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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  4. 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.

  5. 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.

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

    NASA Astrophysics Data System (ADS)

    Jansson, Helén; Bernin, Diana; Ramser, Kerstin

    2015-06-01

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

  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. PMID:23861652

  9. 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.

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

    SciTech Connect

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

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

  13. Mixed alkali effect in nonconventional alkali gallotitanate glasses

    SciTech Connect

    Miyaji, Fumiaki; Hasegawa, Shinya; Yoko, Toshinobu; Sakka, Sumio . Inst. for Chemical Research)

    1993-02-01

    The mixed alkali effect on electrical conductivity, that is, the reduction of conductivity due to alkali mixing, was observed in Na[sub 2]O-K[sub 2]O-Ga[sub 2]O[sub 3]-TiO[sub 2] glasses, which are nonconventional in the sense that glass-forming oxides defined by Zachariasen are not involved. The magnitude of the reduction in conductivity of the present glasses due to alkali mixing was similar to that of corresponding mixed alkali silicate and phosphate glasses. The activation energy for electrical conduction showed a maximum around the composition Na/(Na + K) = 0.5, where the conductivity was at a minimum.

  14. Alkali Silicate Vehicle Forms Durable, Fireproof Paint

    NASA Technical Reports Server (NTRS)

    Schutt, John B.; Seindenberg, Benjamin

    1964-01-01

    The problem: To develop a paint for use on satellites or space vehicles that exhibits high resistance to cracking, peeling, or flaking when subjected to a wide range of temperatures. Organic coatings will partially meet the required specifications but have the inherent disadvantage of combustibility. Alkali-silicate binders, used in some industrial coatings and adhesives, show evidence of forming a fireproof paint, but the problem of high surface-tension, a characteristic of alkali silicates, has not been resolved. The solution: Use of a suitable non-ionic wetting agent combined with a paint incorporating alkali silicate as the binder.

  15. Ion implantation in silicate glasses

    SciTech Connect

    Arnold, G.W.

    1993-12-01

    This review examines the effects of ion implantation on the physical properties of silicate glasses, the compositional modifications that can be brought about, and the use of metal implants to form colloidal nanosize particles for increasing the nonlinear refractive index.

  16. Silicate Glass Corrosion Mechanism revisited

    NASA Astrophysics Data System (ADS)

    Geisler, Thorsten; Lenting, Christoph; Dohmen, Lars

    2015-04-01

    Understanding the mechanism(s) of aqueous corrosion of nuclear waste borosilicate glasses is essential to predict their long-term aqueous durability in a geologic repository. Several observations have been made with compositionally different silicate glasses that cannot be explained by any of the established glass corrosion models. These models are based on diffusion-controlled ion exchange and subsequent structural reorganisation of a leached, hydrated residual glass, leaving behind a so-called gel layer. In fact, the common observation of lamellar to more complex pattern formation observed in experiment and nature, the porous structure of the corrosion layer, an atomically sharp boundary between the corrosion zone and the underlying pristine glass, as well as results of novel isotope tracer and in situ, real time experiments rather support an interface-coupled glass dissolution-silica reprecipitation model. In this model, the congruent dissolution of the glass is coupled in space and time to the precipitation and growth of amorphous silica at an inwardly moving reaction front. We suggest that these coupled processes have to be considered to realistically model the long-term performance of silicate glasses in aqueous environments.

  17. Redox equilibria of multivalent ions in silicate glasses

    NASA Technical Reports Server (NTRS)

    Lauer, H. V., Jr.; Morris, R. V.

    1977-01-01

    Experimental studies were made on the compositional dependence of the redox equilibrium of Eu in synthetic silicate liquids, together with an empirical model describing the observed compositional dependence. Electron paramagnetic resonance (EPR) was used to measure the concentration ratio of Eu(2+) to Eu(3+) in various glasses formed by rapidly quenching silicate liquids. The compositional field studied comprised mixtures of SiO2, TiO2, Al2O3, CaO, MgO, and Na2O. The proposed model describes the Eu(2+)/Eu(3+) ratio over the entire compositional field in terms of parameters easily related to each glass composition. The general applicability and utility of the model is further demonstrated by its application to the Fe(2+)-Fe(3+), Ce(3+)-Ce(4+), and Cr(3+)-Cr(6+) redox reactions in binary alkali oxide silicate glasses of Li, Na, and K.

  18. Fracture of Silicate Glasses: Ductile or Brittle?

    NASA Astrophysics Data System (ADS)

    Guin, Jean-Pierre; Wiederhorn, Sheldon M.

    2004-05-01

    Atomic force microscopy is used to investigate the possibility of cavity formation during crack growth in silicate glasses. Matching areas on both fracture surfaces were mapped and then compared. For silica glass, and soda-lime-silicate glass, the fracture surfaces matched to a resolution of better than 0.3 nm normal to the surface and 5 nm parallel to the surface. We could find no evidence for cavity formation in our study and suggest that completely brittle fracture occurs in glass.

  19. Theory of corrosion of alkali-borosilicate glass

    SciTech Connect

    Clark, D.E.; Hench, L.L.

    1983-01-01

    The alkali-borosilicate (ABS) system provides the basis for a wide variety of commercially important products among which are the nuclear waste glasses. Although a large number of investigations have been undertaken in the last five years, the corrosion mechanisms of the ABS glasses have not been characterized nearly as well as for the soda-lime-silicate (NCS) glasses commonly used for containers. It is well known that the corrosion of the latter glasses involves ion exchange, network dissolution, and precipitation mechanisms resulting in the development of one of five types of surface films. In the present paper we compare the corrosion behavior to the ABS and NCS glasses and discuss our current understanding of ABS glass corrosion in terms of mechanisms, kinetics, surface film formation and thermodynamics.

  20. 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.

  1. 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

  2. Statistics of silicate units in binary glasses

    NASA Astrophysics Data System (ADS)

    Gaddam, Anuraag; Montagne, Lionel; Ferreira, José M. F.

    2016-09-01

    In this paper, we derive a new model to determine the distribution of silicate units in binary glasses (or liquids). The model is based on statistical mechanics and assumes grand canonical ensemble of silicate units which exchange energy and network modifiers from the reservoir. This model complements experimental techniques, which measure short range order in glasses such as nuclear magnetic resonance (NMR) spectroscopy. The model has potential in calculating the amounts of liquid-liquid phase segregation and crystal nucleation, and it can be easily extended to more complicated compositions. The structural relaxation of the glass as probed by NMR spectroscopy is also reported, where the model could find its usefulness.

  3. 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.

  4. 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).

  5. Cooling rate calculations for silicate glasses.

    NASA Astrophysics Data System (ADS)

    Birnie, D. P., III; Dyar, M. D.

    1986-03-01

    Series solution calculations of cooling rates are applied to a variety of samples with different thermal properties, including an analog of an Apollo 15 green glass and a hypothetical silicate melt. Cooling rates for the well-studied green glass and a generalized silicate melt are tabulated for different sample sizes, equilibration temperatures and quench media. Results suggest that cooling rates are heavily dependent on sample size and quench medium and are less dependent on values of physical properties. Thus cooling histories for glasses from planetary surfaces can be estimated on the basis of size distributions alone. In addition, the variation of cooling rate with sample size and quench medium can be used to control quench rate.

  6. 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.

  7. 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.

  8. 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.

  9. Q-Speciation and Network Structure Evolution in Invert Calcium Silicate Glasses.

    PubMed

    Kaseman, Derrick C; Retsinas, A; Kalampounias, A G; Papatheodorou, G N; Sen, S

    2015-07-01

    Binary silicate glasses in the system CaO-SiO2 are synthesized over an extended composition range (42 mol % ≤ CaO ≤ 61 mol %), using container-less aerodynamic levitation techniques and CO2-laser heating. The compositional evolution of Q speciation in these glasses is quantified using (29)Si and (17)O magic angle spinning nuclear magnetic resonance spectroscopy. The results indicate progressive depolymerization of the silicate network upon addition of CaO and significant deviation of the Q speciation from the binary model. The equilibrium constants for the various Q species disproportionation reactions for these glasses are found to be similar to (much smaller than) those characteristic of Li (Mg)-silicate glasses, consistent with the corresponding trends in the field strengths of these modifier cations. Increasing CaO concentration results in an increase in the packing density and structural rigidity of these glasses and consequently in their glass transition temperature Tg. This apparent role reversal of conventional network-modifying cations in invert alkaline-earth silicate glasses are compared and contrasted with that in their alkali silicate counterparts. PMID:26047056

  10. Infrared and Raman spectroscopic studies on alkali borate glasses: evidence of mixed alkali effect.

    PubMed

    Padmaja, G; Kistaiah, P

    2009-03-19

    A lithium-potassium-borate glass system containing manganese and iron cations has been thoroughly investigated in order to obtain information about the mixed alkali effect and the structural role of both the manganese and iron in such glass hosts. Mixed alkali borate glasses of the (30 - x)Li(2)O - xK(2)O - 10CdO/ZnO - 59B(2)O(3) (x = 0, 10, 15, 20, and 30) doped with 1MnO(2)/1Fe(2)O(3) system were prepared by a melt quench technique. The amorphous phase of the prepared glass samples was confirmed from their X-ray diffraction. The spectroscopic properties of glass samples were studied using infrared (IR) and Raman spectroscopic techniques. The density of all the prepared glasses was measured using Archimedes principle. Molar volumes were estimated from the density data. IR spectra of these glasses revealed a dramatic variation of three- and four-coordinated boron structures as a function of mixed alkali concentration. The vibrations due to Li-O, K-O, and MnO(4)/FeO(4) arrangements are consistent in all the compositions and show a nonlinear variation in the intensity with alkali content. Raman spectra of different alkali combinations with CdO and ZnO present drastic changes in the intensity of various Raman bands. The observation of disappearance and reappearance of IR and Raman bands as a function of various alkali concentrations is an important result pertaining to the mixed alkali effect in borate glasses. Acting as complementary spectroscopic techniques, both types of measurements, IR and Raman, revealed that the network structure of the studied glasses is mainly based on BO(3) and BO(4) units placed in different structural groups, the BO(3) units being dominant. The measured IR and Raman spectra of different glasses are used to clarify the optical properties of the present glasses correlating them with their structure and composition. PMID:19235995

  11. 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.

  12. 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.

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

    PubMed

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

    2014-11-01

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

  14. Alkali oxide containing mesoporous bioactive glasses: synthesis, characterization and in vitro bioactivity.

    PubMed

    Vaid, Chitra; Murugavel, Sevi

    2013-03-01

    We report, for the first time, the synthesis of sodium oxide containing mesoporous bioactive quaternary glasses and compared with two different mesoporous ternary silicate systems by modified sol-gel process. With the aid of three different glass systems, a systematic analysis has been made on phosphorous-bearing (P-bearing) and phosphorous-free (P-free) mesoporous bioactive glasses to investigate the role of phosphorus on in vitro bioactivity of various silicate glasses with constant alkali oxide content. The combined use of multiple analytical techniques XRD, FTIR, SEM, nitrogen adsorption/desorption analysis before and after soaking in the SBF solution allowed us to establish strong correlation between composition, pore structure and bioactivity. We find that the P-bearing mesoporous glasses show the rapid hydroxycarbonate apatite (HCA) crystallization than P-free mesoporous glasses independent of calcium content. The present study reveals that the presence of phosphorous jointly with calcium in the bioactive glass system significantly enhances the rate of apatite formation as well as crystallization of apatite phase. Additionally, we find that a glass with sodium orthophosphate rich phase enhances the solubility when immersed in SBF and further accelerate the kinetics of apatite formation. The influences of the chemical composition and their superior textural properties on bioactivity are explained in terms of the unique structure of mesoporous bioactive glasses.

