspar-silica radial intergrowths with an occasional brown glass nucleus. Carbonate- and glass-free spherulites give up to 4.45 wt% L.O.I. The hydrous nature of these silicates and the absence of magnetite in the spherulites is a strong indication of oxidizing conditions. The spherulites contain hydrous feldspars with up to ∼6 wt% H2O, and they develop by diffusion and devitrification of glass in the rhyolite tuff at ∼800 °C. Owing to higher undercooling due to supersaturation, the radial hydrous phases within spherulites might grow faster and led to coagulation. The polygonal contacts between spherulites and the ∼120° dihedral angle suggest solid-state modification and recrystallization as the process of devitrification proceeds as low as ∼300 °C. The sum of FeO + MgO is positively correlated with total alkalies along with magnetite oxidation in the matrix to Fe-oxyhydroxides, and to the incorporation of OH- into silicates within the spehrulites themselves. Structural H2O in glass of the Jabal Shama perlite (obsidian) is considerable (∼9-12 wt%) with 3.72-5.6 wt% L.O.I. of the whole-rock. The presence of deleterious silica impurities would lower the ore grade due to

  12. Basic Research on Oxynitride Glasses.

    DTIC Science & Technology

    1982-07-01

    silicates, yttrium-aluminum silicates, or nitrogen apatite (Y4 Si4OllN 2 ). Substitution of nitrogen for oxygen in the crystal- line yttrium silicates may... oxygen in a wide variety of silicate system to produce oxynitride glasses with improved properties. Nitrogen contents as high as 12 at% have been...transition temperature, hardness, fracture toughness, and density all increase, and the thermal expansion coefficient decreases with increased nitrogen content

  13. 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.

  14. Performance of Straight Steel Fibres Reinforced Alkali Activated Concrete

    NASA Astrophysics Data System (ADS)

    Faris, Meor Ahmad; Bakri Abdullah, Mohd Mustafa Al; Nizar Ismail, Khairul; Muniandy, Ratnasamy; Putra Jaya, Ramadhansyah

    2016-06-01

    This paper focus on the performance of alkali activated concrete produced by using fly ash activated by sodium silicate and sodium hydroxide solutions. These alkali activated concrete were reinforced with straight steel fibres with different weight percentage starting from 0 % up to 5 %. Chemical composition of raw material in the production alkali activated concrete which is fly ash was first identified by using X-ray fluorescence. Results reveal there have an effect of straight steel fibres inclusion to the alkali activated concrete. Highest compressive strength of alkali activated concrete which is 67.72 MPa was obtained when 3 % of straight fibres were added. As well as flexural strength, highest flexural strength which is 6.78 MPa was obtained at 3 % of straight steel fibres inclusions.

  15. Bonding strength of resin cement to silicate glass ceramics for dental CAD/CAM systems is enhanced by combination treatment of the bonding surface.

    PubMed

    Shimakura, Yusuke; Hotta, Yasuhiro; Fujishima, Akihiro; Kunii, Jun; Miyazaki, Takashi; Kawawa, Tadaharu

    2007-09-01

    To increase the bond strength of CAD/CAM-fabricated, leucite-reinforced glass ceramics with a resin cement, the effects of the following were investigated: surface modification by tribochemical (TBC) treatment, followed by combined application of a silane coupling agent and a functional monomer as a primer. Bond strength was evaluated by a shear bond test. It was found that a silane coupling agent was useful for all the surfaces, particularly for the TBC-treated surface. This was because of the presence of a silica layer on the modified surface. The combination of a silane coupling agent and a functional monomer on the TBC surface allowed marked improvement in bonding, whereby the bonding endured 20,000 cycles of thermal cycling. Therefore, TBC treatment in combination with a silane coupling agent and a functional monomer as a primer substantially increased the bond strength of CAD/CAM-fabricated glass ceramics with resin cement, if the treatment conditions were appropriate.

  16. 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.

  17. 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.

  18. Local modification of speed of sound in lithium alumino-silicate glass/ceramic material by pulsed laser irradiation and thermal processing.

    PubMed

    Kim, Y; Helvajian, H

    2013-11-21

    Glass and glass/ceramics are now used in modern devices with increasing frequency. A list of the notable material properties commonly will not include a capability to guide ultrasonic waves. The photosensitive glass ceramics (PSGCs), an old invention with recent technological rebirth, may enable this capability. The speed of sound (SoS) has been measured at an ultrasonic frequency (75 MHz) in a commercially available PSGC material. The measurements are made using a pulse echo time-of-flight (TOF) technique as a function of UV laser exposure and thermal processing. The measured increase in the SoS correlates with the density of crystalline matter present, which can be metered by controlling the exposure dose. For the Li2SiO3 crystalline phase, the results show the shear (transverse) wave mode velocity can be increased by 4.8% relative to an unexposed area where no crystalline matter exists. The maximum change in velocity for the longitudinal (compressional) wave mode is only 2%. However, by altering the thermal processing protocols to grow the high temperature Li2Si2O5 crystalline phase, the measured change in the SoS increases to 11% and 9%, respectively. These results permit the volumetric patterning of delay lines by laser direct write techniques for generating complex profile ultrasonic wave patterns. Moreover, by patterned 3D shaping (i.e., photostructuring), ultrasound energy can be harnessed and utilized to advantage.

  19. Amorphous Silicates in Primitive Meteoritic Materials: Acfer 094 and IDPs

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Nakamura-Messenger, K.; Messenger, S.; Walker, Robert M.

    2009-01-01

    The abundance of presolar grains is one measure of the primitive nature of meteoritic materials. Presolar silicates are abundant in meteorites whose matrices are dominated by amorphous silicates such as the unique carbonaceous chondrite Acfer 094. Presolar silicates are even more abundant in chondritic-porous interplanetary dust particles (CP-IDPs). Amorphous silicates in the form of GEMS (glass with embedded metal and sulfides) grains are a major component of CP IDPs. We are studying amorphous silicates in Acfer 094 matrix in order to determine whether they are related to the GEMS grains in CPIDPs

  20. 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 ...

  1. Alteration of alkali reactive aggregates autoclaved in different alkali solutions and application to alkali-aggregate reaction in concrete (II) expansion and microstructure of concrete microbar

    SciTech Connect

    Lu Duyou . E-mail: duyoulu@njut.edu.cn; Mei Laibao; Xu Zhongzi; Tang Mingshu; Mo Xiangyin; Fournier, Benoit

    2006-06-15

    The effect of the type of alkalis on the expansion behavior of concrete microbars containing typical aggregate with alkali-silica reactivity and alkali-carbonate reactivity was studied. The results verified that: (1) at the same molar concentration, sodium has the strongest contribution to expansion due to both ASR and ACR, followed by potassium and lithium; (2) sufficient LiOH can completely suppress expansion due to ASR whereas it can induce expansion due to ACR. It is possible to use the duplex effect of LiOH on ASR and ACR to clarify the ACR contribution when ASR and ACR may coexist. It has been shown that a small amount of dolomite in the fine-grained siliceous Spratt limestone, which has always been used as a reference aggregate for high alkali-silica reactivity, might dedolomitize in alkaline environment and contribute to the expansion. That is to say, Spratt limestone may exhibit both alkali-silica and alkali-carbonate reactivity, although alkali-silica reactivity is predominant. Microstructural study suggested that the mechanism in which lithium controls ASR expansion is mainly due to the favorable formation of lithium-containing less-expansive product around aggregate particles and the protection of the reactive aggregate from further attack by alkalis by the lithium-containing product layer.

  2. Alteration of alkali reactive aggregates autoclaved in different alkali solutions and application to alkali-aggregate reaction in concrete

    SciTech Connect

    Lu Duyou; Xu Zhongzi; Tang Mingshu; Fournier, Benoit

    2006-06-15

    Surface alteration of typical aggregates with alkali-silica reactivity and alkali-carbonate reactivity, i.e. Spratt limestone (SL) and Pittsburg dolomitic limestone (PL), were studied by XRD and SEM/EDS after autoclaving in KOH, NaOH and LiOH solutions at 150 deg. C for 150 h. The results indicate that: (1) NaOH shows the strongest attack on both ASR and ACR aggregates, the weakest attack is with LiOH. For both aggregates autoclaved in different alkali media, the crystalline degree, morphology and distribution of products are quite different. More crystalline products are formed on rock surfaces in KOH than that in NaOH solution, while almost no amorphous product is formed in LiOH solution; (2) in addition to dedolomitization of PL in KOH, NaOH and LiOH solutions, cryptocrystalline quartz in PL involves in reaction with alkaline solution and forms typical alkali-silica product in NaOH and KOH solutions, but forms lithium silicate (Li{sub 2}SiO{sub 3}) in LiOH solution; (3) in addition to massive alkali-silica product formed in SL autoclaved in different alkaline solutions, a small amount of dolomite existing in SL may simultaneously dedolomitize and possibly contribute to expansion; (4) it is promising to use the duplex effect of LiOH on ASR and ACR to distinguish the alkali-silica reactivity and alkali-carbonate reactivity of aggregate when both ASR and ACR might coexist.

  3. Chemically bonded phospho-silicate ceramics

    DOEpatents

    Wagh, Arun S.; Jeong, Seung Y.; Lohan, Dirk; Elizabeth, Anne

    2003-01-01

    A chemically bonded phospho-silicate ceramic formed by chemically reacting a monovalent alkali metal phosphate (or ammonium hydrogen phosphate) and a sparsely soluble oxide, with a sparsely soluble silicate in an aqueous solution. The monovalent alkali metal phosphate (or ammonium hydrogen phosphate) and sparsely soluble oxide are both in powder form and combined in a stochiometric molar ratio range of (0.5-1.5):1 to form a binder powder. Similarly, the sparsely soluble silicate is also in powder form and mixed with the binder powder to form a mixture. Water is added to the mixture to form a slurry. The water comprises 50% by weight of the powder mixture in said slurry. The slurry is allowed to harden. The resulting chemically bonded phospho-silicate ceramic exhibits high flexural strength, high compression strength, low porosity and permeability to water, has a definable and bio-compatible chemical composition, and is readily and easily colored to almost any desired shade or hue.

  4. Thermal analysis of reactions in soda-lime silicate glass batches containing melting accelerants: I, one- and two-component systems

    SciTech Connect

    Hong, Kug Sun; Speyer, R.F. )

    1993-03-01

    To identify each glass melting reaction in a multicomponent system, one-component and two-component reaction processes were studied using DTA, TGA, and XRD. Two-component mixtures were prepared by choosing pairs in the same ratio as in a commercial container glass batch composition (sand-soda ash-calcite-dolomite-feldspar). The presence of silica in the silicia-calcite system decreased the termination temperature of the decomposition of calcite, but did not alter the onset of decomposition. Similar behavior was found in the dolomite-silica system. A double carbonate (Na[sub 2]Ca(CO[sub 3])[sub 2]) formed via solid-state reaction in the calcite-soda ash system, and metasilicate/disilicate phases were detected during the fusion process in the soda ash-silica system. The effects of reaction accelerant additions in the soda ash-silica system were investigated using 1 wt% additions of sodium sulfate, sodium nitrate, and sodium chloride. Sodium chloride was the most effective melting accelerant, lowering the termination temperature of CO[sub 2] release by [approximately]80C compared with the soda ash-silica system with no additives. NaCl additions caused complete reaction and/or fusion of Na[sub 2]CO[sub 3] prior to its melting temperature. Sodium sulfate additions acted to suppress metasilicate/disilicate formation by coating quartz grains and shifted consequent CO[sub 2] release to higher temperature.

  5. Thermally responsive aqueous silicate mixtures and use thereof

    SciTech Connect

    Smith, W.H.; Vinson, E.F.

    1987-02-03

    A method is described of plugging or sealing a zone in a subterranean formation comprising: (a) contacting the zone with an aqueous silicate composition consisting essentially of (i) an aqueous solution containing an alkali metal silicate; and, (ii) a thermally responsive gelation activator selected from the group consisting of lactose, dextrose, fructose, galactose, mannose, mantose, xylose and mixtures thereof; and (b) activating the gelation activator in response to a thermal change in the composition within the formation whereby the silicate composition is caused to form a gel in the zone.

  6. Multiple Ca(2+) environments in silicate glasses by high-resolution (43)Ca MQMAS NMR technique at high and ultra-high (21.8 T) magnetic fields.

    PubMed

    Shimoda, Keiji; Tobu, Yasuhiro; Shimoikeda, Yuichi; Nemoto, Takahiro; Saito, Koji

    2007-05-01

    We here show the (43)Ca 5QMAS NMR spectra at high field (16.4 T) and the first 7QMAS spectrum at ultra-high field (21.8 T) for geologically important Ca-containing glasses. The high-resolution MQMAS spectra present a clear evidence of multiple Ca sites in the amorphous structures that have never been identified by other analytical methods. The present study suggests that the Ca(2+) ions are mainly in 7- and 8-fold coordination sites. This will offer valuable insights for dynamic properties of magmatic liquids. The MQMAS NMR technique at high magnetic field is a unique tool to understand the detailed structural information on a specific element in solids including organic and inorganic compounds.

  7. Glass-silicon column

    DOEpatents

    Yu, Conrad M.

    2003-12-30

    A glass-silicon column that can operate in temperature variations between room temperature and about 450.degree. C. The glass-silicon column includes large area glass, such as a thin Corning 7740 boron-silicate glass bonded to a silicon wafer, with an electrode embedded in or mounted on glass of the column, and with a self alignment silicon post/glass hole structure. The glass/silicon components are bonded, for example be anodic bonding. In one embodiment, the column includes two outer layers of silicon each bonded to an inner layer of glass, with an electrode imbedded between the layers of glass, and with at least one self alignment hole and post arrangement. The electrode functions as a column heater, and one glass/silicon component is provided with a number of flow channels adjacent the bonded surfaces.

  8. Silicate Inclusions in the Kodaikanal IIE Iron Meteorite

    NASA Technical Reports Server (NTRS)

    Kurat, G.; Varela, M. E.; Zinner, E.

    2005-01-01

    Silicate inclusions in iron meteorites display an astonishing chemical and mineralogical variety, ranging from chondritic to highly fractionated, silica- and alkali-rich assemblages. In spite of this, their origin is commonly considered to be a simple one: mixing of silicates, fractionated or unfractionated, with metal. The latter had to be liquid in order to accommodate the former in a pore-free way which all models accomplish by assuming shock melting. II-E iron meteorites are particularly interesting because they contain an exotic zoo of silicate inclusions, including some chemically strongly fractionated ones. They also pose a formidable conundrum: young silicates are enclosed by very old metal. This and many other incompatibilities between models and reality forced the formulation of an alternative genetic model for irons. Here we present preliminary findings in our study of Kodaikanal silicate inclusions.

  9. Carbon solution and partitioning between metallic and silicate melts in a shallow magma ocean: Implications for the origin and distribution of terrestrial carbon

    NASA Astrophysics Data System (ADS)

    Dasgupta, Rajdeep; Chi, Han; Shimizu, Nobumichi; Buono, Antonio S.; Walker, David

    2013-02-01

    The origin of bulk silicate Earth carbon inventory is unknown and the fate of carbon during the early Earth differentiation and core formation is a missing link in the evolution of the terrestrial carbon cycle. Here we present high pressure (P)-temperature (T) experiments that offer new constraints upon the partitioning of carbon between metallic and silicate melt in a shallow magma ocean. Experiments were performed at 1-5 GPa, 1600-2100 °C on mixtures of synthetic or natural silicates (tholeiitic basalt/alkali basalt/komatiite/fertile peridotite) and Fe-Ni-C ± Co ± S contained in graphite or MgO capsules. All the experiments produced immiscible Fe-rich metallic and silicate melts at oxygen fugacity (fO2) between ˜IW-1.5 and IW-1.9. Carbon and hydrogen concentrations of basaltic glasses and non-glassy quenched silicate melts were determined using secondary ionization mass spectrometry (SIMS) and speciation of dissolved C-O-H volatiles in silicate glasses was studied using Raman spectroscopy. Carbon contents of metallic melts were determined using both electron microprobe and SIMS. Our experiments indicate that at core-forming, reduced conditions, carbon in deep mafic-ultramafic magmas may dissolve primarily as various hydrogenated species but the total carbon storage capacity, although is significantly higher than solubility of CO2 under similar conditions, remains low (<500 ppm). The total carbon content in our reduced melts at graphite saturation increases with increasing melt depolymerization (NBO/T), consistent with recent spectroscopic studies, and modestly with increasing hydration. Carbon behaves as a metal-loving element during core-mantle separation and our experimental DCmetal/silicate varies between ˜4750 and ⩾150 and increases with increasing pressure and decreases with increasing temperature and melt NBO/T. Our data suggest that if only a trace amount of carbon (˜730 ppm C) was available during early Earth differentiation, most of it was

  10. 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

  11. Carbonatite-silicate immiscible melt inclusion in lamprophyre from Kutch, western India: Implication for plume-lithosphere interaction and initiation of Deccan Trap magmatism

    NASA Astrophysics Data System (ADS)

    Ray, Arijit; Paul, Dalim Kumar; Sen, Gautam; Biswas, Sanjib Kumar

    2014-05-01

    Kutch province of western India has undergone repeated rifting and marine transgression events from late Triassic to the late Cretaceous. Magmatic rocks occur in profusion in Kutch Basin. The southern part is characterized by occurrences of thick flows of tholeiitic basalt of Deccan Trap affinity, central part of Kutch Basin has numerous volcanic plugs of alkali basalt which is also considered as member of Deccan Trap, contain thin, discoidal mantle xenoliths of spinel lherzolite and wehrlite composition. Northern Kutch is dominated by suite of alkaline magmatic rocks similar to magmatic rocks of continental rift zone. The alkaline suite contains alkali pyroxenite, theralite, teschenite, basanite, nepheline syenite and kaersutite bearing lamprophyre (Ray et al., 2006, Das et al., 2007, Paul et al., 2008). The newly discovered east-west trending lamprophyre dyke swarm of northern Kutch (Pachham Island) is camptonite in composition and contains kaersutite phenocrysts in large proportion. These kaersutite phencrysts contain immscible melt/glass phases as melt inclusions. The lamprophyre yields an age of ca. 67 Ma.by Ar-Ar method (Sen et al., 2014 in press) synchronous with alkali basalt of central Kutch. The melt inclusions are fundamentally of two types - calciocarbonatite and alkaline silicate melts. We found sphene within carbonatitic melt and the rare mineral rhonite in silicate melt. Petrographic evidence indicates that carbonatite melt always occurs within alkali silicate melt as immiscible fraction. These carbonatite melts are extremely rich in CaCO3 (upto 95%) which contradicts the experimental results of carbonate melt composition (upto 80% CaCO3) in silicate-carbonate immiscible melt pair by Lee and Wyllie. The abundance of wehrlite xenoliths over lherzolite in alkali basalt, petrographic evidence of orthopyroxene to clinopyroxene transformation in wehrlite xenoliths, occurrence of calcite vein in mantle xenoliths indicate carbonatite metasomatism of spinel

  12. Cd{sub 1−x}Mn{sub x}Te ultrasmall quantum dots growth in a silicate glass matrix by the fusion method

    SciTech Connect

    Dantas, Noelio Oliveira; Lima Fernandes, Guilherme de; Almeida Silva, Anielle Christine; Baffa, Oswaldo; Gómez, Jorge Antônio

    2014-09-29

    In this study, we synthesized Cd{sub 1−x}Mn{sub x}Te ultrasmall quantum dots (USQDs) in SiO{sub 2}-Na{sub 2}CO{sub 3}-Al{sub 2}O{sub 3}-B{sub 2}O{sub 3} glass system using the fusion method. Growth of these Cd{sub 1−x}Mn{sub x}Te USQDs was confirmed by optical absorption, atomic force microscopy (AFM), magnetic force microscopy (MFM), scanning transmission electron microscopy (TEM), and electron paramagnetic resonance (EPR) measurements. The blueshift of absorption transition with increasing manganese concentration gives evidence of incorporation of manganese ions (Mn{sup 2+}) in CdTe USQDs. AFM, TEM, and MFM confirmed, respectively, the formation of high quality Cd{sub 1−x}Mn{sub x}Te USQDs with uniformly distributed size and magnetic phases. Furthermore, EPR spectra showed six lines associated to the S = 5/2 spin half-filled d-state, characteristic of Mn{sup 2+}, and confirmed that Mn{sup 2+} are located in the sites core and surface of the CdTe USQD. Therefore, synthesis of high quality Cd{sub 1−x}Mn{sub x}Te USQDs may allow the control of optical and magnetic properties.

  13. Rapid quantitative determination of major and trace elements in silicate rocks and soils employing fused glass discs using wavelength dispersive X-ray fluorescence spectrometry

    NASA Astrophysics Data System (ADS)

    Krishna, A. Keshav; Khanna, Tarun C.; Mohan, K. Rama

    2016-08-01

    This paper introduces a calibration procedure and provides the data achieved for accuracy, precision, reproducibility and the detection limits for major (Si, Al, Fe, Mn, Mg, Ca, Na, K, Ti, P) and trace (Ba, Cr, Cu, Hf, La, Nb, Ni, Pb, Rb, Sr, Ta, Th, U, Y, Zn, Zr) elements in the routine analysis of geological and environmental samples. Forty-two rock and soil reference materials were used to calibrate and evaluate the analytical method using a sequential wavelength dispersive X-ray fluorescence spectrometer. Samples were prepared as fused glass discs and analysis performed with a total measuring time of thirty-one minutes. Another set of twelve independent reference materials were analyzed for the evaluation of accuracy. The detection limits and accuracy obtained for the trace elements (1-2 mg/kg) are adequate both for geochemical exploration and environmental studies. The fitness for purpose of the results was also evaluated by the quality criteria test proposed by the International Global Geochemical Mapping Program (IGCP) from which it can be deduced that the method is adequate considering geochemical mapping application and accuracy obtained is within the expected interval of certified values in most cases.