  15. ``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

  16. A Calculation of Spatial Range of Colloidal Silicic Acid Deposited Downstream from the Alkali Front

    NASA Astrophysics Data System (ADS)

    Niibori, Yuichi; Iijima, Kazuki; Tamura, Naoyuki; Mimura, Hitoshi

    A high alkali domain spreads out due to the use of cement materials for the construction of the repository of radioactive wastes. Sudden change of pH at this alkali front produces colloidal silicic acid (polymeric silicic acid) in addition to the deposition of supersaturated monomeric silicic acid onto the fracture surface of flow-pathway. The colloidal silicic acid also deposits with relatively small rate-constant in the co-presence of solid phase. Once the flow-path surface is covered with the amorphous silica, the surface seriously degrades the sorption behavior of radionuclides (RNs). Therefore, so far, the authors have examined the deposition rates of supersaturated silicic acid. This study summarized the deposition rate-constants defined by the first-order reaction equation under various conditions of co-presence of amorphous silica powder. Then, using the smallest rate-constant (1.0×10-12 m/s in the co-presence of calcium ions of 1 mM) and a simulation code, COLFRAC-MRL, the spatial range of colloidal silicic acid deposited downstream from the alkali front was estimated. The results suggested the clogging caused by the deposition of colloidal silicic acid in flow-path. The altered spatial range in the flow-path was limited to around 30 m in fracture and to several centimeters in rock matrix.

  17. 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.

  18. Lattice thermal conductivity of dense silicate glass at high pressures

    NASA Astrophysics Data System (ADS)

    Chang, Y. Y.; Hsieh, W. P.

    2015-12-01

    The layered structure of the Earth's interior is generally believed to develop through the magma ocean differentiation in the early Earth. Previous seismic studies revealed the existence of ultra low velocity zones above the core mantle boundary (CMB) which was inferred to be associated with the remnant of a deep magma ocean. The heat flux through the core mantle boundary therefore would strongly depend on the thermal conductivity, both lattice (klat) and radiative (krad) of dense silicate melts and major constituent minerals of the lower mantle. Recent experimental results on the radiative thermal conductivity of dense silicate glasses and lower-mantle minerals suggest that krad of dense silicate glasses could be remarkably lower than krad of the surrounding solid mantle phases. In this case, the dense silicate melts will act as a trap for heat from the Earth's outer core. However, this conclusion remains uncertain because of the lack of direct measurements on lattice thermal conductivities of silicate glasses/melts under lower mantle pressures up to date. Here we report experimental results on lattice thermal conductivities of dense silicate glass with basaltic composition under pressures relevant to the Earth's lower mantle in a diamond-anvil cell using time-domain thermoreflectance method. The study will assist the comprehension of thermal transport properties of silicate melts in the Earth's deep interior and is crucial for understanding the dynamic and thermal evolution of the Earth's internal structure.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Ionic diffusion and the topological origin of fragility in silicate glasses

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

    Mass transport in liquids and glass is intimately connected to the structure and topology of the disordered network. To investigate this problem, we measure the ionic diffusivity and fragility of a series of iron-bearing alkali-alkaline earth silicate glasses, substituting different types of alkali and alkaline earth cations while keeping the same ratio of network modifiers. Diffusion is studied around the glass transition temperature (Tg) under a reducing atmosphere, leading to a reduction of Fe3+ to Fe2+, and inward diffusion of the modifier cations. In the SiO2-CaO-Fe2O3-A2O (A=Na, K, Rb, or Cs) glass series, we find that the Ca2+ ions diffuse faster than alkali ions and that the activation energy of the Ca2+ diffusion decreases with alkali size, a trend that is coincident with a decrease in liquid fragility. We have established a simple model for accurately describing the correlation between the fragility index (m) and Tg based on a topological consideration of the glass network. The model builds on a temperature-dependent constraint approach where the Vogel temperature serves as a rigidity percolation threshold. This follows from our derivation of the Vogel-Fulcher-Tammann equation of viscosity from the more accurate Mauro-Yue-Ellison-Gupta-Allan equation. The established model provides an excellent prediction of the relationship between fragility and Tg, except for the MgO-containing glass where Mg2+ is known to play a unique topological role in the network. This trend is in coincidence with the considerably faster inward diffusion of Mg2+ in comparison to other alkaline earth cations.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    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.

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

    PubMed

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

    2015-02-19

    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.

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

    PubMed

    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

  12. 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

  13. 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)

  14. Dissolution behaviour of iron silicate glass

    NASA Astrophysics Data System (ADS)

    Kubuki, Shiro; Akagi, Kenji; Sakka, Hiroshi; Homonnay, Zoltán; Sinkó, Katalin; Kuzmann, Ernő; Kurimoto, Hiroshi; Nishida, Tetsuaki

    2009-07-01

    A relationship between the water purifying effect and structure of 0.5 xNa2O·0.5 xCaO·5Fe2O3·(95- x)SiO2 glass (Na2O/CaO = 1; NCFS glass) with ‘ x’ of 20 and 50 were investigated by means of 57Fe-Mössbauer spectroscopy, X-ray diffraction (XRD), induced coupled plasma optical emission spectroscopy (ICP-OES), as well as absorption spectroscopy, pH and oxidation-reduction potential (ORP) measurements. In the case NCFS glass with ‘ x’ of 20, dissolved amounts of total Fe, Na + , and Ca2 + were respectively estimated to be 13.6, 39.1 and 36.7 mg/l, after 10 day-leaching test. On the other hand, the dissolved amounts of total Fe, Na + and Ca2 + were determined to be 34.3, 647.6 and 667.6 mg/l, respectively when ‘ x’ was 50. The original pH value of 6.0 was increased to 10.0 and 11.6 after leaching test of NCFS glasses with ‘ x’ of 20 and 50, respectively. At the same time, the ORP value was decreased from 30.0 to -195.8 and -284.7 mV in the glasses with ‘ x’ of 20 and 50, respectively.

  15. Infrared spectroscopy and hydrogen isotope geochemistry of hydrous silicate glasses

    SciTech Connect

    Epstein, S.; Stolper, E.

    1992-01-01

    The focus of this project is the combined appication of infrared spectroscopy and stable isotope geochemistry to the study of hydrogen-bearing species dissolved in silicate melts and glasses. We are conducting laboratory experiments aimed at determining the fractionation of D and H between melt species (OH and H{sub 2}O) and hydrous vapor and the diffusivities of these species in glasses and melts. Knowledge of these parameters is critical to understanding the behavior of hydrogen isotopes during igneous processes and hydrothermal processes. These results also could be valuable in application of glass technology to development of nuclear waste disposal strategies.

  16. 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.

  17. A-thermal elastic behavior of silicate glasses.

    PubMed

    Rabia, Mohammed Kamel; Degioanni, Simon; Martinet, Christine; Le Brusq, Jacques; Champagnon, Bernard; Vouagner, Dominique

    2016-02-24

    Depending on the composition of silicate glasses, their elastic moduli can increase or decrease as function of the temperature. Studying the Brillouin frequency shift of these glasses versus temperature allows the a-thermal composition corresponding to an intermediate glass to be determined. In an intermediate glass, the elastic moduli are independent of the temperature over a large temperature range. For sodium alumino-silicate glasses, the a-thermal composition is close to the albite glass (NaAlSi3O8). The structural origin of this property is studied by in situ high temperature Raman scattering. The structure of the intermediate albite glass and of silica are compared at different temperatures between room temperature and 600 °C. When the temperature increases, it is shown that the high frequency shift of the main band at 440 cm(-1) in silica is a consequence of the cristobalite-like alpha-beta transformation of 6-membered rings. This effect is stronger in silica than bond elongation (anharmonic effects). As a consequence, the elastic moduli of silica increase as the temperature increases. In the albite glass, the substitution of 25% of Si(4+) ions by Al(3+) and Na(+) ions decreases the proportion of SiO2 6-membered rings responsible for the silica anomaly. The effects of the silica anomaly balance the anharmonicity in albite glass and give rise to an intermediate a-thermal glass. Different networks, formers or modifiers, can be added to produce different a-thermal glasses with useful mechanical or chemical properties.

  18. A-thermal elastic behavior of silicate glasses.

    PubMed

    Rabia, Mohammed Kamel; Degioanni, Simon; Martinet, Christine; Le Brusq, Jacques; Champagnon, Bernard; Vouagner, Dominique

    2016-02-24

    Depending on the composition of silicate glasses, their elastic moduli can increase or decrease as function of the temperature. Studying the Brillouin frequency shift of these glasses versus temperature allows the a-thermal composition corresponding to an intermediate glass to be determined. In an intermediate glass, the elastic moduli are independent of the temperature over a large temperature range. For sodium alumino-silicate glasses, the a-thermal composition is close to the albite glass (NaAlSi3O8). The structural origin of this property is studied by in situ high temperature Raman scattering. The structure of the intermediate albite glass and of silica are compared at different temperatures between room temperature and 600 °C. When the temperature increases, it is shown that the high frequency shift of the main band at 440 cm(-1) in silica is a consequence of the cristobalite-like alpha-beta transformation of 6-membered rings. This effect is stronger in silica than bond elongation (anharmonic effects). As a consequence, the elastic moduli of silica increase as the temperature increases. In the albite glass, the substitution of 25% of Si(4+) ions by Al(3+) and Na(+) ions decreases the proportion of SiO2 6-membered rings responsible for the silica anomaly. The effects of the silica anomaly balance the anharmonicity in albite glass and give rise to an intermediate a-thermal glass. Different networks, formers or modifiers, can be added to produce different a-thermal glasses with useful mechanical or chemical properties. PMID:26815634

  19. Structural effects of phosphorus inclusion in bioactive silicate glasses.

    PubMed

    Tilocca, Antonio; Cormack, Alastair N

    2007-12-27

    Molecular dynamics simulations of four bioactive silicate glasses containing between 0 (P0) and 12 (P12) mol % P2O5 have been carried out in order to elucidate the structural role of phosphorus in these materials. In particular, we have focused on structural features which can have a direct role in the bioactive mechanism of dissolution and bone bonding. The higher affinity of modifier Na and Ca cations for coordinating phosphate rather than silicate, together with the formation of P-O-Si linkages, lead to increasing repolymerization of the silicate network with increasing P2O5 content, which in principle would represent a negative effect of P inclusion on the glass bioactivity. However, this effect is counterbalanced by the concomitant increase in the amount of free orthophosphate groups, whose fast release is deemed to enhance the bioactivity. The strong affinity of the orthophosphates for calcium ions leads to a clear tendency toward separation of silicate-rich and phosphate-rich phases for the P12 composition. Although this could reduce the bioactivity in the case of P12, in general, the favorable balance between the effects mentioned above should result in a positive effect of partial Si --> P substitution on the glass bioactivity.

  20. 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.

  1. 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.

  2. 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.

  3. A preliminary investigation of chlorine XANES in silicate glasses

    NASA Astrophysics Data System (ADS)

    Evans, K. A.; Mavrogenes, J. A.; O'Neill, H. S.; Keller, N. S.; Jang, L.-Y.

    2008-10-01

    Chlorine speciation in silicate melts affects volatile exsolution, rheology, and thermodynamic properties of the melt but is poorly known. X-Ray Absorption Near Edge Structure (XANES) spectra have been used to investigate Cl speciation in 26 silicate glasses and to test the hypothesis that Cl in silicate melts is hosted by species that combine Cl and network-modifying cations such as Ca and Mg. Results indicate that Cl in CMAS (CaO-MgO-Al2O3-SiO2) plus Na2O, K2O, or MnO silicate glasses exists as a combination of Ca-Clx and Mg-Clx species or, possibly, as mixed Ca-Mgy-Clx species. The geometry and stoichiometry of the proposed species is unknown, but there are similarities between spectra from Ca-bearing melts and the spectra of hydrated CaCl2.2H2O, suggesting that the Ca-Clx species could have a salt-like atomic arrangement and ionic bonding. Further investigations using XANES, alternative spectroscopic techniques, and forward modeling approaches are required to distinguish between these possibilities.

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  5. Bismuth-doped Mg - Al silicate glasses and fibres

    SciTech Connect

    Bufetov, Igor' A; Vel'miskin, V V; Galagan, B I; Denker, B I; Sverchkov, S E; Semjonov, S L; Firstov, Sergei V; Shulman, I L; Dianov, Evgenii M

    2012-09-30

    This paper compares the optical properties of bulk bismuth-doped Mg - Al silicate glasses prepared in an iridium crucible to those of optical fibres prepared by the powder-in-tube method and having a core identical in composition to the glasses. The bulk glasses and fibres are shown to be similar in luminescence properties. The optical loss in the fibres in their IR luminescence band is about one order of magnitude lower than that in the crucible-melted glasses. The level of losses in the fibres and their luminescence properties suggest that such fibres can be made to lase near 1.15 {mu}m. (optical fibres, lasers and amplifiers. properties and applications)

  6. Lanthanides in silicate glasses: A vibrational spectroscopic study

    NASA Astrophysics Data System (ADS)

    Ellison, Adam J. G.; Hess, Paul C.

    1990-09-01

    Parallel- and perpendicular-polarized Raman and KBr pellet transmission IR spectra of quenched 10K2O-50SiO2-nR2O3 (R = La, Gd, Yb; n = 0, 1, 5, 10 mol) glasses are presented. Increasing lanthanide oxide concentration produces partially-polarized high-frequency bands at 1030, 940, and 860 cm-1, assigned to the symmetric stretching modes of SiO4 tetrahedra containing 1, 2, and 4 nonbridging oxygen, respectively, in which the nonbridging oxygen coordinate primarily with lanthanides. Lanthanides therefore form silicate anions that are depolymerized relative to the bulk liquid and which have no counterparts in R2O3-SiO2 binary systems. The spectra indicate that there is little sharing of nonbridging oxygen by K and lanthanides. The spectra of glasses containing different lanthanides at the same concentration are qualitatively and quantitatively very similar. Lanthanides have energetically unfavorable interactions with the network structure of polymerized liquids compared to cations of lower valence. If lanthanides coordinate nonbridging oxygen without the aid of K, then lanthanide saturation concentrations will show modest increases with increasing (Na,K)/Al in peralkaline liquids, except in liquids in which P2O5 concentration is comparable to the total lanthanide concentration. Since differences in lanthanide ionic radii have small effects upon the spectra, lanthanide solution mechanisms in silicate glasses (and by inference silicate liquids) are probably very similar.

  7. 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).

  8. 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.

  9. Scaling behavior in the conductivity of alkali oxide glasses

    SciTech Connect

    Sidebottom, D.L.; Green, P.F.; Brow, R.K.

    1995-11-01

    Although the frequency dependent conductivity, {sigma}({omega}), of ion-containing glasses displays power law dispersion ({sigma}({omega}) {approx} {omega}{sup n}) that can usually be described by a master curve, several findings have suggested that this scaling fails at low temperatures as indicated by a temperature dependence of the scaling exponent, n. The authors investigate this behavior in the frequency range between 1 Hz and 10{sup 6} Hz for a different materials including alkali metaphosphate glasses and a polymer. They identify two distinct regimes of conductive behavior, {sigma}{sub {vert_bar}} and {sigma}{sub {parallel}}. The first, {sigma}{sub {vert_bar}}, is strongly temperature dependent and appears to obey a master curve representation. The second, {sigma}{sub {parallel}}, exhibits only a weak temperature dependence with a roughly linear frequency dependence. A strong depression of {sigma}{sub {vert_bar}} occurs for the mixed alkali case, but {sigma}{sub {parallel}} is unaffected and occurs at roughly the same location in all the alkali compositions studied. They propose that {sigma}{sub {parallel}} does not arise from cation motion, but rather originates from a second mechanisms likely involving small distortions of the underlying glassy matrix. This assignment of {sigma}{sub {parallel}} is further supported by the roughly universal location of {sigma}{sub {parallel}}, to within an order of magnitude, of a variety of materials, including a polymer electrolyte and a doped crystal. Since {sigma}{sub {vert_bar}}(T) and {sigma}{sub {parallel}}(T {approx} const.) are viewed as separate phenomena, the temperature dependence of the scaling exponent is shown to result merely from a superposition of these two contributions and does not indicate any intrinsic failure of the scaling property of {sigma}{sub {vert_bar}}.

  10. 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.

  11. Structural relaxation dynamics and annealing effects of sodium silicate glass.

    PubMed

    Naji, Mohamed; Piazza, Francesco; Guimbretière, Guillaume; Canizarès, Aurélien; Vaills, Yann

    2013-05-01

    Here we report high-precision measurements of structural relaxation dynamics in the glass transition range at the intermediate and short length scale for a strong sodium silicate glass during long annealing times. We evidence for the first time the heterogeneous dynamics at the intermediate range order by probing the acoustic longitudinal frequency in the GHz region by Brillouin light scattering spectroscopy. Or, from in-situ Raman measurements, we show that relaxation is indeed homogeneous at the interatomic length scale. Our results show that the dynamics at the intermediate range order contains two distinct relaxation time scales, a fast and a slow component, differing by about a 10-fold factor below Tg and approaching to one another past the glass transition. The slow relaxation time agrees with the shear relaxation time, proving that Si-O bond breaking constitutes the primary control of structural relaxation at the intermediate range order.

  12. 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.

  13. Optical properties of gamma irradiated soda-lime silicate glasses exchanged with copper

    NASA Astrophysics Data System (ADS)

    Macalik, B.

    2003-01-01

    The effect of copper ion exchange upon the optical absorption and room temperature gamma colouration of soda lime silicate glasses has been investigated. After ion exchange performed at 720 K, copper ions substitute mainly the alkali ions and do modify the optical absorption spectra of the specimens. It has been shown that gamma irradiation does not induce the formation of colloidal copper. Moreover, the colouration process itself is independent of the presence of copper ions. The generated colour centres are rather related to the presence of sodium and potassium ions. The optical bleaching by the UV light occurs in two stages. First disappear centres related to the Na-type defects and next those related to the K-type defects.

  14. Humidity sensing by nanocomposites of silver in silicate glass ceramics

    NASA Astrophysics Data System (ADS)

    Pal, B. N.; Kundu, T. K.; Banerjee, S.; Chakravorty, D.

    2003-04-01

    Silver nanoparticles of diameters in the range 3.4 to 13.2 nm were grown within a silicate glass ceramics containing barium titanate phase. The glass ceramics were filled with silver particles by subjecting the former to a Na+-Ag+ ion exchange process followed by a reduction treatment in hydrogen. Silver particles were formed at the interfaces of the silicate glass and the barium titanate phases, respectively. The silver particle sizes could be varied by controlling the fractal structure of the crystalline phase by prior heat treatment. Electrical resistivity measurements were carried out on cold-pressed specimens of nanocomposite powders prepared as just stated. A five order of magnitude resistivity change was recorded in the case of nanocomposite specimen with a silver particle diameter of 10.1 nm in the relative humidity range of 25% to 85%. The resistivity of the nanocomposites was found to be controlled by a variable range hopping conduction. It is believed that the silver nanoparticles provide sites where physisorption of water molecules takes place which increases the number of localized states near the Fermi level.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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).

  20. 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

  1. 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.

  2. 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.

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

    PubMed

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

    2015-07-17

    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.

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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. PMID:25605624

  9. 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.

  10. 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.

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

    SciTech Connect

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

    2014-05-15

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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Internal friction of hydrated soda-lime-silicate glasses.

    PubMed

    Reinsch, S; Müller, R; Deubener, J; Behrens, H

    2013-11-01

    The internal friction of hydrated soda-lime-silica glasses with total water content (C(W)) up to 1.9 wt. % was studied by dynamic mechanical analysis (DMA) using temperature-frequency sweeps from 723 K to 273 K and from 1 s(-1) to 50 s(-1). Total water content and concentrations of H2O molecules (C(H2O)) and OH groups (C(OH)) in the DMA specimens were determined by infrared spectroscopy. For low water contents (C(W) ≈ C(OH) < 0.25 wt. %) two discrete internal friction peaks below the glass transition (α relaxation) were assigned to the low-temperature motion of alkali ions (γ relaxation) and cooperative movements of dissimilar mobile species under participation of OH at higher temperature (β(OH) relaxation). For large water contents (C(W) > 1 wt. %), where significant amounts of molecular water are evident (C(H2O) > 0.15 wt. %), however, internal friction spectra change unexpectedly: the β(OH) peak heights saturate and a low temperature shoulder appears on the β-relaxation peak. This emerging relaxation mode (β(H2O) relaxation) was assigned to the motions of H2O molecules. β(H2O) relaxation was found to be faster than β(OH) but slower than γ relaxation. Activation energy of the different relaxation modes increased in the order γ < β(H2O) < β(OH) < α. PMID:24206315

  18. 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.

  19. 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.

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

    PubMed

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

    2015-12-28

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

  1. 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.

  2. Compressibility of magnesium silicate glasses in comparison with those of aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    Kuryaeva, R. G.

    2013-10-01

    The refractive index of the Na2MgSi6O14 glass in the pressure range up to 6.0 GPa has been measured using a polarization-interference microscope and an apparatus with diamond anvils. The changes in relative density which characterize the compressibility of the glass have been estimated in the pressure range under investigation from the measured refractive indices within the framework of the theory of photoelasticity. The results have been compared with the data previously obtained for the NaAlSi3O8 and CaAl2Si6O16 glasses. A comparison of the changes in relative density of the aluminosilicate and magnesium silicate glasses has been demonstrated that the difference in the compressibility is not so much significant as should be expected from the replacement of network-forming ions by modifiers ions. Estimated by different methods the degree of depolymerization of the Na2MgSi6O14 glass (NBO/T ≅ 0.2) is compared to those for the aluminosilicate glasses. The decrease in the compressibility in the series NaAlSi3O8, CaAl2Si6O16, Na2MgSi6O14 glasses is in agreement with an increase of the degree of depolymerization in the same series.

  3. Sensitivity of Structural Results to Initial Configurations and Quench Algorithms of Lead Silicate Glass

    SciTech Connect

    Hemesath, Eric R.; Corrales, Louis R.

    2005-06-15

    The sensitivity of resulting structures to starting configurations and quench algorithms were characterized using molecular dynamics (MD) simulations. The classical potential model introduced by Damodaran, Rao, and Rao (DRR) Phys. Chem. Glasses 31, 212 (1990) for lead silicate glass was used. Glasses were prepared using five distinct initial configurations and four glass forming algorithms. In previous MD work of bulk lead silicate glasses the ability of this potential model to provide good structural results were established by comparing to experimental results. Here the sensitivity of the results to the simulation methodology and the persistence of clustering with attention to details of molecular structure are determined.

  4. 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.

  5. 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

  6. The influence of alkali and alkaline earths on the working range for bioactive glasses.

    PubMed

    Brink, M

    1997-07-01

    Viscosity-temperature dependence has been investigated for glasses in a system where bioactive compositions are found. A glass is called bioactive when living bone can bond to it. In this work, high-temperature microscopy was used to determine viscosity-temperature behaviour for 40 glasses in the system Na2O-K2O-MgO-CaO-B2O3-P2O5-SiO2. The silica content in the glasses was 39-70 wt% % All glasses containing < 54 mol % SiO2 devitrified during the viscosity measurements. Generally, glasses that devitrified contained more alkali but less alkaline earths than glasses with a large working range. A working range is the temperature interval at which forming of a glass can take place. This temperature interval can, for bioactive glasses, be enlarged by decreasing the amount of alkali, especially Na2O, in the glass and by increasing the amount of alkaline earths, especially MgO. Optionally, B2O3 and P2O5 can be added to the glass. An enlarged working range is a prerequisite for an expanded medical use of bioactive glasses as e.g., sintered and blown products, and fibers. PMID:9212395

  7. Polymerization of silicate and aluminate tetrahedra in glasses, melts and aqueous solutions—II. The network modifying effects of Mg 2+ , K +, Na +, Li +, H +, OH -, F -, Cl -, H 2O, CO 2 and H 3O + on silicate polymers

    NASA Astrophysics Data System (ADS)

    de Jong, B. H. W. S.; Brown, Gordon E., Jr.

    1980-11-01

    The effect of the group IA and VIIA ions, as well as Mg 2+, and the molecules H 2O, CO 2, H 3O + and OH - on the energy of the Si-O bond in a H 6Si 2O 7 cluster has been calculated using semiempirical molecular orbital calculations (CNDO/2). Three types of elementary processes, i.e. substitution, addition, and polymerization reactions have been used to interpret data on the dynamic viscosity, surface tension and surface charge, hydrolytic weakening, diffusivity, conductivity, freezing point depression, and degree of polymerization of silicates in melts, glasses, and aqueous solutions. As a test of our calculational procedure, observed X-ray emission spectra of binary alkali silicate glasses were compared with calculated electronic spectra. The well known bondlength variations between the bridging bond [Si-O(br)] and the non-bridging bond [Si-O(nbr)] in alkali silicates are shown to be due to the propagation of oscillating bond-energy patterns through the silica framework. A kinetic interpretation of some results of our calculations is given in terms of the Bell-Evans-Polanyi reaction principle.

  8. 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.