  14. The effect of boron oxide on the composition, structure, and adsorptivity of glass surfaces

    NASA Astrophysics Data System (ADS)

    Schaut, Robert A.

    Boron oxide has been added to commercial silicate glasses for many years to aid in lowering melting temperatures, lowering thermal expansion, and controlling chemical durability. The fact that simple borate glasses have rather high thermal expansion and low chemical durability attests to the unique influence of boron oxide additions upon the properties of silicate glasses. However, the impact of boron oxide additions upon surface properties of multicomponent borosilicates such as adsorption and reactivity is not yet well understood. In particular, the presence of multiple coordination states for boron is expected to introduce adsorption sites with different acidic or basic behavior, but their existence is yet unproven. To investigate these effects, multicomponent sodium aluminosilicate glasses have been prepared with varying sodium and boron concentrations and drawn into moderately high-surface-area continuous filament fibers. A relatively new technique, boron K-edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy is applied to study the local boron coordination at fracture and melt-derived fiber surfaces of these glasses. This structural information is combined with surface compositional information by X-ray Photoelectron Spectroscopy (XPS) to characterize the local atomic structure of boron at the as-formed glass surface. Finally, this information is used to interpret the adsorptivity of these as-formed and leached surfaces toward short-chain alcohol molecules through a new Inverse Gas Chromatography---Temperature Programmed Desorption (IGC-TPD) experiment. The results clearly show that boron additions to alkali-free glass surfaces introduce a unique adsorption site which is not present on boron-free glass surfaces and is easily removed by leaching in acidic solutions.

  15. Cementitious binders from activated stainless steel refining slag and the effect of alkali solutions.

    PubMed

    Salman, Muhammad; Cizer, Özlem; Pontikes, Yiannis; Snellings, Ruben; Vandewalle, Lucie; Blanpain, Bart; Van Balen, Koen

    2015-04-09

    With an aim of producing high value cementitious binder, stainless steel refining slag containing a high amount of CaO in γ-dicalcium silicate form was activated with NaOH and Na-silicate as well as KOH and K-silicate solutions, followed by steam curing at 80 °C. Higher levels of alkali-silicate in the activating solution resulted in higher cumulative heat suggesting accelerated reaction kinetics. With respect to compressive strength, higher levels of alkali silicate resulted in higher strength and the mortars with Na activator were found to have higher early strength than the ones with K activator. The long term strength was found to be similar, regardless of the alkali metal. Thermogravimetric, QXRD and FTIR analyses showed an increase in the amount of reaction products (C-S-H type) over time, further confirming the reactivity of the crystalline slag. Batch leaching results showed lower leaching of heavy metals and metalloids with K activator compared to the Na activator. These results demonstrate that the alkali type and the ratio of hydroxide to silicates have a significant impact on the hydration and mechanical strength development of the stainless steel slag. The above findings can aid in the recycling and valorization of these type of slags which otherwise end up landfilled.

  16. Properties Of Soda/Yttria/Silica Glasses

    NASA Technical Reports Server (NTRS)

    Angel, Paul W.; Hann, Raiford E.

    1994-01-01

    Experimental study of glass-formation compositional region of soda/ yttria/silicate system and of selected physical properties of glasses within compositional region part of continuing effort to identify glasses with high coefficients of thermal expansion and high softening temperatures, for use as coatings on superalloys and as glass-to-metal seals.

  17. The effect of melt composition on the partitioning of oxidized sulfur between silicate melts and magmatic volatiles

    NASA Astrophysics Data System (ADS)

    Zajacz, Zoltán

    2015-06-01

    Experiments were conducted at 500 MPa and 1240 °C in a piston cylinder apparatus to assess the effect of melt composition on the melt/volatile partition coefficient of sulfur (DSmelt/volatile) , which was used as a measure of the silicate melt's capacity to dissolve oxidized sulfur species. Iron-free, three- and four-component silicate melts were equilibrated with H2O-S fluids with sulfur concentrations ⩽2 mol% at an oxygen fugacity imposed by the Re-ReO2 buffer (1.4 log units above the Ni-NiO buffer). At these conditions, SO2 (S4+) is predicted to be the dominant sulfur species in the volatile phase and sulfate (S6+) is the dominant sulfur species in the silicate melt. The values of DSmelt /volatile were calculated by mass balance. The results show that DSmelt /volatile values increase exponentially with decreasing the degree of polymerization of the silicate melt structure. For example, in calcium-aluminosilicate melts, DSmelt /volatile changes from 0.005 to 0.3 as the degree of melt polymerization changes from the equivalent of a rhyolite to the equivalent of a basalt. At a constant degree of melt polymerization, DSmelt /volatile in equilibrium with sodium-aluminosilicate (NAS) melts is more than an order of magnitude higher than in equilibrium with calcium-aluminosilicate (CAS) melts, and more than two orders of magnitude higher than in equilibrium with magnesium-aluminosilicate (MAS) melts. The value of DSmelt /volatile changes from 0.014 in MAS glasses to 3.4 in NAS glasses for the most depolymerized compositions in each series. Potassium has a similar effect on sulfate dissolution to that of Na. The variation of DSmelt /volatile in equilibrium with various calcium-sodium aluminosilicate (CNAS), magnesium-sodium aluminosilicate (MNAS) and magnesium-potassium aluminosilicate (MKAS) melts indicates that alkalis are only available for sulfate complexation when they are present in excess compared to the required amount to charge balance for the Si4+ to Al3

  18. Effect of different glasses in glass bonded zeolite

    SciTech Connect

    Lewis, M.A.; Ackerman, J.P.; Verma, S.

    1995-05-01

    A mineral waste form has been developed for chloride waste salt generated during the pyrochemical treatment of spent nuclear fuel. The waste form consists of salt-occluded zeolite powders bound within a glass matrix. The zeolite contains the salt and immobilizes the fission products. The zeolite powders are hot pressed to form a mechanically stable, durable glass bonded zeolite. Further development of glass bonded zeolite as a waste form requires an understanding of the interaction between the glass and the zeolite. Properties of the glass that enhance binding and durability of the glass bonded zeolite need to be identified. Three types of glass, boroaluminosilicate, soda-lime silicate, and high silica glasses, have a range of properties and are now being investigated. Each glass was hot pressed by itself and with an equal amount of zeolite. MCC-1 leach tests were run on both. Soda-lime silicate and high silica glasses did not give a durable glass bonded zeolite. Boroaluminosilicate glasses rich in alkaline earths did bind the zeolite and gave a durable glass bonded zeolite. Scanning electron micrographs suggest that the boroaluminosilicate glasses wetted the zeolite powders better than the other glasses. Development of the glass bonded zeolite as a waste form for chloride waste salt is continuing.

  19. Photoactive transparent nano-crystalline glass-ceramic for remazole red dye degradation

    SciTech Connect

    Gad-Allah, Tarek A.; Margha, Fatma H.

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ► Preparation and characterization of novel transparent nanocrystalline glass-ceramic. ► Precipitation of photoactive phases by using controlled heat-treatment. ► Conservation of transparency along with photoactivity. ► Using the prepared nanocrystalline glass-ceramic in water purification. -- Abstract: Transparent glass ceramic material was prepared from alkali-borosilicate glass containing titania by proper heat treatment scheme. The prepared samples were characterized using differential thermal analysis, X-ray diffraction, transmission electron microscope, selected area electron diffraction and UV–visible spectroscopy. The applied heat treatment program allowed the crystallization of nano-crystalline anatase, rutile, barium titanate, titanium borate and silicate phases while maintaining the transparency. The precipitated nano-crystalline anatase and rutile phases were responsible for the observed high photocatalytic activity of the prepared samples. Samples of 24.29 and 32.39 TiO{sub 2} wt% showed better efficiency for the decolorization of remazole red dye compared with commercial-TiO{sub 2} used in preparation of glass-ceramic. The reuse of prepared glass-ceramic photocatalyst with nearly same efficiency for different times was also proved.

  20. Evolution of carbonated melt to alkali basalt in the South China Sea

    NASA Astrophysics Data System (ADS)

    Zhang, Guo-Liang; Chen, Li-Hui; Jackson, Matthew G.; Hofmann, Albrecht W.

    2017-01-01

    CO2 is considered to play a key role in the melting of the deep upper mantle, and carbonated silicate melts have been widely predicted by partial melting experiments to exist at mantle depths of greater than 80 km. However, such melts have not been shown to exist in nature. Thus, the relationship between CO2 and the origin of silicate melts is highly speculative. Here we present geochemical analyses of rocks sampled from the South China Sea, at the Integrated Ocean Discovery Program Site U1431. We identify natural carbonated silicate melts, which are enriched in light rare earth elements and depleted in Nb and Ta, and show that they were continuously transformed to alkali basalts that are less enriched in light rare earth elements and enriched in Nb and Ta. This shows that carbonated silicate melts can survive in the shallow mantle and penetrate through the hot asthenosphere. Carbonated silicate melts were converted to alkali basaltic melts through reactions with the lithospheric mantle, during which precipitation of apatite accounts for reduction of light rare earth elements and genesis of positive Nb-Ta anomalies. We propose that an extremely thin lithosphere (less than 20 km in the South China Sea) facilitates extrusion of the carbonated silicate melts, whereas a thickened lithosphere tends to modify carbonated silicate melt to alkali basalt.

  1. Activity composition relationships in silicate melts. Final report

    SciTech Connect

    Glazner, A.F.

    1990-12-31

    Equipment progress include furnace construction and electron microprobe installation. The following studies are underway: phase equilibria along basalt-rhyolite mixing line (olivine crystallization from natural silicic andensites, distribution of Fe and Mg between olivine and liquid, dist. of Ca and Na between plagioclase and liquid), enthalpy-composition relations in magmas (bulk heat capacity of alkali basalt), density model for magma ascent and contamination, thermobarometry in igneous systems (olivine/plagioclase phenocryst growth in Quat. basalt), high-pressure phase equilibria of alkali basalt, basalt-quartz mixing experiments, phase equilibria of East African basalts, and granitic minerals in mafic magma. (DLC)

  2. Structural Investigation of Alkali Activated Clay Minerals for Application in Water Treatment Systems

    NASA Astrophysics Data System (ADS)

    Bumanis, G.; Bajare, D.; Dembovska, L.

    2015-11-01

    Alkali activation technology can be applied for a wide range of alumo-silicates to produce innovative materials with various areas of application. Most researches focuse on the application of alumo-silicate materials in building industry as cement binder replacement to produce mortar and concrete [1]. However, alkali activation technology offers high potential also in biotechnologies [2]. In the processes where certain pH level, especially alkaline environment, must be ensured, alkali activated materials can be applied. One of such fields is water treatment systems where high level pH (up to pH 10.5) ensures efficient removal of water pollutants such as manganese [3]. Previous investigations had shown that alkali activation technology can be applied to calcined clay powder and aluminium scrap recycling waste as a foam forming agent to create porous alkali activated materials. This investigation focuses on the structural investigation of calcined kaolin and illite clay alkali activation processes. Chemical and mineralogical composition of both clays were determined and structural investigation of alkali activated materials was made by using XRD, DTA, FTIR analysis; the microstructure of hardened specimens was observed by SEM. Physical properties of the obtained material were determined. Investigation indicates the essential role of chemical composition of the clay used in the alkali activation process, and potential use of the obtained material in water treatment systems.