  9. The role of Gd2O3 and Y2O3 in corrosion of soda lime silicate glass

    NASA Astrophysics Data System (ADS)

    Wang, Mitang; Li, Mei; Cheng, Jinshu; He, Feng; Liu, Zhaogang; Hu, Yanhong

    2013-02-01

    Corrosion of soda-lime-silicate glasses containing Gd and Y has been carried out by solution and solid analyses, to investigate the effect of Gd and Y on the chemical durability of silicate glass. The results showed that the incorporation of Gd and Y into silicate glass decreases glass constituent releases and increases chemical durability. The morphology of glass surface and thickness of altered layer were observed that the degree of corroding of the soda lime silicate glass doped with Gd and Y was significantly less than that of the base glass. EDS microanalyses revealed that the effect of Gd and Y on the altered layer is different, the non-congruent dissolution process is observed in the case of Gd doped glasses. Besides, the improving effect of Gd and Y on acid and alkaline resistance of silicate glasses can attribute to their larger ionic radius and higher cation field strength.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. Cation-network interactions in binary alkali metal borate glasses. A far-infrared study

    SciTech Connect

    Kamitsos, E.I.; Karakassides, M.A.; Chryssikos, G.D.

    1987-10-22

    The far-infrared spectra of compositions probing the glass-forming regions of all five binary alkali metal borate systems chi M/sub 2/O x (1 - chi)B/sub 2/O/sub 3/ (0 < chi less than or equal to 0.40, M = Na; and 0 < chi less than or equal to 0.35, M = K, Rb, Cs) have been measured and analyzed to systematically study the alkali metal cation-network interactions and their compositional dependence. Band deconvolution of the measured spectra showed the presence of two distinct distributions of alkali metal cation sites in Li, Na, and K glasses. Similar results have been obtained for rubidium and cesium borate glasses of compositions chi > 0.25. One distribution of cation sites has been observed for the lower alkali metal content Rb and Cs glasses. The fractions of cations in the two different network sites have also been evaluated. The squares of the frequencies of the cation-motion bands were found to vary linearly with composition, and exhibit kinks at chi similarly ordered 20, for all but the Cs glasses. This behavior was explained on the basis of the network structural changes known to occur at this composition.

  15. Structure and topology of soda-lime silicate glasses: implications for window glass.

    PubMed

    Laurent, O; Mantisi, B; Micoulaut, M

    2014-11-01

    The structural and topological properties of soda-lime silicate glasses of the form (1-2x)SiO2-xNa2O-xCaO are studied from classical molecular dynamics using a Buckingham type potential. Focus is made on three compositions (x = 6%, 12%, and 18%) which are either silica-rich or modifier-rich. We compare the results to available experimental measurements on structural properties and find that the simulated pair correlation function and total structure factor agree very well with available experimental measurements from neutron diffraction. The detail of the structural analysis shows that the Na and Ca coordination numbers tend to evolve with composition, and with increasing modifier content, changing from 5.0 to 5.6 and from 4.0 to 5.0 for Ca and Na, respectively. The analysis from topological constraints shows that the picture derived on a heuristic basis using classical valence rules remains partially valid. Ultimately, typical elastic phases are identified from the application of rigidity theory, and results indicate that the 6% system is stressed-rigid, whereas the modifier-rich composition (18%) is flexible. These results receive support from a full analysis of the vibrational density of states showing the low-energy bands at E < 20 meV increase as the system becomes flexible, providing another indirect signature of the presence of rigid to flexible transitions in this archetypal glass. Consequences for window glass are discussed under this perspective. PMID:25295377

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  18. 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.

  19. 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. PMID:25946963

  20. Effect of Fe2O3 on the physical and structural properties of bismuth silicate glasses

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

    Iron containing bismuth silicate glasses with compositions 70SiO2ṡ(100-x)Bi2O3ṡxFe2O3 have been prepared using conventional melt-quenching method and their amorphous nature has been investigated using XRD. Density has been measured using Archimedes' principle and molar volume (Vm) have also been estimated. With increase in Fe2O3 content, there is a decrease in density and molar volume of the glass samples. The glass transition temperature (Tg) have been determined using Differential Scanning Calorimetry (DSC) and are observed to increase with increase in Fe2O3 content. In the present glass system bismuth and iron plays the role of network modifier and the symmetry of silicate network goes on increasing with Fe2O3 content and it modifies the physical and structural properties of these glasses.

  1. Plutonium silicate alteration phases produced by aqueous corrosion of borosilicate glass.

    SciTech Connect

    Fortner, J. A.; Mertz, C. J.; Bakel, A. J.; Finch, R. J.; Chamerlain, D. B.

    1999-11-22

    Borosilicate glasses loaded with {approx}10 wt % plutonium were found to produce plutonium-silicate alteration phases upon aqueous corrosion under a range of conditions. The phases observed were generally rich in lanthanide (Ln) elements and were related to the lanthanide orthosilicate phases of the monoclinic Ln{sub 2}SiO{sub 5} type. The composition of the phases was variable regarding [Ln]/[Pu] ratio, depending upon type of corrosion test and on the location within the alteration layer. The formation of these phases likely has implications for the incorporation of plutonium into silicate alteration phases during corrosion of titanate ceramics, high-level waste glasses, and spent nuclear fuel.

  2. Quantitative structure-property relationships of potentially bioactive fluoro phospho-silicate glasses.

    PubMed

    Lusvardi, G; Malavasi, G; Tarsitano, F; Menabue, L; Menziani, M C; Pedone, A

    2009-07-30

    In this work, the glass transition temperature and chemical durability of bioactive phospho-silicate glasses were experimentally determined and correlated to the structural descriptor Fnet derived from classical molecular dynamics simulations. The replacement of CaF2 for Na2O in the parent glass 45S5 enhances both chemical durability and density, while the replacement of CaF2 for CaO lowers chemical durability. The proposed descriptor, Fnet, provides satisfactorily correlations with glass transition temperature and chemical durability over a wide range of compositions.

  3. Computational study on ionic diffusion and dynamic properties in silicate and bioactive glasses

    NASA Astrophysics Data System (ADS)

    Xiang, Ye; Du, Jincheng

    2011-03-01

    Ionic diffusion and dynamic properties in silicate glasses have been extensively studied experimentally due to its importance in understanding ion conduction and glass dissolution. In this study, computational study on ionic diffusion and dynamic properties was carried out using molecular dynamics simulations with effective partial charge potentials. The simulated structure models were validated by comparing with experimental data and systematic discussions on effects of system size, simulation thermal ensemble and temperature range were carried out. The dynamic properties were also related to structural changes with the glass. Finally, investigation of SrO/CaO substitution effect on the diffusion behaviors in 45S glasses is provided.

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

    SciTech Connect

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

    2012-04-01

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

  5. Morphology of potassium sodium niobate based silicate glass system

    NASA Astrophysics Data System (ADS)

    Yongsiri, Ploypailin; Eitssayeam, Sukum; Sirisoonthorn, Somnuk; Pengpat, Kamonpan

    2013-11-01

    In this research, the fabrication of lead-free ferroelectric glass-ceramics from the (K0.5Na0.5)NbO3 system via incorporation method was carried out. For the incorporation method, calcined KNN was added into glass batches as a heterogeneous nucleating agent. Glass-ceramics KNNs were prepared from two compositions of KNN-SiO2 with a ratio of 75 : 25 (C1) and 80 : 20 (C2) mol.%. Thermal properties resulting from DTA showed samples C1 and C2 having glass transition temperatures of 532°C and 520°C and crystallization temperatures of 645°C and 620°C, respectively. The prepared glasses were subsequently subjected to a heat treatment schedule in a temperature range of 500°C - 575°C for crystallization. XRD results showed that the KNN phase occurred in C1. The C2 glass-ceramic samples contained unidentified phases together with the KNN phase. From SEM observation, it was found that bulk crystals with an equiaxed shape of KNN phase dispersed well in all glass-ceramic matrices. Crystal sizes increased with increasing heat treatment temperatures. In C2 glass-ceramics, unidentified phases were found together with the KNN phase.

  6. 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.

  7. Silicate glass alteration enhanced by iron: origin and long-term implications.

    PubMed

    Michelin, A; Burger, E; Rebiscoul, D; Neff, D; Bruguier, F; Drouet, E; Dillmann, P; Gin, S

    2013-01-15

    Silicate glasses are used as containment matrices for deep geological disposal of nuclear waste arising from spent fuel reprocessing. Understanding the dissolution mechanisms of glasses in contact with iron, an element present in large amounts in the immediate environment (overpack, claystone, etc.) would be a major breakthrough toward predicting radionuclide release in the geosphere after disposal. Two different reacted glass-iron interfaces-a short-term nuclear system and a long-term archeological system-were examined using a multiscale and multianalytical approach including, for the first time on samples of this type, STXM under synchrotron radiation. Comparisons revealed remarkable similarities between the two systems and shed light on Fe-Si interactions, including migration of iron within a porous gel layer and precipitation of Fe-silicates that locally increase short-term glass alteration and are sustainable over the long-term.

  8. 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.

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

    SciTech Connect

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

    2008-02-15

    Lithium zinc silicate glasses of composition (mol%): 17.5Li{sub 2}O-(72-x)SiO{sub 2}-xZnO-5.1Na{sub 2}O-1.3P{sub 2}O{sub 5}-4.1B{sub 2}O{sub 3}, 5.5{<=}x{<=}17.7, were prepared by conventional melt-quenched technique and converted to glass-ceramic by controlled crystallization process. {sup 29}Si and {sup 31}P MAS-NMR was used to characterize the structure of both glass and glass-ceramic samples. Despite the complex glass composition, Q{sup 2}, Q{sup 3} and Q{sup 4} sites are identified from {sup 29}Si MAS-NMR, which relative intensities are found to vary with the ZnO content, indicating a network depolymerization by ZnO. Moreover, well separated Q{sup 3} and Q{sup 4} resonances for low ZnO content indicates the occurrence of phase separation. From {sup 31}P MAS-NMR, it is seen that phosphorus is mainly present in the form of ortho-(Q{sup 0}) and pyro-phosphate (Q{sup 1}) 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{sub 2}Si{sub 2}O{sub 5}), lithium zinc ortho-silicate (Li{sub 3}Zn{sub 0.5}SiO{sub 4}), tridymite (SiO{sub 2}) and cristobalite (SiO{sub 2}) were identified as major silicate crystalline phases. Using {sup 29}Si MAS-NMR, quantification of these silicate crystalline phases is carried out and correlated with the ZnO content in the glass-ceramics samples. In addition, {sup 31}P spectra unambiguously revealed the presence of crystalline Li{sub 3}PO{sub 4} and (Na,Li){sub 3}PO{sub 4} in the glass-ceramics. - Graphical abstract: {sup 29}Si and {sup 31}P MAS-NMR analyses were carried out on multi-component Li{sub 2}O-SiO{sub 2}-ZnO-Na{sub 2}O-P{sub 2}O{sub 5}-B{sub 2}O{sub 3} glasses and glass-ceramics developed for sealing application. Structural data are reported, including phase separation process and quantification of amorphous and crystalline phases.

  10. Abnormal acoustic wave velocities in basaltic and (Fe,Al)-bearing silicate glasses at high pressures

    NASA Astrophysics Data System (ADS)

    Liu, Jin; Lin, Jung-Fu

    2014-12-01

    We have measured acoustic VP and VS velocities of (Fe,Al)-bearing MgSiO3 silicate glasses and an Icelandic basalt glass up to 25 GPa. The velocity profiles of the (Fe,Al)-bearing and basaltic silicate glasses display decreased VP and VS with minima at approximately 5 and 2 GPa, respectively, which could be explained by the mode softening in the aluminosilicate networks. Our results represent the first observation of such velocity softening extending into the chemically complex basaltic glass at a relatively low transition pressure, which is likely due to its degree of polymerization, while the Fe and Al substitutions reduce sound velocities in MgSiO3 glass. If the velocity softening in the basaltic and silicate glasses can be used as analogs for understanding melts in Earth's interior, these observations suggest that the melt fraction needed to account for the velocity reduction in the upper mantle low-velocity zone may be smaller than previously thought.

  11. 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.

  12. 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.

  13. 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.

  14. Infrared spectroscopy and hydrogen isotope geochemistry of hydrous silicate glasses. Progress report

    SciTech Connect

    Epstein, S.; Stolper, E.