  3. In situ alkali-silica reaction observed by x-ray microscopy

    SciTech Connect

    Kurtis, K.E.; Monteiro, P.J.M.; Brown, J.T.; Meyer-Ilse, W.

    1997-04-01

    In concrete, alkali metal ions and hydroxyl ions contributed by the cement and reactive silicates present in aggregate can participate in a destructive alkali-silica reaction (ASR). This reaction of the alkalis with the silicates produces a gel that tends to imbibe water found in the concrete pores, leading to swelling of the gel and eventual cracking of the affected concrete member. Over 104 cases of alkali-aggregate reaction in dams and spillways have been reported around the world. At present, no method exists to arrest the expansive chemical reaction which generates significant distress in the affected structures. Most existing techniques available for the examination of concrete microstructure, including ASR products, demand that samples be dried and exposed to high pressure during the observation period. These sample preparation requirements present a major disadvantage for the study of alkali-silica reaction. Given the nature of the reaction and the affect of water on its products, it is likely that the removal of water will affect the morphology, creating artifacts in the sample. The purpose of this research is to observe and characterize the alkali-silica reaction, including each of the specific reactions identified previously, in situ without introducing sample artifacts. For observation of unconditioned samples, x-ray microscopy offers an opportunity for such an examination of the alkali-silica reaction. Currently, this investigation is focusing on the effect of calcium ions on the alkali-silica reaction.

  4. Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

    NASA Technical Reports Server (NTRS)

    Day, Delbert E.; Ray, Chandra S.

    2003-01-01

    This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one1 of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on earth (1g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials. The classical theories for nucleation and crystal growth for a glass or melt do not contain any parameter that is directly dependent upon the g-value, so it is not readily apparent why glasses prepared in microgravity should be

  5. Synergistic capture mechanisms for alkali and sulphur species from combustion. Quarterly report No. 10, December 1992--February 1993

    SciTech Connect

    Peterson, T.W.; Shadman, F.; Wendt, J.O.L.; Wu, Baochun

    1993-07-26

    A number of sorbents with alumina-silicate base and sulfur capturing active sites have been developed for simultaneous removal of alkali metal compounds and sulfur dioxide. Current report will focus on bauxite sorbents, which includes experiments on sulfur dioxide absorption, alkali capturing and alkali/sulfur absorption simultaneously by bauxite-based sorbents. The alkali compound used here is sodium chloride. Experiments show an effective adsorption of sulfur or alkali separately, and the combined adsorption of alkali/sulfur. Atomic absorption analysis of reaction products shows that there is a much higher sodium content in the combined reaction products than that of the single reaction of alkali absorption by bauxite. Further X-ray diffraction analysis shows that there is sodium sulfate in the final products of simultaneous reaction, which indicates the formation and then condensation of sodium sulfate in the reaction system.

  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. Understanding the composition-structure-bioactivity relationships in diopside (CaO·MgO·2SiO₂)-tricalcium phosphate (3CaO·P₂O₅) glass system.

    PubMed

    Kapoor, Saurabh; Semitela, Ângela; Goel, Ashutosh; Xiang, Ye; Du, Jincheng; Lourenço, Ana H; Sousa, Daniela M; Granja, Pedro L; Ferreira, José M F

    2015-03-01

    The present work is an amalgamation of computation and experimental approach to gain an insight into composition-structure-bioactivity relationships of alkali-free bioactive glasses in the CaO-MgO-SiO2-P2O5 system. The glasses have been designed in the diopside (CaO·MgO·2SiO2; Di)-tricalcium phosphate (3CaO·P2O5; TCP) binary join by varying the Di/TCP ratio. The melt-quenched glasses have been investigated for their structure by molecular dynamic (MD) simulations as well as by nuclear magnetic resonance spectroscopy (NMR). In all the investigated glasses silicate and phosphate components are dominated by Q(2) (Si) and Q(0) (P) species, respectively. The apatite forming ability of the glasses was investigated using X-ray diffraction (XRD), infrared spectroscopy after immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1 h and 14 days, while their chemical degradation has been studied in Tris-HCl in accordance with ISO 10993-14. All the investigated glasses showed good bioactivity without any substantial variation. A significant statistical increase in metabolic activity of human mesenchymal stem cells (hMSCs) when compared to the control was observed for Di-60 and Di-70 glass compositions under both basal and osteogenic conditions.

  8. Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: Application to a nuclear glass specimen altered 25 years in a granitic environment

    SciTech Connect

    Gin, Stephane; Ryan, Joseph V.; Schreiber, Daniel K.; Neeway, James J.; Cabie, M.

    2013-04-08

    Here, we report and discuss results of atom probe tomography (APT) and energy-filtered transmission electron microscopy (EFTEM) applied to a borosilicate glass sample of nuclear interest altered for nearly 26 years at 90°C in a confined granitic medium in order to better understand the rate-limiting mechanisms under conditions representative of a deep geological repository for vitrified radioactive waste. The APT technique allows the 3D reconstruction of the elemental distribution at the reactive interphase with sub-nanometer precision. Profiles of the B distribution at pristine glass/hydrated glass interface obtained by different techniques are compared to show the challenge of accurate measurements of diffusion profiles at this buried interface on the nanometer length scale. Our results show that 1) Alkali from the glass and hydrogen from the solution exhibit anti-correlated 15 ± 3 nm wide gradients located between the pristine glass and the hydrated glass layer, 2) boron exhibits an unexpectedly sharp profile located just at the outside of the alkali/H interdiffusion layer; this sharp profile is more consistent with a dissolution front than a diffusion-controlled release of boron. The resulting apparent diffusion coefficients derived from the Li and H profiles are DLi = 1.5 × 10-22 m2.s-1 and DH = 6.8 × 10-23 m2.s-1. These values are around two orders of magnitude lower than those observed at the very beginning of the alteration process, which suggests that interdiffusion is slowed at high reaction progress by local conditions that could be related to the porous structure of the interphase. As a result, the accessibility of water to the pristine glass could be the rate-limiting step in these conditions. More generally, these findings strongly support the importance of interdiffusion coupled with hydrolysis reactions of the silicate network on the long-term dissolution

  9. Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: Application to a nuclear glass specimen altered 25 years in a granitic environment

    DOE PAGES

    Gin, Stephane; Ryan, Joseph V.; Schreiber, Daniel K.; ...

    2013-04-08

    Here, we report and discuss results of atom probe tomography (APT) and energy-filtered transmission electron microscopy (EFTEM) applied to a borosilicate glass sample of nuclear interest altered for nearly 26 years at 90°C in a confined granitic medium in order to better understand the rate-limiting mechanisms under conditions representative of a deep geological repository for vitrified radioactive waste. The APT technique allows the 3D reconstruction of the elemental distribution at the reactive interphase with sub-nanometer precision. Profiles of the B distribution at pristine glass/hydrated glass interface obtained by different techniques are compared to show the challenge of accurate measurements ofmore » diffusion profiles at this buried interface on the nanometer length scale. Our results show that 1) Alkali from the glass and hydrogen from the solution exhibit anti-correlated 15 ± 3 nm wide gradients located between the pristine glass and the hydrated glass layer, 2) boron exhibits an unexpectedly sharp profile located just at the outside of the alkali/H interdiffusion layer; this sharp profile is more consistent with a dissolution front than a diffusion-controlled release of boron. The resulting apparent diffusion coefficients derived from the Li and H profiles are DLi = 1.5 × 10-22 m2.s-1 and DH = 6.8 × 10-23 m2.s-1. These values are around two orders of magnitude lower than those observed at the very beginning of the alteration process, which suggests that interdiffusion is slowed at high reaction progress by local conditions that could be related to the porous structure of the interphase. As a result, the accessibility of water to the pristine glass could be the rate-limiting step in these conditions. More generally, these findings strongly support the importance of interdiffusion coupled with hydrolysis reactions of the silicate network on the long-term dissolution rate, contrary to what has been suggested by recent interfacial dissolution

  10. 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.

  11. 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.

  12. Loss of halogens from crystallized and glassy silicic volcanic rocks

    USGS Publications Warehouse

    Noble, D.C.; Smith, V.C.; Peck, L.C.

    1967-01-01

    One hundred and sixty-four F and Cl analyses of silicic welded tuffs and lavas and glass separates are presented. Comparison of the F and Cl contents of crystallized rocks with those of nonhydrated glass and hydrated glassy rocks from the same rock units shows that most of the halogens originally present were lost on crystallization. An average of about half of the F and four-fifths of the Cl originally present was lost. Analyses of hydrated natural glasses and of glassy rocks indicate that in some cases significant amounts of halogens may be removed from or added to hydrated glass through prolonged contact with ground water. The data show that the original halogen contents of the groundmass of a silicic volcanic rock can be reliably determined only from nonhydrated glass. ?? 1967.

  13. XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass

    NASA Technical Reports Server (NTRS)

    Fuss, T.; Mogus-Milankovic, A.; Ray, C. S.; Lesher, C. E.; Youngman, R.; Day, D. E.

    2006-01-01

    The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

  14. 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.

  15. Cumulate Fragments in Silicic Ignimbrites

    NASA Astrophysics Data System (ADS)

    Bachmann, O.; Ellis, B. S.; Wolff, J.

    2014-12-01

    Increasingly, studies are concluding that silicic ignimbrites are the result of the amalgamation of multiple discrete magma batches. Yet the existence of discrete batches presents a conundrum for magma generation and storage; if silicic magma batches are not generated nearly in situ in the upper crust, they must traverse, and reside within, a thermally hostile environment with large temperature gradients, resulting in low survivability in their shallow magmatic hearths. The Snake River Plain (Idaho, USA) is a type example of this 'multi-batch' assembly with ignimbrites containing multiple populations of pyroxene crystals, glass shards, and crystal aggregates. The ubiquitous crystal aggregates hint at a mechanism to facilitate the existence of multiple, relatively small batches of rhyolite in the upper crust. These aggregates contain the same plagioclase, pyroxene, and oxide mineral compositions as single phenocrysts of the same minerals in their host rocks, but they have significantly less silicic bulk compositions and lack quartz and sanidine, which occur as single phenocrysts in the deposits. This implies significant crystallization followed by melt extraction from mushy reservoir margins. The extracted melt then continues to evolve (crystallizing sanidine and quartz) while the melt-depleted margins provide an increasingly rigid and refractory network segregating the crystal-poor batches of magma. The hot, refractory, margins insulate the crystal-poor lenses, allowing (1) extended residence in the upper crust, and (2) preservation of chemical heterogeneities among batches. In contrast, systems that produce cumulates richer in low-temperature phases (quartz, K-feldspars, and/or biotite) favour remelting upon recharge, leading to less segregation of eruptible melt pockets and the formation of gradationally zoned ignimbrites. The occurrence of similar crystal aggregates from a variety of magmatic lineages suggests the generality of this process.