    1992-03-01

    The focus of this project is the combined appication of infrared spectroscopy and stable isotope geochemistry to the study of hydrogen-bearing species dissolved in silicate melts and glasses. We are conducting laboratory experiments aimed at determining the fractionation of D and H between melt species (OH and H{sub 2}O) and hydrous vapor and the diffusivities of these species in glasses and melts. Knowledge of these parameters is critical to understanding the behavior of hydrogen isotopes during igneous processes and hydrothermal processes. These results also could be valuable in application of glass technology to development of nuclear waste disposal strategies.

  15. 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.

  16. Enthalpies of Mixing in Sodium Silicate Glasses and Relevance to Adam-Gibbs Theory

    NASA Astrophysics Data System (ADS)

    Hovis, G.; Jarry, P.; Toplis, M.; Richet, P.

    2003-12-01

    Solution calorimetric measurements have been made in 20.1 wt % hydrofluoric acid at 50° C on binary Na2O-SiO2 glasses ranging in composition from 0 to 50 mol % Na2O. The initial calorimetric data for compositions between 20 and 50 mol % Na2O were highly variable, determined later to be due to the development of Na carbonate on the glass surfaces. However, additional measurements using minimally-ground specimens that had been remelted shortly before the calorimetric dissolutions produced highly reproducible results. After adjustment of the data for glass transition temperature (Richet et al., 1984, J. Amer. Ceram. Soc.), the results show nearly linear ("ideal") behavior of the heats of solution between 50 % Na2O and 30-35 % Na2O. However, positive enthalpies of mixing (Hex) are evident in the compositional region between 0 and 30-35 mol % Na2O, with maximum magnitudes of Hex on the order of 5 kJ/mol relative to 0 and 35 % Na2O end members. Within the framework of the Adam-Gibbs theory of structural relaxation, viscosity and heat capacity data may be combined to determine configurational entropies of silicate glasses. When applied to sodium silicate glasses (Toplis, 2001, Chemical Geology), positive entropies of mixing (Sex) are calculated for compositions between 0 and 30 mole % Na2O, a compositional region where liquid immiscibility also is known to occur (Haller et al., 1974, J. Amer. Ceram. Soc.) and where Gibbs free energies of mixing (Gex) therefore must be positive. Because positive entropies of mixing contribute negatively (-TSex) to Gex, the observed immiscibility requires positive enthalpies of mixing (Hex) in the silicic part of the compositional range. The present study confirms such positive enthalpies of mixing and supports the usefulness of Adam-Gibbs theory for the prediction of viscosity/entropy behavior of silicate glasses and liquids.

  17. Contact fatigue mechanisms as a function of crystal aspect ratio in baria-silicate glass ceramics

    NASA Astrophysics Data System (ADS)

    Suputtamongkol, Kallaya

    2003-10-01

    Ceramic materials are potentially useful for dental applications because of their esthetic potential and biocompatibility. However, the existence of fatigue damage in ceramics raises considerable concern regarding its effect on the life prediction of dental prostheses. During normal mastication, dental restorations are subjected to repeated loading more than a thousand times per day and relatively high clinical failure rates for ceramic prostheses have been reported. To simulate the intraoral loads, Hertzian indentation loading was used in this study to characterize the fatigue failure mechanisms of ceramic materials using clinically relevant parameters. The baria-silicate system was chosen because of the nearly identical composition between the crystal and the glass matrix. Little or no residual stress is expected from the elastic modulus and thermal expansion mismatches between the two phases. Crystallites with different aspect ratios can also be produced by controlled heat treatment schedules. The objective of this study was to characterize the effect of crystal morphology on the fatigue mechanisms of bariasilicate glass-ceramics under clinically relevant conditions. The results show that the failure of materials with a low toughness such as baria-silicate glass (0.7 MPa•m1/2) and glass-ceramic with an aspect ratio of 3/1 (1.3 MPa•m1/2) initiated from a cone crack developed during cyclic loading for 103 to 105 cycles. The mean strength values of baria-silicate glass and glass-ceramic with an aspect ratio of 3/1 decreased significantly as a result of the presence of a cone crack. Failure of baria-silicate glass-ceramics with an aspect ratio of 8/1 (Kc = 2.1 MPa•m1/2) was initiated from surface flaws caused by either polishing or cyclic loading. The gradual decrease of fracture stress was observed in specimens with an aspect ratio of 8/1 after loading in air for 103 to 10 5 cycles. A reduction of approximately 50% in fracture stress levels was found for

  18. 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

  19. 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.

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

    PubMed

    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

  1. 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.

  2. 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

  3. Trace-element sanidine/glass distribution coefficients for peralkaline silicic rocks and their implications to peralkaline petrogenesis

    NASA Astrophysics Data System (ADS)

    Drexler, J. W.; Bornhorst, T. J.; Noble, D. C.

    1983-10-01

    Sanidine/glass distribution coefficients for 11 trace elements have been determined on six peralkaline and two subalkaline silicic rocks. Distribution coefficients for Na, Sc, Fe, Cs, La, Ce, Sm, Tb and Lu from this study and the literature show little variation, within analytical uncertainty, for silicic rocks of peralkaline and subalkaline affinity. Distribution coefficients for Eu and Rb show a marked decrease with increasing peralkalinity. This variation may be the result of the decrease in the degree of polymerization from subalkaline to peralkaline silicic melts. Previous studies involving modelling of peralkaline rocks have selected, incorrectly, Eu and Rb sanidine/glass distribution coefficients determined from subalkaline silicic rocks.

  4. 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.

  5. 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.

  6. 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. PMID:9665879

  7. Cauchy's dispersion equation reconsidered : dispersion in silicate glasses.

    SciTech Connect

    Smith, D. Y.; Inokuti, M.; Karstens, W.; Physics; Univ. of Vermont; St. Michael's College

    2002-01-01

    We formulate a novel method of characterizing optically transparent substances using dispersion theory. The refractive index is given by a generalized Cauchy dispersion equation with coefficients that are moments of the uv and ir absorptions. Mean dispersion, Abbe number, and partial dispersion are combinations of these moments. The empirical relation between index and dispersion for families of glasses appears as a consequence of Beer's law applied to the uv spectra.

  8. Effects of the degree of polymerization on the structure of sodium silicate and aluminosilicate glasses and melts: An 17O NMR study

    NASA Astrophysics Data System (ADS)

    Lee, Sung Keun; Stebbins, Jonathan F.

    2009-02-01

    Revealing the atomic structure and disorder in oxide glasses, including sodium silicates and aluminosilicates, with varying degrees of polymerization, is a challenging problem in high-temperature geochemistry as well as glass science. Here, we report 17O MAS and 3QMAS NMR spectra for binary sodium silicate and ternary sodium aluminosilicate glasses with varying degrees of polymerization (Na 2O/SiO 2 ratio and Na 2O/Al 2O 3 ratio), revealing in detail the extent of disorder (network connectivity and topological disorder) and variations of NMR parameters with the glass composition. In binary sodium silicate glasses [Na 2O- k(SiO 2)], the fraction of non-bridging oxygens (NBOs, Na-O-Si) increases with the Na 2O/SiO 2 ratio ( k), as predicted from the composition. The 17O isotropic chemical shifts ( 17O δiso) for both bridging oxygen (BO) and NBO increase by about 10-15 ppm with the SiO 2 content (for k = 1-3). The quadrupolar coupling products of BOs and NBOs also increase with the SiO 2 content. These trends suggest that both NBOs and BOs strongly interact with Na; therefore, the Na distributions around BOs and NBOs are likely to be relatively homogenous for the glass compositions studied here, placing some qualitative limits on the extent of segregation of alkali channels from silica-enriched regions as suggested by modified random-network models. The peak width (in the isotropic dimension) and thus bond angle and length distributions of Si-O-Si and Na-O-Si increase with the SiO 2 content, indicating an increase in the topological disorder with the degree of polymerization. In the ternary aluminosilicate glasses [Na 2O] x[Al 2O 3] 1-xSiO 2, the NBO fraction decreases while the Al-O-Si and Al-O-Al fractions apparently increase with increasing Al 2O 3 content. The variation of oxygen cluster populations suggests that deviation from "Al avoidance" is more apparent near the charge-balanced join (Na/Al = 1). The Si-O-Si fraction, which is closely related to the activity

  9. Barium silicate glass/Inconel X-750 interaction. [PWR

    SciTech Connect

    Kelsey, Jr., P. V.; Siegel, W. T.; Miley, D. V.

    1980-01-01

    Water reactor safety programs at the Idaho National Engineering Laboratory have required the development of specialized instrumentation. An example is the electrical conductivity-sensitive liquid level transducer developed for use in pressurized-water reactors (PWRs) in which the operation of the sensing probe relies upon the passage of current through the water between the center pin of the electrode and its shell such that when water is present the resulting voltage is low, and conversely, when water is absent the voltage is high. The transducer's ceramic seal is a hot-pressed glass ceramic; its metal housing is Inconel X-750. The ceramic material provides an essential dielectric barrier between the center pin and the outer housing. The operation of the probe as well as the integrity of the PWR environment requires a hermetically-bonded seal between the ceramic and the metal. However, during testing, an increasing number of probe assemblies failed owing to poor glass-to-metal seals as well as void formation within the ceramic. Therefore, a program was initiated to characterize the metallic surface with respect to pre-oxidation treatment and determine optimum conditions for wetting and bonding of the metal by the glass to obtain baseline data relevant to production of acceptable transducer seals.

  10. 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.

  11. 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).

  12. 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).

  13. Crystallization of neodymium-rich phases in silicate glasses developed for nuclear waste immobilization

    NASA Astrophysics Data System (ADS)

    Caurant, D.; Majerus, O.; Loiseau, P.; Bardez, I.; Baffier, N.; Dussossoy, J. L.

    2006-08-01

    Glass-ceramics containing neodymium-rich crystalline phases can be obtained by crystallization of silicate glasses (nucleation + crystal growth heat treatments) or by controlled cooling of melts. Such materials could be envisaged as durable matrices for conditioning minor actinides- and Pu-rich nuclear wastes if the partitioning ratio of the wastes between crystalline phase and residual glass is high (principle of double containment barrier). In radioactive waste forms, Nd would be partially substituted by actinides and neutron absorbers (Gd). In this work, two silicate glass compositions leading to efficient nucleation and crystallization of either zirconolite (Ca 1- xNd xZrTi 2- xAl xO 7, x < 1) or apatite (Ca 2Nd 8Si 6O 26) in their bulk were studied as potential waste forms. The effect of the method used to prepare glass-ceramics (controlled cooling from the melt or nucleation + crystal growth from the glass) on both the microstructure and the structure of the neodymium-rich crystalline phase was studied. The highest number of zirconolite or apatite crystals in the bulk was obtained using the nucleation + crystal growth method. However, the percentage of neodymium incorporated in zirconolite crystals remained too small to make realistic the use of such materials for the conditioning of actinides in comparison with more durable bulk ceramics.

  14. Cation mass dependence of the nearly constant dielectric loss in alkali triborate glasses.

    PubMed

    Rivera, A; León, C; Varsamis, C P E; Chryssikos, G D; Ngai, K L; Roland, C M; Buckley, L J

    2002-03-25

    Electrical ac conductivity measurements on alkali triborate glasses ( M2O x 3B2O3, M = Li, Na, K, and Rb) were performed at temperatures down to 8 K and frequencies up to 1 GHz. All samples show a nearly constant dielectric loss (NCL), at the limit of high frequencies and/or low temperatures. The magnitude of the NCL is found to decrease as m(-1/3) with increasing alkali ion mass m. This quantitative result for the NCL, closely related to the mean-square displacement of ions, indicates that the origin of the NCL might be related to vibrational relaxation of the ions in the anharmonic potentials that cage them, and the cage is decaying very slowly with time. PMID:11909481

  15. Infrared Spectroscopic Study For Structural Investigation Of Lithium Lead Silicate Glasses

    SciTech Connect

    Ahlawat, Navneet; Aghamkar, Praveen; Ahlawat, Neetu; Agarwal, Ashish; Monica

    2011-12-12

    Lithium lead silicate glasses with composition 30Li{sub 2}O{center_dot}(70-x)PbO{center_dot}xSiO{sub 2}(where, x = 10, 20, 30, 40, 50 mol %)(LPS glasses) were prepared by normal melt quench technique at 1373 K for half an hour in air to understand their structure. Compositional dependence of density, molar volume and glass transition temperature of these glasses indicates more compactness of the glass structure with increasing SiO{sub 2} content. Fourier transform infrared (FTIR) spectroscopic data obtained for these glasses was used to investigate the changes induced in the local structure of samples as the ratio between PbO and SiO{sub 2} content changes from 6.0 to 0.4. The observed absorption band around 450-510 cm{sup -1} in IR spectra of these glasses indicates the presence of network forming PbO{sub 4} tetrahedral units in glass structure. The increase in intensity with increasing SiO{sub 2} content (upto x = 30 mol %) suggests superposition of Pb-O and Si-O bond vibrations in absorption band around 450-510 cm{sup -1}. The values of optical basicity in these glasses were found to be dependent directly on PbO/SiO{sub 2} ratio.

  16. Bioactivity of electro-thermally poled bioactive silicate glass.

    PubMed

    Mariappan, C R; Yunos, D M; Boccaccini, A R; Roling, B

    2009-05-01

    A 45S5 bioactive glass (nominal composition: 46.1 mol.% SiO2, 2.6 mol.% P2O5, 26.9 mol.% CaO, 24.4 mol.% Na2O) was electrothermally poled by applying voltages up to 750 V for 45 min at 200 degrees C, and the thermally stimulated depolarization currents (TSDCs) were recorded. Changes in chemical composition and electrical properties after poling were investigated by TSDC measurements, impedance spectroscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX). The poling led to the formation of interfacial layers underneath the surface in contact with the electrodes. Under the positive electrode, the layer was characterized by Na+ ion depletion and by a negative charge density, and the layer was more resistive than the bulk. The influence of poling on the bioactivity was studied by immersion of samples in simulated body fluid (SBF) with subsequent cross-sectional SEM/EDX and X-ray diffraction analysis. It was found that poling leads to morphological changes in the silica-rich layer and to changes in the growth rate of amorphous calcium phosphate and bone-like apatite on the glass surface. The bone-like apatite layer under the positive electrode was slightly thicker than that under the negative electrode.

  17. The role of alkalis in the solubility of H2O and CO2in silicate melts

    NASA Astrophysics Data System (ADS)

    Vetere, F.; Behrens, H.; Botcharnikov, R. E.; Holtz, F.; Fanara, S.

    2013-12-01

    In order to investigate the role of alkalis on the behavior of H2O and CO2 in magmatic systems, the solubility of volatiles in phonotephritic melts was investigated experimentally and compared to other melt compositions. The investigated compositions have Na2O/K2O ratios (in wt %) of 0.26 (Ab1, natural phonotephrite from Alban Hills, Italy), 0.98 (Ab2) and 3.82 (Ab3). Experiments were run at 1250°C and 500 MPa in an internally heated gas pressure vessel. The mole fraction of water (XH2O) in the fluid phase composed of H2O and CO2 varied in the range from 0 to 1. For the calibration of carbon-related IR bands in glasses, the total carbon content of synthesized glass standards was measured by combustion and subsequent IR spectroscopy using an ELTRA CS800 analyzer. Karl Fischer Titration method was used to quantify the H2O content of the glasses. Absorption spectra were recorded in the mid-infrared (MIR) using a Bruker IFS88 FTIR spectrometer coupled with an IR-ScopeII microscope. CO2 is bounded in the investigated glasses as CO32- exclusively and its concentration was quantified by the peak height of the 1430 cm-1 band. A drastic change was observed in the absorption coefficients, ɛ, with values of 294 × 35, 329 × 40 and 244 × 23 L/(mol cm) , for Ab1, Ab2, and Ab3, respectively, so that the highest ɛ value is related to the Na-rich composition. There is no evident effect of the Na/K ratio on the concentrations of dissolved H2O and CO2 in the melts. The solubility of CO2 and H2O in those melts at 500 MPa is 0.95 wt % CO2 and 10.07 wt% H2O for XH2O of 0 and 1, respectively. Results are compared with the existing literature data and models and confirm the very high solubility of CO2 in phonotephritic melts [1]. Our experimental data indicate that the melt composition in terms of alkali contents influences significantly the extinction coefficient values for CO2 and that appropriate coefficients must be selected to estimate accurately the amount of dissolved CO2 in

  18. Study of the surface of reduced lead silicate glasses by electron emission

    SciTech Connect

    Artamonov, O.M.; Kostikov, Y.P.; Novolodskii, V.A.; Redina, I.V.; Sattarov, D.K.

    1986-03-01

    The authors determine the composition of the emitting surface of reduced lead silicate glasses by electron emission and the change in it as a function of the various effects which affect the working of the devices made from RLSG, such as electron multipliers. Preliminary studies were made using an electron spectroscopy for chemical analysis method which showed that the original surface was significantly contaminated by carbon, whose concentration exceeded that of silicon by 7-18 times in different specimens. The surface composition of specimens of reduced lead silicate glasses changes weakly as a function of the reducing regime in hydrogen. Electron bombardment and heating in vaccum at a pressure of 10/sup -9/ torr lead to an increase in the concentration of carbon in the specimen.

  19. 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.

  20. 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.

  1. 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.

  2. An intrinsic luminescence in binary lead silicate glasses

    NASA Astrophysics Data System (ADS)

    Zatsepin, А. F.; Zhidkov, I. S.; Kukharenko, A. I.; Zatsepin, D. А.; Andronov, М. P.; Cholakh, S. О.

    2012-03-01

    The low-temperature photoluminescence (PL) of xPbO · (1 - x)SiO2 glasses (x = 0.20-0.75) was studied at Т = 10 K. The recorded PL-spectra are a superposition of three spectral components with maxima located at 1.8 eV (identified as Pb 6p → metal-bridging O2p radiative electron transition, the "R"-band), 2.0 eV (Pb 6p → non-bridging O2p, the "O"-band) and 2.55 eV (Pb 6p → Pb 6s, the "B"-band), respectively. It was found the essential link for "R", "O" and "B" PL-bands with chemical composition x of the glasses under study. These concentration dependences are expressed as mutual PL-intensity variations for each recorded luminescence band that allowed to determine their origin. The shape of established dependences well coincides with numerical data on NBO- and MBO-density of chemical bonding, reported previously. The overall PL-manner within the temperature range of 10-295 K is described by an empirical Street's law. It was shown that experimental photoluminescence quenching curves may be precisely approximated as a superposition of Mott relationships for nonequivalent luminescence centers. The obtained distribution of PL-centers on the activation energy for luminescence quenching reflects the essential donation of the low-energy states into the overall PL-process. The width of this energy distribution affects by the type of PL-emission band and the disordering degree in the arrangement of local PL-centers of a certain kind.

  3. 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.

  4. 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.

  5. The structural role of manganese ions in soil active silicate-phosphate glasses.

    PubMed

    Szumera, Magdalena

    2014-08-14

    Silicate-phosphate glasses of SiO2P2O5K2OMgOCaO system containing manganese ions were synthesized by the melt-quenching technique and were investigated to obtain information about the influence of Mn-cations on the glass structure and their chemical activity. Structural properties were studied using X-ray method, FTIR and Raman spectroscopies. The chemical activity of analyzed glasses in the 2 wt.% citric acid solution was measured by chemical analysis (ICP-AES, EDS) and SEM observations. It has been found that increasing amount of MnO2 in the structure of investigated glasses causes their gradual depolymerization. This process is more apparent in the case of the silico-oxygen subnetwork than phospho-oxygen one. This is related to increasing amounts of SiO4 tetrahedra containing two nonbridging oxygen atoms in silico-oxygen subnetwork. It has been also found that the presence of "weaker" chemical bonds of SiOMn type in comparison to SiOCa and SiOMg bonds is responsible for the increase in solubility of the analyzed silicate-phosphate glasses in conditions simulating natural soil environment.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. The influence of SrO and CaO in silicate and phosphate bioactive glasses on human gingival fibroblasts.

    PubMed

    Massera, J; Kokkari, A; Närhi, T; Hupa, L

    2015-06-01

    In this paper, we investigate the effect of substituting SrO for CaO in silicate and phosphate bioactive glasses on the human gingival fibroblast activity. In both materials the presence of SrO led to the formation of a CaP layer with partial Sr substitution for Ca. The layer at the surface of the silicate glass consisted of HAP whereas at the phosphate glasses it was close to the DCPD composition. In silicate glasses, SrO gave a faster initial dissolution and a thinner reaction layer probably allowing for a continuous ion release into the solution. In phosphate glasses, SrO decreased the dissolution process and gave a more strongly bonded reaction layer. Overall, the SrO-containing silicate glass led to a slight enhancement in the activity of the gingival fibroblasts cells when compared to the SrO-free reference glass, S53P4. The cell activity decreased up to 3 days of culturing for all phosphate glasses containing SrO. Whereas culturing together with the SrO-free phosphate glass led to complete cell death at 7 days. The glasses containing SrO showed rapid cell proliferation and growth between 7 and 14 days, reaching similar activity than glass S53P4. The addition of SrO in both silicate and phosphate glasses was assumed beneficial for proliferation and growth of human gingival fibroblasts due to Sr incorporation in the reaction layer at the glass surface and released in the cell culture medium.

  12. 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.

  13. 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).

  14. Crystal growth and optical properties of CdS-doped lead silicate glass

    SciTech Connect

    Liu Hao; Liu Qiming; Zhao Xiujian . E-mail: zhaoxj@public.wh.hb.cn

    2007-01-15

    The crystal growth and optical properties of CdS microcrystallite-doped lead silicate glass is investigated in this paper. The existence of CdS nanocrystals was confirmed via X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results reveal that a two-stage heat-treat procedure can produce a better size distribution of CdS nanocrystals than a one-stage heat-treat procedure in glasses. The second harmonic generation (SHG) from the base glass and CdS microcrystallite doped glasses was observed, and the effects of the heat treatments and the thermal poling temperature on the crystallization of CdS and second-order harmonic (SH) intensity were discussed, respectively. It is indicated that samples doped with CdS microcrystallite showed larger SH intensity than that of the base glass. Use of a higher thermal poling temperature than the glass transformation temperature does not result in a good SH intensity in glasses.

  15. Molten glass corrosion resistance of immersed combustion-heating tube materials in soda-lime-silicate glass

    SciTech Connect

    Sundaram, S.K.; Hsu, J.Y.; Speyer, R.F. . School of Materials Science and Engineering)

    1994-06-01

    The corrosion resistance of molybdenum, molybdenum disilicide, and a SiC[sub (p)]/Al[sub 2]O[sub 3] composite to molten soda-lime-silicate glass was studied. The ASTM-C621-84 corrosion test method was modified because of inherent inaccuracies in the method and Si attack of platinum crucibles. Specimen-glass interfacial regions were characterized using XRD, SEM, and EDS. After 48 h of exposure at 1,565 C, the half-down corrosion recessions of Mo, MoSi[sub 2], and SiC[sub (p)]/Al[sub 2]O[sub 3] were 0.11, 0.316, and 0.26 mm, respectively. Mo oxidized to form a MoO[sub 2] surface scale which cracked, allowing glass seepage and further oxidation. Silicon was leached out of MoSi[sub 2] into the glass, leaving a Mo[sub 5]Si[sub 3] interface and particles of Mo near the interface. For the SiC[sub (p)]/Al[sub 2]O[sub 3] composite, bubbles observed at the interfacial regions formed from oxidation of SiC to form CO. Thermodynamic modeling corroborated these experimental observations. The work discussed herein is part of a larger research thrust to develop materials for immersed gas-fired radiant burner tubes for glass melters.

  16. 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.

  17. 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.

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

    SciTech Connect

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

    2011-07-15

    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{sup +} ions with a fluence of 10{sup 13} ions/cm{sup 2} 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{sup +} ions as revealed by the broad emission around 500 nm.

  19. 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

    2015-01-01

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

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

  1. 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,

  2. Visible to infrared photoluminescence from gold nanoparticles embedded in germano-silicate glass fiber.

    PubMed

    Lin, Aoxiang; Son, Dong Hoon; Ahn, Il Ho; Song, G Hugh; Han, Won-Taek

    2007-05-14

    Germano-silicate glass fiber containing gold nanoparticles was developed by modified chemical vapor deposition and solution doping processes. Pumping with 488 nm Argon ion laser, we firstly report on the visible to infrared photoluminescence of the gold nanoparticles embedded in the core of the germano-silicate fibers. The surface plasmon resonance absorption peak at 498.4 nm and the visible to infrared photoluminescence over the range of 600 nm approximately 1560 nm were found and explained according to the interband and intraband electronic transitions of Au atoms. The averaged quantum efficiencies of the photoluminescence at 833 nm and 1536 nm were estimated to be 5.75 x 10(-8) and 2.01 x 10(-9), respectively.