  16. Trace element studies of silicate-rich inclusions in the Guin (UNGR) and Kodaikanal (IIE) iron meteorites

    NASA Astrophysics Data System (ADS)

    Kurat, Gero; Zinner, Ernst; Varela, Maria Eugenia

    2007-08-01

    A devitrified glass inclusion from the Guin (UNGR) iron consists of cryptocrystalline feldspars, pyroxenes, and silica and is rich in SiO2, Al2O3, and Na2O. It contains a rutile grain and is in contact with a large Cl apatite. The latter is very rich in rare earth elements (REEs) (˜80 × CI), which display a flat abundance pattern, except for Eu and Yb, which are underabundant. The devitrified glass is very poor in REEs (<0.1 × CI), except for Eu and Yb, which have positive abundance anomalies. Devitrified glass and Cl apatite are out of chemical equilibrium and their complementary REE patterns indicate a genesis via condensation under reducing conditions. Inclusion 1 in the Kodaikanal (IIE) iron consists of glass only, whereas inclusion 2 consists of clinopyroxene, which is partly overgrown by low-Ca pyroxene, and apatite embedded in devitrified glass. All minerals are euhedral or have skeletal habits indicating crystallization from the liquid precursor of the glass. Pyroxenes and the apatite are rich in trace elements, indicating crystallization from a liquid that had 10-50 × CI abundances of REEs and refractory lithophile elements (RLEs). The co-existing glass is poor in REEs (˜0.1-1 × CI) and, consequently, a liquid of such chemical composition cannot have crystallized the phenocrysts. Glasses have variable chemical compositions but are rich in SiO2, Al2O3, Na2O, and K2O as well as in HFSEs, Be, B, and Rb. The REE abundance patterns are mostly flat, except for the glass-only inclusion, which has heavy rare earth elements (HREEs) > light rare earth elements (LREEs) and deficits in Eu and Yb—an ultrarefractory pattern. The genetic models suggested so far cannot explain what is observed and, consequently, we offer a new model for silicate inclusion formation in IIE and related irons. Nebular processes and a relationship with E meteorites (Guin) or Ca-Al-rich inclusions (CAIs) (Kodaikanal) are indicated. A sequence of condensation (CaS, TiN or refractory

  17. Spectroscopic study of biologically active glasses

    NASA Astrophysics Data System (ADS)

    Szumera, M.; Wacławska, I.; Mozgawa, W.; Sitarz, M.

    2005-06-01

    It is known that the chemical activity phenomenon is characteristic for some inorganic glasses and they are able to participate in biological processes of living organisms (plants, animals and human bodies). An example here is the selective removal of silicate-phosphate glass components under the influence of biological solutions, which has been applied in designing glasses acting as ecological fertilizers of controlled release rate of the nutrients for plants. The structure of model silicate-phosphate glasses containing the different amounts of the glass network formers, i.e. Ca 2+ and Mg 2+, as a binding components were studied. These elements besides other are indispensable of the normal growth of plants. In order to establish the function and position occupied by the particular components in the glass structure, the glasses were examined by FTIR spectroscopy (with spectra decomposition) and XRD methods. It has been found that the increasing amount of MgO in the structure of silicate-phosphate glasses causes the formation of domains the structure of which changes systematically from a structure of the cristobalite type to a structure corresponding to forsterite type. Whilst the increasing content of CaO in the structure of silicate-phosphate glasses causes the formation of domains the structure of which changes from a structure typical for cristobalite through one similar to the structure of calcium orthophosphate, to a structure corresponding to calcium silicates. The changing character of domains structure is the reason of different chemical activity of glasses.

  18. Alkali metal ion battery with bimetallic electrode

    DOEpatents

    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.

  19. Ideas about Acids and Alkalis.

    ERIC Educational Resources Information Center

    Toplis, Rob

    1998-01-01

    Investigates students' ideas, conceptions, and misconceptions about acids and alkalis before and after a teaching sequence in a small-scale research project. Concludes that student understanding of acids and alkalis is lacking. (DDR)

  20. 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.

  1. "Low-Li2O" Frits: Selecting Glasses that Support the Melt Rate Studies and Challenge the Current Durability Model

    SciTech Connect

    Peeler, D. K.; Edwards, T. B.

    2005-07-30

    During the progressive development of the cold cap model (as it applies to a potential melt rate predictive tool), the formation of an Al-Li-silicate phase was identified as an intermediate reaction phase that could possibly hinder melt rate for SB4. To test this theory, six glasses were designed (using Frit 320's composition as the baseline) to maintain a constant 20 wt% sum of alkali content (in frit) by varying Na{sub 2}O to Li{sub 2}O ratios. The Li{sub 2}O concentration ranged from 8 wt% down to 0% in either 2% or 1% increments with the differences being accounted for by an increase in Na{sub 2}O concentration. Although the primary objective of the ''lower Li{sub 2}O'' frits was to evaluate the potential for melt rate improvements, assessments of durability (as measured by the Product Consistency Test (PCT)) were also performed. The results suggest that durable glasses can be produced with these ''lower Li{sub 2}O'' frits should it be necessary to pursue this option for improving melt rate. In addition to the series of glasses to support melt rate assessments, a series of frits were also developed to challenge the current durability model based on the limits proposed by Edwards et al. (2004). Although the ''new'' limits allow access into compositional regions of interest (i.e., higher alkali systems) which can improve melt rate and/or waste loading, there may still be ''additional'' conservatism. In this report, two series of glasses were developed to challenge the ''new'' durability limits for the SB4 system. In the first series, the total alkali of the Frit 320-based glasses (designed to support the melt rate program) was increased from 20 wt% to 21 wt% (in the frit), but the series also evaluated the possible impact of various Na{sub 2}O and Li{sub 2}O mass ratio differences. The second series pushed the alkali limit in the frit even further with frits containing either 22 or 24 wt% total alkali as well as various Na{sub 2}O and Li{sub 2}O mass ratios. The

  2. Oxygen isotope partitioning between rhyolitic glass/melt and CO{sub 2}: An experimental study at 550-950{degrees}C and 1 bar

    SciTech Connect

    Palin, J.M.; Epstein, S.; Stolper, E.M.

    1996-06-01

    Oxygen isotope partitioning between gaseous CO{sub 2} and a natural rhyolitic glass and melt (77.7 wt% SiO{sub 2}, 0.16 wt% H{sub 2}O{sub total}) has been measured at 550-950{degrees}C and approximately 1 bar. Equilibrium oxygen isotope fractionation factors ({alpha}{sub CO2-rhyolite} = ({sup 18}O/{sup 16}O){sub rhyolite}) determined in exchange experiments of 100-255 day duration. These values agree well with predictions based on experimentally determined oxygen isotope fractionation factors for CO{sub 2}-silica glass and CO{sub 2}-albitic glass/melt, if the rhyolitic glass is taken to be a simple mixture of normative silica and alkali feldspar components. The results indicate that oxygen isotope partitioning in felsic glasses and melts can be modeled by linear combinations of endmember silicate constituents. Rates of oxygen isotope exchange observed in the partitioning experiments are consistent with control by diffusion of molecular H{sub 2}O dissolved in the glass/melt and are three orders of magnitude faster than predicted for rate control solely by diffusion of dissolved molecular CO{sub 2} under the experimental conditions. Additional experiments using untreated and dehydrated (0.09 wt% H{sub 2}O{sub total}) rhyolitic glass quantatively support these interpretations. We conclude that diffusive oxygen isotope exchange in rhyolitic glass/melt, and probably other polymerized silicate materials, it controlled by the concentrations and diffusivities of dissolved oxygen-bearing volatile species rather than diffusion of network oxygen under all but the most volatile-poor conditions. 25 refs., 6 figs., 1 tab.

  3. An Evaluation of Ethyl Silicate-Based Grouts for Weathered Silicate Stones

    NASA Astrophysics Data System (ADS)

    Dolph, Brittany Helen

    Culturally significant monuments made of weathered siliceous stone often display sub-surface condition issues such as cracks and voids. These issues require grouts that are ideally compatible with the composition and properties of the substrate. Based on the successful application of ethyl silicates as consolidants in recent literature, this study examines possible formulation pathways for the development of a grout incorporating ethyl silicate. Tetraethylorthosilicate (TEOS), dibutyltin dilaurate (DBTL) as a catalyst, silicone oil (PDMS), various grades of ground quartz, sepiolite, and hollow glass spheres were used in differing concentrations to create samples. These were visually and physically assessed on workability, separation, shrinkage, cracking, strength, and flexibility. Quantitative analysis was performed on selected formulations using UV-Vis-NIR reflectance spectroscopy in coordination with a weight loss experiment to investigate kinetics, dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). Successful formulations tended to include oligomeric TEOS, crushed quartz of mixed grades, sepiolite powder, and PDMS, and show promise for future investigations.

  4. 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)

  5. SUMMARY OF 2010 DOE EM INTERNATIONAL PROGRAM STUDIES OF WASTE GLASS STRUCTURE AND PROPERTIES

    SciTech Connect

    Fox, K.; Choi, A.; Marra, J.; Billings, A.

    2011-02-07

    Collaborative work between the Savannah River National Laboratory (SRNL) and SIA Radon in Russia was divided among three tasks for calendar year 2010. The first task focused on the study of simplified high level waste glass compositions with the objective of identifying the compositional drivers that lead to crystallization and poor chemical durability. The second task focused on detailed characterization of more complex waste glass compositions with unexpectedly poor chemical durabilities. The third task focused on determining the structure of select high level waste glasses made with varying frit compositions in order to improve models under development for predicting the melt rate of the Defense Waste Processing Facility (DWPF) glasses. The majority of these tasks were carried out at SIA Radon. Selection and fabrication of the glass compositions, along with chemical composition measurements and evaluations of durability were carried out at SRNL and are described in this report. SIA Radon provided three summary reports based on the outcome of the three tasks. These reports are included as appendices to this document. Briefly, the result of characterization of the Task 1 glasses may indicate that glass compositions where iron is predominantly tetrahedrally coordinated have more of a tendency to crystallize nepheline or nepheline-like phases. For the Task 2 glasses, the results suggested that the relatively low fraction of tetrahedrally coordinated boron and the relatively low concentrations of Al{sub 2}O{sub 3} available to form [BO{sub 4/2}]{sup -}Me{sup +} and [AlO{sub 4/2}]{sup -}Me{sup +} tetrahedral units are not sufficient to consume all of the alkali ions, and thus these alkali ions are easily leached from the glasses. All of the twelve Task 3 glass compositions were determined to be mainly amorphous, with some minor spinel phases. Several key structural units such as metasilicate chains and rings were identified, which confirms the current modeling

  6. Oxygen isotope and petrological study of silicate inclusions in IIE iron meteorites and their relationship with H chondrites

    NASA Astrophysics Data System (ADS)

    McDermott, Kathryn H.; Greenwood, Richard C.; Scott, Edward R. D.; Franchi, Ian A.; Anand, Mahesh

    2016-01-01

    supported by our new data. However, derivation of both groups from one parent body seems unlikely. Instead, both groups probably sampled similar precursor materials and accreted at a similar nebular location. Our data suggest that the IIE meteorites formed on an internally heated H/HH chondrite-like body that experienced the initial stages of differentiation in response to radiogenic heating. However, prior to full differentiation the IIE parent body experienced a major hit-and-run style collision that resulted in silicate-metal mixing. The initial stages of this event involved a phase of rapid cooling that prevented unmixing of metal and silicates. Reassembly of the IIE parent body produced a large regolith blanket that facilitated subsequent slow cooling. The IIE parent body has probably experienced numerous subsequent less catastrophic collisions. The development of alkali glass textures in some differentiated inclusions is probably the result of one of these later events.