  3. Long-term stable, low-temperature remote silicate phosphor thick films printed on a glass substrate.

    PubMed

    Kim, Jun Sik; Kwon, Oh Hyeon; Jang, Jin Woo; Lee, Sung Hyun; Han, Sung Jun; Lee, Joo Hong; Cho, Yong Soo

    2015-04-13

    A critical step in providing better phosphor solution for white light emitting diode (LED) is to utilize inexpensive silicate phosphors with strong thermal stability. Here, we demonstrate yellow silicate phosphor-embedded glass thick films with a high luminous efficacy of ∼32 lm/W at 200 mA as a nonconventional remote-phosphor approach. The simple screen-printing process of a paste consisting of (Ba,Sr,Ca)₂SiO₄:Eu²⁺ phosphor and a low softening point glass creates a planar remote structure on a regular soda lime silicate glass with controllable film thickness and location (top vs bottom) of the phosphor layer. The glass matrix provides promising densification and adhesion with the substrate at the optimal low temperature of 410 °C, with the long-term stability in luminous efficacy over 500 h of operation. The proposed phosphor structure has important implications to overcome current limitations as phosphors.

  4. 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.

  5. 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. PMID:24364938

  6. 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.

  7. 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.

  8. Optical waveguides in Er3+/Yb3+-codoped silicate glasses fabricated by proton implantation

    NASA Astrophysics Data System (ADS)

    Liu, Chun-Xiao; Fu, Li-Li; Zhu, Xu-Feng; Guo, Hai-Tao; Li, Wei-Nan; Lin, She-Bao; Wei, Wei

    2016-07-01

    In this work, a planar waveguide was fabricated by proton implantation in Er3+/Yb3+-codoped silicate glasses with energies of (500 + 550) keV and fluences of (1 + 2) × 1016 ions/cm2. The end-face coupling method was employed to determine whether the light could be confined in the waveguide or not. The prism coupling technique was applied to measure the guided mode spectrum and the intensity calculation method was used to construct the refractive index profile. With the profile, a near-field intensity distribution was calculated by the finite difference beam propagation method. The obtained results may be helpful in developing integrated optical devices.

  9. 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.

  10. 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.

  11. 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.

  12. The dissolution mechanisms of silicate and glass-ionomer dental cements.

    PubMed

    Kuhn, A T; Wilson, A D

    1985-11-01

    The mechanism of dissolution of two dental cements of the acid-base setting types (silicate and glass-ionomer) is considered. Dissolution is incongruent, probably because most of the leached species can derive both from the matrix (polysalt gel) and the partly reacted glass particles. The release occurs by means of three discrete mechanisms, surface wash-off, diffusion through pores and cracks or diffusion through the bulk. Such behaviour is shown to be capable of being modelled with extremely high goodness-of-fit values, using equations such as y = const + at1/2 + bt. Analogies with research from the fields of geochemistry and nuclear fuel storage are made and these systems obey similar relationships. The dental cement systems differ, however, in that their dissolution is to some extent reversible. This is explained in terms of formation of insoluble complexes, either by reaction of the constituent ions, or by replacement of OH-, for example, with F-.

  13. 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.

  14. Strongly Composition-Dependent Partial Molar Compressibility of Water in Silicate Glasses

    NASA Astrophysics Data System (ADS)

    Whittington, A. G.; Richet, P.; Polian, A.

    2010-12-01

    Water and other volatiles have long been known to play a fundamental role in igneous processes, yet their influence on the physical properties of melts are still not well enough understood. Of particular interest is the density contrast between liquid and solid phases, which facilitates melt extraction and migration. Owing to its low molecular weight, dissolved water must decrease magma density, but the way it does so as a function of pressure remains largely to be determined. Studies on quenched melts (glasses) provide useful information because the glass has the same structure as the melt. We measured compressional and shear wave velocities of seven series of hydrous aluminosilicate glasses by Brillouin scattering at room temperature and pressure. The glasses were quenched from high temperature and 2 or 3 kbar pressure. The dry end-members range from highly polymerized albitic and granitic compositions, to depolymerized synthetic analogues of mantle-derived melts. For each set of glasses, the adiabatic shear and bulk moduli have been calculated from the measured sound velocities and densities. These moduli are linear functions of water content up to 5 wt % H2O, the highest concentration investigated, indicating that both are independent of water speciation in all series. For water-free glasses, the bulk modulus decreases from about 65 to 35 GPa with increasing degree of polymerization. Sympathetically, the partial molar bulk modulus of the water component decreases from 114 to 8 GPa, such that dissolved water amplifies the differences in rigidity between the anhydrous glasses. This strong variation indicates that the solubility mechanisms of water depend strongly on silicate composition. Depolymerized liquids are also much less compressible than their polymerized counterparts, suggesting that the partial molar compressibility of dissolved water approaches zero in depolymerized liquids. If this is correct, hydrous mantle melts formed beneath volcanic arcs would be

  15. High-pressure radiative conductivity of dense silicate glasses with potential implications for dark magmas.

    PubMed

    Murakami, Motohiko; Goncharov, Alexander F; Hirao, Naohisa; Masuda, Ryo; Mitsui, Takaya; Thomas, Sylvia-Monique; Bina, Craig R

    2014-01-01

    The possible presence of dense magmas at Earth's core-mantle boundary is expected to substantially affect the dynamics and thermal evolution of Earth's interior. However, the thermal transport properties of silicate melts under relevant high-pressure conditions are poorly understood. Here we report in situ high-pressure optical absorption and synchrotron Mössbauer spectroscopic measurements of iron-enriched dense silicate glasses, as laboratory analogues for dense magmas, up to pressures of 85 GPa. Our results reveal a significant increase in absorption coefficients, by almost one order of magnitude with increasing pressure to ~50 GPa, most likely owing to gradual changes in electronic structure. This suggests that the radiative thermal conductivity of dense silicate melts may decrease with pressure and so may be significantly smaller than previously expected under core-mantle boundary conditions. Such dark magmas heterogeneously distributed in the lower mantle would result in significant lateral heterogeneity of heat flux through the core-mantle boundary. PMID:25384573

  16. Unusual anti-thermal degradation of bismuth NIR luminescence in bismuth doped lithium tantalum silicate laser glasses.

    PubMed

    Tan, Linling; Wang, Liping; Peng, Mingying; Xu, Shanhui; Zhang, Qinyuan

    2016-08-01

    For application of bismuth laser glasses in either fiber amplifier or laser, their performance stability in long run should be understood especially in extreme conditions. However, so far, there are few reports on it. Here, we found, after the cycle experiments on heating and cooling, that the proper increase of lithium content in lithium tantalum silicate laser glass can lead to unusual anti-thermal degradation of bismuth NIR luminescence, which completely differs from the scenario in germanate glass. FTIR, 29Si MAS NMR spectra, absorption and dynamic photoluminescence spectra are employed to unravel how this happens. The results illustrate that it should be due to the decrease of polymerization of silicate glass network, which in turn allows the regeneration at 250°C, and therefore, the content increase of bismuth NIR emission centers. In the meanwhile, we noticed though Bi luminescence can be thermally quenched its peak does not shift along with temperature, which seldom appears in laser materials. The unique property might guarantee the unshift of Bi fiber laser wavelength once such glass was made into fiber devices even as the environmental temperature changes. The role of lithium is discussed in the evolution of glass structures, the suppression of glass heterogeneity, and the thermal stability of Bi luminescence, and it should be helpful to design homogeneous silicate laser glass with outstanding thermal stability.

  17. Unusual anti-thermal degradation of bismuth NIR luminescence in bismuth doped lithium tantalum silicate laser glasses.

    PubMed

    Tan, Linling; Wang, Liping; Peng, Mingying; Xu, Shanhui; Zhang, Qinyuan

    2016-08-01

    For application of bismuth laser glasses in either fiber amplifier or laser, their performance stability in long run should be understood especially in extreme conditions. However, so far, there are few reports on it. Here, we found, after the cycle experiments on heating and cooling, that the proper increase of lithium content in lithium tantalum silicate laser glass can lead to unusual anti-thermal degradation of bismuth NIR luminescence, which completely differs from the scenario in germanate glass. FTIR, 29Si MAS NMR spectra, absorption and dynamic photoluminescence spectra are employed to unravel how this happens. The results illustrate that it should be due to the decrease of polymerization of silicate glass network, which in turn allows the regeneration at 250°C, and therefore, the content increase of bismuth NIR emission centers. In the meanwhile, we noticed though Bi luminescence can be thermally quenched its peak does not shift along with temperature, which seldom appears in laser materials. The unique property might guarantee the unshift of Bi fiber laser wavelength once such glass was made into fiber devices even as the environmental temperature changes. The role of lithium is discussed in the evolution of glass structures, the suppression of glass heterogeneity, and the thermal stability of Bi luminescence, and it should be helpful to design homogeneous silicate laser glass with outstanding thermal stability. PMID:27505827

  18. A Raman model for determining the chemical composition of silicate glasses

    NASA Astrophysics Data System (ADS)

    Di Genova, Danilo; Morgavi, Daniele; Hess, Kai-Uwe; Neuville, Daniel R.; Perugini, Diego; Dingwell, Donald B.

    2015-04-01

    Raman spectroscopy is a spectroscopic technique based on inelastic scattering of monochromatic light which provides information about molecular vibrations of the investigated sample. Since the discovery of the Raman Effect (1928) in scattered light from liquids, the Raman investigation has been extended to a large number of substances at different pressure-temperature conditions. Recently, the Raman instrument setup has rapidly grown thanks to the progress in development of lasers, charge coupled devices and confocal systems (see Neuville et al. 2014 for a review). Here we present the first Raman model able to determine the chemical composition of silicate glasses. In this study we combine chemical analysis from magma mixing experiments between remelted basaltic and rhyolitic melts, with a high spatial resolution Raman spectroscopy investigation; we focus on tracking the evolution of the Raman spectrum with chemical composition of silicate glasses. The mixing process is driven by a recently-developed apparatus that generates chaotic streamlines in the melts (Morgavi et al., 2013), mimicking the development of magma mixing in nature. From these experiments we obtained a glassy filament with a chemical composition ranging from a basalt to a rhyolite. Raman and microprobe measurements have been performed on a filament of ~1000 μm diameter, every 2.5-20 μm. The evolution of the acquired Raman spectra with the measured chemical composition has been parametrized by combining both the Raman spectra of the basaltic and rhyolitic end-members. Using the developed Raman model we have been able to determine the chemical composition (mol% of SiO2, Al2O3, FeO, CaO, MgO, Na2O and K2O) of the investigated filament. Additionally, the proposed Raman model has been successfully tested using external remelted natural samples; reference glasses (Jochum et al., 2000), a remelted basalt, andesite from Etna and Montserrat respectively. Finally, as the Raman spectrum depends on the

  19. Investigation of the structural environment of Ta in a silicate glass and water system under high P–T conditions

    SciTech Connect

    Mayanovic, Robert A.; Yan, Hao; Anderson, Alan J.; Solferino, Giulio

    2013-05-01

    In situ Ta L3-edge XAS measurements have been made from a Ta (~ 1400 ppm)-bearing peraluminous silicate glass + H2O system to 960 °C and ~ 0.6 GPa. A white-line doublet separated by ~ 4 eV occurs in the Ta L3-edge XANES and results from octahedral crystal field splitting of the Ta 5d levels due to the local structure surrounding Ta coordinated by Qn-species (n = number of bridging oxygen atoms shared between SiO4 and AlO4 units) in the silicate glass/melt + H2O system. The XANES spectra measured from the hydrous silicate glass/melt and from the silicate-rich aqueous fluid have been analyzed using multi-peak fitting techniques. The white-line doublet intensity varies with increasing P–T conditions of the silicate glass/melt + water system, indicating a shift in the electronic density of states in the vicinity of quasi bound Ta 5d states probed by the 2p3/2 core photoelectron. Ab initio modeling of the XANES indicates that water dissolution causes distortion of local structure surrounding the 6-fold coordinated Ta–Qn clusters in the hydrous silicate glass/melt and in the silicate-rich aqueous fluid. Calculation of the angular-momentum projected density of states (l-DOS) shows that the upper doublet level quasi-bound d-DOS is steadily reduced with increasing distortion of the local structure surrounding Ta–Qn clusters.