  7. Characterizing Amorphous Silicates in Extraterrestrial Materials

    NASA Astrophysics Data System (ADS)

    Fu, X.; Wang, A.; Krawczynski, M. J.

    2015-12-01

    Amorphous silicates are common in extraterrestrial materials. They are seen in the matrix of carbonaceous chondrites as well as in planetary materials. Tagish Lake is one of the most primitive carbonaceous meteorites in which TEM and XRD analyses found evidence for poorly crystalline phyllosilicate-like species; Raman spectra revealed amorphous silicates with variable degree of polymerization and low crystallinity. On Mars, CheMin discovered amorphous phases in all analyzed samples, and poorly crystalline smectite in mudstone samples. These discoveries pose questions on the crystallinity of phyllosilicates found by remote sensing on Mars, which is directly relevant to aqueous alteration during geologic history of Mars. Our goal is to use spectroscopy to better characterize amorphous silicates. We use three approaches: (1) using silicate glasses synthesized with controlled chemistry to study the effects of silicate polymerization and (2) using phyllosilicates synthesized with controlled hydrothermal treatment to study the effect of crystallinity on vibrational spectroscopy, finally (3) to use the developed correlations in above two steps to study amorphous phases in meteorites, and those found in future missions to Mars. In the 1st step, silicate glasses were synthesized from pure oxides in a range of NBO/T ratios (from 0 to 4). Depending on the targeted NBO/T and composition of mixed oxides, temperatures for each experiment fell in a range from 1260 to 1520 °C, run for ~ 4 hrs. The melt was quenched in liquid N2 or water. Homogeneity of glass was checked under optical microscopy. Raman spectra were taken over 100 spots on small chips free of bubbles and crystals. We have observed that accompanying an increase of NBO/T, there is a strengthening and a position shift of the Raman peak near 1000 cm-1 (Si-Onon-bridging stretching mode), and the weakening of broad Raman peaks near 500 cm-1 (ring breathing mode) and 700cm-1 (Si-Obridging-Si mode). We are building the

  8. Cesium titanium silicate and method of making

    DOEpatents

    Balmer, Mari L.

    1997-01-01

    The invention is the new material, a ternary compound of cesium, silica, and titania, together with a method of making the ternary compound, cesium titanium silicate pollucite. More specifically, the invention is Cs.sub.2 Ti.sub.2 Si.sub.4 O.sub.13 pollucite which is a new crystalline phase representing a novel class of Ti-containing zeolites. Compositions contain relatively high Cs.sub.2 O and TiO.sub.2 loadings and are durable glass and ceramic materials. The amount of TiO.sub.2 and Cs.sub.2 that can be incorporated into these glasses and crystalline ceramics far exceeds the limits set for the borosilicate high level waste glass.

  9. Cesium titanium silicate and method of making

    DOEpatents

    Balmer, M.L.

    1997-01-07

    The invention is the new material, a ternary compound of cesium, silica, and titania, together with a method of making the ternary compound, cesium titanium silicate pollucite. More specifically, the invention is Cs{sub 2}Ti{sub 2}Si{sub 4}O{sub 13} pollucite which is a new crystalline phase representing a novel class of Ti-containing zeolites. Compositions contain relatively high Cs{sub 2}O and TiO{sub 2} loadings and are durable glass and ceramic materials. The amount of TiO{sub 2} and Cs{sub 2} that can be incorporated into these glasses and crystalline ceramics far exceeds the limits set for the borosilicate high level waste glass. 10 figs.

  10. Summary of research on the effect of LiNO{sub 3} on alkali-silica reaction in new concrete

    SciTech Connect

    Feng, X.; Thomas, M.D.A.; Bremner, T.W.; Folliard, K.J.; Fournier, B.

    2010-04-15

    This paper summarizes findings from a research study conducted at the University of New Brunswick in collaboration with the University of Texas at Austin, and CANMET-MTL, on the effect of LiNO{sub 3} on ASR in new concrete. The studies included expansion testing, silica dissolution measurements and microstructural examinations of cement systems containing glass and two different reactive aggregates (NB and NS). Only a small proportion of the data are presented here for the purpose of highlighting the principal findings of this investigation. Based on these findings, it is proposed that the inhibiting effect of LiNO{sub 3} against ASR in new concrete is attributed to the formation of two reaction products in the presence of lithium, these being a crystalline lithium silicate compound (Li{sub 2}SiO{sub 3}) crystal and a Li-bearing, low Ca silica gel. These two phases could serve as a diffusion barrier and protective layer to prevent the reactive silica from further attack by alkalis. It was found that the reason the two reactive aggregates selected responded differently to LiNO{sub 3} was due to the difference in their textural features. The NB aggregate contained reactive volcanic glass particles, the surface of which was immediately and equally available to sodium, potassium and lithium, and thus a Li-Si barrier was able to form quickly. The reactive phase in the NS aggregate was microcrystalline and strained quartz, which was embedded in a dense matrix of a non-reactive predominantly alumino-silicate phase and was not easily accessible to lithium.

  11. Mineral stimulation of subsurface microorganisms: release of limiting nutrients from silicates

    USGS Publications Warehouse

    Roger, Jennifer Roberts; Bennett, Philip C.

    2004-01-01

    Microorganisms play an important role in the weathering of silicate minerals in many subsurface environments, but an unanswered question is whether the mineral plays an important role in the microbial ecology. Silicate minerals often contain nutrients necessary for microbial growth, but whether the microbial community benefits from their release during weathering is unclear. In this study, we used field and laboratory approaches to investigate microbial interactions with minerals and glasses containing beneficial nutrients and metals. Field experiments from a petroleum-contaminated aquifer, where silicate weathering is substantially accelerated in the contaminated zone, revealed that phosphorus (P) and iron (Fe)-bearing silicate glasses were preferentially colonized and weathered, while glasses without these elements were typically barren of colonizing microorganisms, corroborating previous studies using feldspars. In laboratory studies, we investigated microbial weathering of silicates and the release of nutrients using a model ligand-promoted pathway. A metal-chelating organic ligand 3,4 dihydroxybenzoic acid (3,4 DHBA) was used as a source of chelated ferric iron, and a carbon source, to investigate mineral weathering rate and microbial metabolism.In the investigated aquifer, we hypothesize that microbes produce organic ligands to chelate metals, particularly Fe, for metabolic processes and also form stable complexes with Al and occasionally with Si. Further, the concentration of these ligands is apparently sufficient near an attached microorganism to destroy the silicate framework while releasing the nutrient of interest. In microcosms containing silicates and glasses with trace phosphate mineral inclusions, microbial biomass increased, indicating that the microbial community can use silicate-bound phosphate inclusions. The addition of a native microbial consortium to microcosms containing silicates or glasses with iron oxide inclusions correlated to

  12. 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.

  13. Polymeric, Metallic, and Other Glasses in Introductory Chemistry

    ERIC Educational Resources Information Center

    Hawkes, Stephen J.

    2008-01-01

    Non-ceramic glasses are not adequately discussed in introductory chemistry. Such glasses include polycarbonate, which many corrective lenses are made of, amber, enamel, gelatin, hard candy, coal, refrigerated glycerol, and metallic glasses that have been marketed in recent decades. What is usually discussed in elementary texts is siliceous glass,…

  14. Mesoscale Molecular Dynamics of Geomaterials: the Glass Transition, Long-Range Structure of Amorphous Silicates and Relation between Structure, Dynamics and Properties of geomaterials at elevated Temperature and Pressure

    SciTech Connect

    Frank Spera

    2006-07-31

    Objectives: Our aims were (1) Large particle-number Molecular Dynamics (MD) simulations of molten silicate and aluminosilicate geomaterials (e.g., CaAl{sub 2}Si{sub 2}O{sub 8}, MgSiO{sub 3}, Mg{sub 2}SiO{sub 4}) with emphasis on understanding the connection between atomic structure and properties at temperatures and pressures characteristic of Earth's mantle (2) Study of the transport properties and equations of state for silicate liquids based on the MD results (3) Development of geochemical models for the evolution of crustal magma bodies undergoing simultaneous assimilation, fractional crystallization, periodic recharge and periodic eruption and application to magmatic systems (4) Study of current-day rates of generation and eruption of magma on earth.

  15. Mecanismes d'action des fines et des granulats de verre sur la reaction alcali-silice et la reaction pouzzolanique

    NASA Astrophysics Data System (ADS)

    Idir, Rachida

    Recycling composite glass with different colours in order to be manufactured into new glass products is at present not economically viable. Therefore, the search for new issues other than stockpile areas or dumping sites could be a serious opportunity. To a certain extent, one of the possible solutions is to use the recycled glass in manufacturing cements and in the preparation of concrete mixtures. However, it is essential to manage the two main behaviours that the glass can have when used in cement-based materials: (1) the use of glass as coarse aggregates reveals harmful behaviour related to alkali-silica reaction; (2) on the other hand, it can result in useful behaviour related to pozzolanic reaction if used as fine particles. Furthermore, the significant alkali content should not be overlooked as their mass corresponds to about 13% of the total mass of the glass and as they may activate the alkali-silica reaction. An experimental programme was conducted to provide answers to the various questions raised about the use of glass in cement-based materials. The first part of this work was primarily devoted to the evaluation of the reactive potential of glass in mortars (alkali and pozzolanic reactions). At this stage, nine classes of glass particles ranging from 3mum to 2.5 mm were considered. Then, fine glass particles were used in order to counteract the negative effect of some classes of coarse aggregates having revealed alkali-reactive behaviour. The second part of this work was performed to study the mechanisms that could explain the behaviours of fine and coarse particles in aqueous and concentrated environments. Different answers have been proposed to explain the observed behaviour in terms of grain sizes of glass. Keywords: Glass, Powder, Pozzolan, aggregates, alkali-reaction, alkali-aggregate reaction, alkali-silica reaction, Pouzzolanicity, alkalis, Mortars

  16. Structural investigations of borosilicate glasses containing MoO 3 by MAS NMR and Raman spectroscopies

    NASA Astrophysics Data System (ADS)

    Caurant, D.; Majérus, O.; Fadel, E.; Quintas, A.; Gervais, C.; Charpentier, T.; Neuville, D.

    2010-01-01

    High molybdenum concentration in glass compositions may lead to alkali and alkaline-earth molybdates crystallization during melt cooling that must be controlled particularly during the preparation of highly radioactive nuclear glassy waste forms. To understand the effect of molybdenum addition on the structure of a simplified nuclear glass and to know how composition changes can affect molybdates crystallization tendency, the structure of two glass series belonging to the SiO 2-B 2O 3-Na 2O-CaO-MoO 3 system was studied by 29Si, 11B, 23Na MAS NMR and Raman spectroscopies by increasing MoO 3 or B 2O 3 concentrations. Increasing MoO 3 amount induced an increase of the silicate network reticulation but no significant effect was observed on the proportion of BO4- units and on the distribution of Na + cations in glass structure. By increasing B 2O 3 concentration, a strong evolution of the distribution of Na + cations was observed that could explain the evolution of the nature of molybdate crystals (CaMoO 4 or Na 2MoO 4) formed during melt cooling.

  17. Barstow heliostat mirror glass characterization

    NASA Astrophysics Data System (ADS)

    Lind, M. A.; Buckwalter, C. Q.

    1980-09-01

    The technical analysis performed on the special run of low iron float glass for a ten megawatt solar thermal/electric pilot power plant is discussed. The topics that are addressed include the optical properties and the relative durability of the glass. Two optical parameters, solar transmittance and optical flatness, were measured as referenced in the specification and found to be better than the stated tolerances. The average solar transmittance exceeded 0.890 transmittance units. The glass also exhibited optical angular flatness deviations less than + or - 1.0 mrad as required. Both qualitative and quantitative accelerated weathering tests were performed on the glass in order to compare its durability to other soda lime float glass and alternate composition glasses of interest to the solar community. In both the quantitative leaching experiments and the more qualitative room temperature and elevated temperature water vapor exposure experiments the heliostat glass exhibited the same characteristics as the other soda lime silicate float glasses.

  18. 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

  19. Alkalis in alternative biofuels

    SciTech Connect

    Miles, T.R.; Miles, T.R. Jr.; Bryers, R.W.; Baxter, L.L.; Jenkins, B.M.; Oden, L.L.

    1994-12-31

    The alkali content and behavior of inorganic material of annually produced biofuels severely limits their use for generating electrical power in conventional furnaces. A recent eighteen-month investigation of the chemistry and firing characteristics of 26 different biofuels has been conducted. Firing conditions were simulated in the laboratory for eleven biofuels. This paper describes some results from the investigation including fuel properties, deposits, deposition mechanisms, and implications for biomass boiler design, fuel sampling and characterizations. Urban wood fuel, agricultural residues, energy crops, and other potential alternate fuels are included in the study. Conventional methods for establishing fuel alkali content and determining ash sticky temperatures were deceptive. The crux of the problem was found to be the high concentration of potassium in biofuels and its reactions with other fuel constituents which lower the ``sticky temperature`` of the ash to the 650 C to 760 C (1,200 F-1,400 F).

  20. 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.

  1. Determination of boron in silicates after ion exchange separation

    USGS Publications Warehouse

    Kramer, H.

    1955-01-01

    Existing methods for the determination of boron in silicates are not entirely satisfactory. Separation as the methyl ester is lengthy and frequently erratic. An accurate and rapid method applicable to glass, mineral, ore, and water samples uses ion exchange to remove interfering cations, and boron is determined titrimetrically in the presence of mannitol, using a pH meter to indicate the end point.

  2. Final report on the safety assessment of potassium silicate, sodium metasilicate, and sodium silicate.

    PubMed

    Elmore, Amy R

    2005-01-01

    Potassium Silicate, Sodium Metasilicate, and Sodium Silicate combine metal cations with silica to form inorganic salts used as corrosion inhibitors in cosmetics. Sodium Metasilicate also functions as a chelating agent and Sodium Silicate as a buffering and pH adjuster. Sodium Metasilicate is currently used in 168 formulations at concentrations ranging from 13% to 18%. Sodium Silicate is currently used in 24 formulations at concentrations ranging from 0.3% to 55%. Potassium Silicate and Sodium Silicate have been reported as being used in industrial cleaners and detergents. Sodium Metasilicate is a GRAS (generally regarded as safe) food ingredient. Aqueous solutions of Sodium Silicate species are a part of a chemical continuum of silicates based on an equilibrium of alkali, water, and silica. pH determines the solubility of silica and, together with concentration, determines the degree of polymerization. Sodium Silicate administered orally is readily absorbed from the alimentary canal and excreted in the urine. The toxicity of these silicates has been related to the molar ratio of SiO2/Na2O and the concentration being used. The Sodium Metasilicate acute oral LD50 ranged from 847 mg/kg in male rats to 1349.3 mg/kg in female rats and from 770 mg/kg in female mice to 820 mg/kg in male mice. Gross lesions of variable severity were found in the oral cavity, pharynx, esophagus, stomach, larynx, lungs, and kidneys of dogs receiving 0.25 g/kg or more of a commercial detergent containing Sodium Metasilicate; similar lesions were also seen in pigs administered the same detergent and dose. Male rats orally administered 464 mg/kg of a 20% solution containing either 2.0 or 2.4 to 1.0 ratio of sodium oxide showed no signs of toxicity, whereas doses of 1000 and 2150 mg/kg produced gasping, dypsnea, and acute depression. Dogs fed 2.4 g/kg/day of Sodium Silicate for 4 weeks had gross renal lesions but no impairment of renal function. Dermal irritation of Potassium Silicate, Sodium

  3. Low-temperature heat capacity of diopside glass (CaMgSi2O6): A calorimetric test of the configurational-entropy theory applied to the viscosity of liquid silicates

    USGS Publications Warehouse

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

    1986-01-01

    Heat-capacity measurements have been made between 8 and 370 K on an annealed and a rapidly quenched diopside glass. Between 15 and 200 K, Cp does not depend significantly on the thermal history of the glass. Below 15 K Cp is larger for the quenched than for the annealed specimen. The opposite is true above 200 K as a result of what is interpreted as a secondary relaxation around room temperature. The magnitude of these effects, however, is small enough that the relative entropies S(298)-S(0) of the glasses differ by only 0.5 J/mol K, i.e., a figure within the combined experimental uncertainties. The insensitivity of relative entropies to thermal history supports the assumption that the configurational heat capacity of the liquid may be taken as the heat capacity difference between the liquid and the glass (??Cp). Furthermore, this insensitivity allows calculation of the residual entropies at 0 K of diopside glasses as a function of the fictive temperature from the entropy of fusion of diopside and the heat capacities of the crystalline, glassy and liquid phases. For a glass with a fictive temperature of 1005 K, for example, this calorimetric residual entropy is 24.3 ?? 3 J/mol K, in agreement with the prediction made by RICHET (1984) from an analysis of the viscosity data with the configurational-entropy theory of relaxation processes of Adam and Gibbs (1965). In turn, all the viscosity measurements for liquid diopside, which span the range 0.5-4?? 1013 poise, can be quantitatively reproduced through this theory with the calorimetrically determined entropies and ??Cp data. Finally, the unclear significance of "activation energies" for structural interpretations of viscosity data is emphasized, and the importance of ??Cp and glass-transition temperature systematics for determining the composition and temperature dependences of the viscosity is pointed out. ?? 1986.

  4. Summary Report: Glass-Ceramic Waste Forms for Combined Fission Products

    SciTech Connect

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

    2011-09-23

    Glass-ceramic waste form development began in FY 2010 examining two combined waste stream options: (1) alkaline earth (CS) + lanthanide (Ln), and (2) + transition metal (TM) fission-product waste streams generated by the uranium extraction (UREX+) separations process. Glass-ceramics were successfully developed for both options however; Option 2 was selected over Option 1, at the conclusion of 2010, because Option 2 immobilized all three waste streams with only a minimal decrease in waste loading. During the first year, a series of three glass (Option 2) were fabricated that varied waste loading-WL (42, 45, and 50 mass%) at fixed molar ratios of CaO/MoO{sub 3} and B{sub 2}O{sub 3}/alkali both at 1.75. These glass-ceramics were slow cooled and characterized in terms of phase assemblage and preliminary irradiation stability. This fiscal year, further characterization was performed on the FY 2010 Option 2 glass-ceramics in terms of: static leach testing, phase analysis by transmission electron microscopy (TEM), and irradiation stability (electron and ion). Also, a new series of glass-ceramics were developed for Option 2 that varied the additives: Al{sub 2}O{sub 3} (0-6 mass%), molar ratio of CaO/MoO{sub 3} and B{sub 2}O{sub 3}/alkali (1.75 to 2.25) and waste loading (50, 55, and 60 mass%). Lastly, phase pure powellite and oxyapatite were synthesized for irradiation studies. Results of this fiscal year studies showed compositional flexibility, chemical stability, and radiation stability in the current glass-ceramic system. First, the phase assemblages and microstructure of all of the FY 2010 and 2011 glass-ceramics are very similar once subjected to the slow cool heat treatment. The phases identified in these glass-ceramics were oxyapatite, powellite, cerianite, and ln-borosilicate. This shows that variations in waste loading or additives can be accommodated without drastically changing the phase assemblage of the waste form, thus making the processing and performance

  5. Calcium silicate insulation structure

    DOEpatents

    Kollie, Thomas G.; Lauf, Robert J.

    1995-01-01

    An insulative structure including a powder-filled evacuated casing utilizes a quantity of finely divided synthetic calcium silicate having a relatively high surface area. The resultant structure-provides superior thermal insulating characteristics over a broad temperature range and is particularly well-suited as a panel for a refrigerator or freezer or the insulative barrier for a cooler or a insulated bottle.

  6. Lithium metaborate flux in silicate analysis

    USGS Publications Warehouse

    Ingamells, C.O.

    1970-01-01

    Lithium metaborate is an effective flux for silicates and other rock-forming minerals. The glass resulting from fusion is mechanically strong, reasonably nonhygroscopic, and is readily soluble in dilute acids. These characteristics lead to its use in X-ray spectrography and in methods which require whole-rock solutions, such as atomic absorption and emission spectrometry. Difficulties have been encountered in the use of such techniques : a high-quality reagent has been difficult to obtain ; fusion conditions must be rather closely controlled; graphite crucibles used in the fusions need special treatment. Methods for overcoming these difficulties are outlined. Selected procedures for various instrumental methods of analysis are described. ?? 1970.

  7. Viscous sealing glass compositions for solid oxide fuel cells

    SciTech Connect

    Kim, Cheol Woon; Brow, Richard K.

    2016-12-27

    A sealant for forming a seal between at least two solid oxide fuel cell components wherein the sealant comprises a glass material comprising B.sub.2O.sub.3 as a principal glass former, BaO, and other components and wherein the glass material is substantially alkali-free and contains less than 30% crystalline material.

  8. Silicic volcanism in Iceland: Composition and distribution within the active volcanic zones

    NASA Astrophysics Data System (ADS)

    Jónasson, Kristján

    2007-01-01

    Silicic volcanic rocks within the active volcanic zones of Iceland are mainly confined to central volcanoes. The volcanic zones of Iceland can be divided into rift zones and flank zones. Each of these zones contains several central volcanoes, most of which have produced minor amounts of silicic rocks. The silicic rocks occur as lavas and domes or as tephra layers, welded tuffs and ignimbrites, formed both in effusive and explosive eruptions. They tend to be glassy or very fine-grained, containing small amounts of phenocrysts. Plagioclase (andesine-oligoclase), anorthoclase or occasionally sanidine coexist with minerals such as augite, fayalite, pigeonite, orthopyroxene and magnetite. Quartz phenocrysts are exceedingly rare. Zoning of phenocrysts is limited and the pattern is variable. A set of 90 samples representing all active central volcanoes that have erupted silicic rocks was analysed for major- and trace-elements. The silicic rocks can be classified as dacites, trachytes, low-alkali rhyolites and alkalic rhyolites. Some of the trachytes and alkalic rhyolites are peralkaline (mostly comenditic). Trachytes and alkalic rhyolites are only found within the flank zones, while dacites and low-alkali rhyolites are mostly confined to the rift zones. The Icelandic rhyolites plot close to the thermal minimum in the "granite" system, while dacites and trachytes plot within the plagioclase field and towards the alkali feldspar temperature minimum. The silicic rocks are relatively Fe-rich and Ca-poor indicating low water pressure in the source. Trace element concentrations follow similar patterns in most central volcanoes. Exceptions are Torfajökull where silicic rocks display a negative correlation of Ba to Th and unusually high Th-contents, and the western flank zone where Ba-concentrations are highly variable. The ratios of different high field-strength elements are generally similar within each central volcano or region, which probably reflects different ratios in the

  9. Micro-PIXE analysis of silicate reference standards

    USGS Publications Warehouse

    Czamanske, G.K.; Sisson, T.W.; Campbell, J.L.; Teesdale, W.J.

    1993-01-01

    The accuracy and precision of the University of Guelph proton microprobe have been evaluated through trace-element analysis of well-characterized silicate glasses and minerals, including BHVO-1 glass, Kakanui augite and hornblende, and ten other natural samples of volcanic glass, amphibole, pyroxene, and garnet. Using the 2.39 wt% Mo in a NIST steel as the standard, excellent precision and agreement between reported and analyzed abundances were obtained for Fe, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, and Nb. -from Authors

  10. 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.

  11. 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.

  12. 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.

  13. Crystallization, Fluid Exsolution, and Eruption of Extremely Volatile-rich Silicate Magma at Oldoinyo Lengai Volcano, East African Rift

    NASA Astrophysics Data System (ADS)

    de Moor, J.; Fischer, T. P.; King, P. L.; Hervig, R. L.; Hilton, D. R.

    2011-12-01

    Oldoinyo Lengai volcano (OL) is famous for producing natrocarbonatite (NC) lava flows, yet its magmatic products are volumetrically dominated by silicate pyroclastic deposits [1]. After ~25 years of NC effusion, OL erupted explosively in 2007-2008 to produce nephelinite ash. NC effusion resumed in 2009, completing the typical historical eruptive cycle observed at OL [2]. Here we investigate the processes of magma differentiation and volatile exsolution resulting in this behavior through the study of major, trace, and volatile element compositions of nepheline-hosted melt inclusions (MI) and matrix glass (MG) in nephelinite scoria erupted in 2007-2008. The nephelinite scoria are extremely crystal rich, with nepheline and clinopyroxene dominating the phenocryst assemblage. Other phenocryst and accessory minerals include garnet, wollastonite, combeite, melilite, and sulfides. The glasses span a wide range in composition and define a cohesive evolutionary trend of decreasing SiO2 from ~46 wt% in the MI to ~38 wt% in the MG. The decrease in SiO2 is accompanied by strong enrichment in alkalis and depletion in Al2O3, resulting in extremely peralkaline MG. Rare earth elements and other incompatible elements are also strongly enriched in the MG relative to the MI. For example, the least evolved MI contain ~55 ppm Ce whereas the MG attains concentrations of >1000 ppm. Fractional crystallization modeling indicates that the evolutionary trends observed in the major element data are consistent with ~90% crystallization of the melt between the time of MI entrapment and eruption. The MI are exceptionally rich in volatiles and contain the highest CO2 concentrations (up to 2.5 wt%) ever measured in natural silicate glass, high H2O (up to 6 wt%), and high S (0.3-1.3 wt%). Immiscible NC coexists with nephelinite glass in many MI, providing clear evidence that the NC lavas and nephelinitic pyroclastics at OL are derived from a common magma [3]. The silicate MI are extremely CO2-rich

  14. 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.

  15. 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)

  16. 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.

  17. Silicates in Alien Asteroids

    NASA Technical Reports Server (NTRS)

    2009-01-01

    This plot of data from NASA's Spitzer Space Telescopes shows that asteroid dust around a dead 'white dwarf' star contains silicates a common mineral on Earth. The data were taken primarily by Spitzer's infrared spectrograph, an instrument that breaks light apart into its basic constituents. The yellow dots show averaged data from the spectrograph, while the orange triangles show older data from Spitzer's infrared array camera. The white dwarf is called GD 40.

  18. Thin glass processing with various laser sources

    NASA Astrophysics Data System (ADS)

    Collins, Adam R.; Milne, David; Prieto, Camilo; O'Connor, Gerard M.

    2015-03-01

    Laser processing of thin glass has proven problematic due to the inefficient coupling of optical energy into glass and the difficulty achieving an economical processing speed while maintaining cut quality. Laser glass processing is pertinent to touch screen display, microfluidic, microoptic and photovoltaic applications. The results of the laser scribing of 110 μm thick alkali free glass with various laser sources are presented. The laser sources include a CO₂ laser, nanosecond UV laser and femtosecond IR laser. The contrasting absorption mechanisms are discussed. Cut quality and processing speed are characterised using SEM and optical microscopy techniques. Alternative laser techniques for thin glass processing are also considered.

  19. Thermochemistry of Silicates

    NASA Technical Reports Server (NTRS)

    Costa, Gustavo; Jacobson, Nathan

    2015-01-01

    The thermodynamic properties of vapor and condensed phases of silicates are crucial in many fields of science. These quantities address fundamental questions on the formation, stability, transformation, and physical properties of silicate minerals and silicate coating compositions. Here the thermodynamic activities of silica and other species in solid solution have been measured by the analysis of the corresponding high temperature vapors using Knudsen Effusion Mass Spectrometry (KEMS). In first set of experiments KEMS has been used to examine the volatility sequence of species (Fe, SiO, Mg, O2 and O) present in the vapor phase during heating of fosterite-rich olivine (Fo93Fa7) up to 2400 C and to measure the Fe, SiO and Mg activities in its solid solution. The data of fosterite-rich olivine are essential for thermochemical equilibrium models to predict the atmospheric and surface composition of hot, rocky exoplanets (Lava Planets). In the second set of experiments the measured thermodynamic activities of the silica in Y2O3-SiO2 and Yb2O3-SiO2 systems are used to assess their reactivity and degradation recession as environmental barrier coatings (EBCs) in combustion environments (e.g. non-moveable parts of gas turbine engine).

  20. Spherulite Crystallization Induces Fe-Redox Redistribution in Silicic Melt

    SciTech Connect

    Castro, J.; Cottrell, E; Tuffen, H; Logan, A; Kelley, K

    2009-01-01

    Rhyolitic obsidians from Krafla volcano, Iceland, record the interaction between mobile hydrous species liberated during crystal growth and the reduction of ferric iron in the silicate melt. We performed synchrotron {mu}-FTIR and {mu}-XANES measurements along a transect extending from a spherulite into optically distinct colorless and brown glass zones. Measurements show that the colorless glass is enriched in OH groups and depleted in ferric iron, while the brown glass shows the opposite relationship. The color shift between brown and clear glass is sharp, suggesting that the colorless glass zone was produced by a redox front that originated from the spherulite margin and moved through surrounding melt during crystallization. We conclude that the most likely reducing agent is hydrogen, produced by magnetite crystallization within the spherulite. The Krafla obsidians dramatically capture redox disequilibrium on the micoscale and highlight the importance of hydrous fluid liberation and late-stage crystallization to the redox signature of glassy lavas.

  1. Discovery of ancient silicate stardust in a meteorite.

    PubMed

    Nguyen, Ann N; Zinner, Ernst

    2004-03-05

    We have discovered nine presolar silicate grains from the carbonaceous chondrite Acfer 094. Their anomalous oxygen isotopic compositions indicate formation in the atmospheres of evolved stars. Two grains are identified as pyroxene, two as olivine, one as a glass with embedded metal and sulfides (GEMS), and one as an Al-rich silicate. One grain is enriched in 26Mg, which is attributed to the radioactive decay of 26Al and provides information about mixing processes in the parent star. This discovery opens new means for studying stellar processes and conditions in various solar system environments.

  2. EVIDENCE THAT POLYWATER IS A COLLOIDAL SILICATE SOL.

    DTIC Science & Technology

    A study was made of the ’anomalous’ condensation of water and its conversion to ’ polywater ’ in glass and silica capillaries. The condensate was...to contain significant amounts of silicon and sodium. These results suggest that the unusual properties of ’ polywater ’ may be due to the presence of...silica or silicate. It is further shown that, since alkaline silicate solutions can absorb CO2, the infrared spectra of ’ polywater ’ may actually be due, in part, to bicarbonate ion. (Author)

  3. The application of silicon and silicates in dentistry: a review.

    PubMed

    Lührs, A-K; Geurtsen, Werner

    2009-01-01

    Silicates and silicate-based compounds are frequently used materials in dentistry. One of their major applications is their use as fillers in different dental filling materials such as glass-ionomer cements, compomers, composites, and adhesive systems. In these materials, the fillers react with acids during the setting process or they improve the mechanical properties by increasing physical resistance, thermal expansion coefficient and radiopacity in acrylic filling materials. They also reduce polymerization shrinkage, and increase esthetics as well as handling properties. Furthermore, silicates are used for the tribochemical silication of different surfaces such as ceramics or alloys. The silicate layer formed in this process is the chemical basis for silanes that form a bond between this layer and the organic composite matrix. It also provides a micromechanical bond between the surface of the material and the composite matrix. Silicates are also a component of dental ceramics, which are frequently used in dentistry, for instance for veneers, inlays, and onlays, for denture teeth, and for full-ceramic crowns or as crown veneering materials.

  4. Ion-Exchange Interdiffusion Model with Potential Application to Long-Term Nuclear Waste Glass Performance

    SciTech Connect

    Neeway, James Joseph; Kerisit, Sebastien N.; Liu, Jia; Zhang, Jiandong; Zhu, Zihua; Riley, Brian Joseph; Ryan, Joseph Vincent

    2016-05-05

    Abstract: Ion exchange is an integral mechanism influencing the corrosion of glasses. Due to the formation of alteration layers in aqueous conditions, it is difficult to conclusively deconvolute the process of ion exchange from other processes, principally dissolution of the glass matrix. Therefore, we have developed a method to isolate alkali diffusion that involves contacting glass coupons with a solution of 6LiCl dissolved in functionally inert dimethyl sulfoxide. We employ the method at temperatures ranging