  20. 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.

  1. 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.

  2. Optical band gap and spectroscopic study of lithium alumino silicate glass containing Y 3+ ions

    NASA Astrophysics Data System (ADS)

    Shakeri, M. S.; Rezvani, M.

    2011-09-01

    The effect of different amounts of Y 2O 3 dopant on lithium alumino silicate (LAS) glass has been studied in this work. Glasses having 14.8Li 2O-20Al 2O 3-65.2SiO 2 (wt%) composition accompanied with Y 2O 3 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 Y 3+ 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 Y 3+ ions as the network former in the track of SiO 4 tetrahedrals.

  3. 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. PMID:21689980

  4. 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

  5. Estimation of Fe3+/Fetot. ratio in natural silicate glasses and analogues for extra-terrestrial basalt using Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Di Genova, D.; Hess, K. U.; Chevrel, M. O.; Dingwell, D. B.

    2015-12-01

    The effect of iron oxidation state (Fe3+/Fetot.) on the Raman spectra of pantelleritic (from Pantelleria island) and basaltic glasses (from Etna) and synthetic analogues for extra-terrestrial basaltic glasses (iron-rich martian basalt analogues; Chevrel et al. 2014) has been investigated. The Raman spectra of pantellerite glasses show dramatic changes in the high wavelength region of the spectrum (800-1200cm-1) as iron oxidation state changes. In particular the 970 cm-1 band intensity increases with increasing oxidation state of the glass (Fe3+/Fetot. ratio from 0.24 to 0.83). In contrast, Raman spectra of the basaltic glasses (natural and synthetic) do not show the same oxidation state sensitivity as the pantelleritic samples (Fe3+/Fetot. ratio from 0.15 to 0.79). A shift, however, of the 950 cm-1 band to high wavenumber with decreasing iron oxidation state can be observed. To help develop Raman spectroscopy as a quantitative tool in both geosciences and planetary science we present here an empirical, compositionally-independent model, based on an ideal mixing equation applied to the acquired Raman spectra. This model yields estimates of the iron oxidation state of anhydrous and hydrous silicate glasses of basaltic and pantelleritic composition for Fe3+/Fetot. ranging between 0.15 and 0.83 and water contents up to 2.4 wt.%. The model has been validated using independently characterized natural and synthetic silicate glasses (both anhydrous and hydrous) with a FeO content varying from ~8 to ~22 wt%. The results of this study contribute to increase the compositionally-dependent database previously presented by Di Genova et al. (2015) for Raman spectra of complex silicate glasses. The applications of this model range from microanalysis of silicate glasses (e.g. melt inclusions) to handheld in situ terrestrial field studies and under extreme conditions (e.g. extraterrestrial, volcanic and submarine environments).

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2006-08-01

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

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

    SciTech Connect

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

    2010-06-15

    Lithium aluminum silicate (LAS) glass of composition (mol%) 20.4Li{sub 2}O-4.0Al{sub 2}O{sub 3}-68.6SiO{sub 2}-3.0K{sub 2}O-2.6B{sub 2}O{sub 3}-0.5P{sub 2}O{sub 5}-0.9TiO{sub 2} was prepared by melt quenching. The glass was then nucleated and crystallized based on differential thermal analysis (DTA) data and was characterized by {sup 29}Si, {sup 31}P, {sup 11}B and {sup 27}Al MAS-NMR. XRD and {sup 29}Si NMR showed that lithium metasilicate (Li{sub 2}SiO{sub 3}) is the first phase to c form followed by cristobalite (SiO{sub 2}) and lithium disilicate (Li{sub 2}Si{sub 2}O{sub 5}). {sup 29}Si MAS-NMR revealed a change in the network structure already for the glasses nucleated at 550 {sup o}C. Since crystalline Li{sub 3}PO{sub 4}, as observed by {sup 31}P MAS-NMR, forms concurrently with the silicate phases, we conclude that crystalline Li{sub 3}PO{sub 4} does not act as a nucleating agent for lithium silicate phases. Moreover, {sup 31}P NMR indicates the formation of M-PO{sub 4} (M=B, Al or Ti) complexes. The presence of BO{sub 3} and BO{sub 4} structural units in all the glass/glass-ceramic samples is revealed through {sup 11}B 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{sub 3}) increases at the expense of tetrahedrally coordinated B (BO{sub 4}). The {sup 27}Al MAS-NMR spectra indicate the presence of tetrahedrally coordinated Al species, which are only slightly perturbed by the crystallization. - Graphical abstract: {sup 11}B MAS-NMR spectra of LAS glass heat treated at different temperatures, showing the evolution of the residual glass matrix during the crystallization treatment. High-field (18.8 T) NMR enables us to record high resolution spectra, from which the glass network modifications could be related to the formation of intermediate lithium silicate crystalline phases.

  9. Chromium speciation in oxide-type compounds: application to minerals, gems, aqueous solutions and silicate glasses

    NASA Astrophysics Data System (ADS)

    Farges, François

    2009-09-01

    Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO4 2- moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.

  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. Light induced dielectric constant of Alumina doped lead silicate glass based on silica sands

    NASA Astrophysics Data System (ADS)

    Diantoro, Markus; Natalia, Desi Ayu; Mufti, Nandang; Hidayat, Arif

    2016-04-01

    Numerous studies on glass ceramic compounds have been conducted intensively. Two major problems to be solved are to simplify the fabrication process by reducing melting temperature as well as improving various properties for various fields of technological application. To control the dielectric constant, the researchers generally use a specific dopant. So far there is no comprehensive study to control the dielectric constant driven by both of dopant and light intensity. In this study it is used Al2O3 dopant to increase the light induced dielectric constant of the glass. The source of silica was taken from local silica sands of Bancar Tuban. The sands were firstly leached using hydrochloric acid to improve the purity of silica which was investigated by means of XRF. Fabricating the glass samples were performed by using melting-glass method. Silica powder was mixed with various ratio of SiO2:Na2CO3:PbO:Al2O3. Subsequently, a mixture of various Al2O3 doped lead silicate glasses were melted at 970°C and directy continued by annealed at 300°C. The samples were investigated by XRD, FTIR, SEM-EDX and measuring dielectric constant was done using dc-capacitance meter with various light intensities. The investigation result of XRD patterns showed that the crystal structures of the samples are amorphous state. The introduction of Al2O3 does not alter the crystal structure, but significantly change the structure of the functional glass bonding PbO-SiO2 which was shown by the FTIR spectra. It was noted that some new peak peaks were exist in the doped samples. Measuring result of dielectricity shows that the dielectric constant of glass increases with the addition of Al2O3. Increasing the light intensity gives rise to increase their dielectric constant in general. A detail observation of the dielectric seen that there are discontinuous step-like of dielectric. Most likely a specific quantization mechanism occurs when glass exposed under light.

  12. Evaluation of alkali concentration in conditions relevant to oxygen/natural gas glass furnaces by laser-induced breakdown spectroscopy.

    SciTech Connect

    Walsh, Peter M.; Molina, Alejandro; Shaddix, Christopher R.; Blevins, Linda Gail; Sickafoose, Shane M.

    2005-01-01

    A number of industrial combustion systems are adopting oxygen-enhanced firing to improve heat transfer characteristics and reduce emissions. The exhaust gas from these systems is dominated by H2O and CO2 and therefore has substantially different gas properties from traditional combustion exhaust. In the past, laser-induced breakdown spectroscopy (LIBS) has been successfully used for the evaluation of alkali aerosol concentrations in air-based combustion systems. This paper presents results of LIBS measurements of alkali concentrations in a laboratory calibration setup and in an oxygen/natural gas container glass furnace. It shows how both gas conditions (composition and temperature) and the molecular form of the alkali species affect the LIBS signals. The paper proposes strategies for mitigating these effects in future applications of LIBS in oxygen-enhanced combustion systems.

  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. 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.

  15. Further Investigations of the Effect of Replacing Lithium by Sodium on Lithium Silicate Scintillating Glass Efficiency

    SciTech Connect

    Bliss, Mary; Aker, Pamela M.; Windisch, Charles F.

    2012-02-15

    Ce3+ doped lithium (6Li) silicate glasses are thermal neutron detectors. Prior work showed that when sodium (Na) is substituted for Li the scintillation efficiency, under beta particle stimulation, increased and then decreased as the sodium (Na) content was increased [1]. When all the 6Li was replaced by Na no scintillation was observed. Raman spectra, acquired using a visible excitation source provided no evidence of anomalous behavior. SEM microscopy did show some phase separation, but there was no obvious correlation with the scintillation efficiency. We have reexamined these glass samples using deep UV Raman excitation which reduces fluorescence interference. The newly acquired spectra show evidence of phase separation in the glasses. Specifically we see a peak at 800 cm-1 Raman shift which can be assigned to a vitreous silica moiety that results from phase separation. There is a strong correlation between this peak's area, the scintillation efficiency, and the Na content. The observed trend suggests that phase separation enhances scintillation and addition of Na reduces the amount of phase separation. We also see evidence of at least two defect structures that can be tentatively assigned to a three-membered ring structure and an oxygen vacancy. The latter is fairly strongly correlated with enhanced scintillation efficiency.

  16. Raman study of potassium silicate glasses containing Rb +, Sr 2+, Y 3+ and Zr 4+: Implications for cation solution mechanisms in multicomponent silicate liquids

    NASA Astrophysics Data System (ADS)

    Ellison, Adam J. G.; Hess, Paul C.

    1994-04-01

    The parallel- and perpendicular-polarized Raman spectra of (1 - x)K 2O · xM 2/zz+O · 4SiO 2e glasses are presented, where M is one of the Period V cations Rb +, Sr 2+, Y 3+ or Zr 4+. These compositions represent the equal-oxygen substitution of a Period V cation for K +, which preserves the ratio of non-bridging oxygen (NBO) to Si atoms but not, in general, the ratio of all oxygen to all cations. Rb + and K + occupy very similar sites and appear to share the same NBO with virtually no energetic penalty. As the valence of the Period V cation increases, so does the tendency of the cation to form silicate species that are depolymerized relative to the species dominating the structure of the bulk glass. The tendency to form regions comparatively rich in Si-O-Si bonds increases in the same sense. The dominant silicate species are those with 0 or 1 NBO in all glasses. The spectra indicate that K+ shares NBO with Rb + or Sr 2+, that there is relatively little sharing of NBO by K + and Y 3+, and that K + and Zr 4+ share the same NBO in what appears to be a nearly fixed bulk stoichiometric K:Zr ratio of 2:1. The latter provides a mechanism for the substantial increase in ZrO 2 solubility seen in peralkaline liquids. A novel means of expressing homogeneous equilibria in silicate liquids is presented, whereby it is possible to make concrete predictions about the coordination numbers of cations in silicate liquids and to predict how they might be affected by the presence of other cations.

  17. 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.

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

    SciTech Connect

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

    2010-01-15

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

  19. Kinetics of reactions at an interface: functionalisation of silicate glass with porphyrins via covalent bonds.

    PubMed

    Fujimoto, Takahiro; Furuta, Nao; Mizutani, Tadashi

    2015-03-21

    Porphyrins carrying either a primary alcohol, a tertiary alcohol or a primary bromide linker group were allowed to react with the surface silanol groups on silicate glass thermally at 80-240 °C to obtain a monolayer film. The kinetics of the reaction was analysed based on the pseudo-second order equation. The tertiary alcohol and the primary bromide reacted much slower than the primary alcohol. Arrhenius plots indicated that higher activation energies can account for the slower reaction of both tertiary alcohol and primary bromide linkers. The introduction of six dodecyl chains into hydroxyporphyrin accelerated the anchoring reaction by a factor of 50 owing to the larger frequency factor of the reaction, demonstrating that the dynamics of the interface is one of the dominant factors regulating the reaction kinetics.

  20. Direct force measurement between bio-colloidal Giardia lamblia cysts and colloidal silicate glass particles.

    PubMed

    Virtanen, Anne-Mari J; Considine, Robert F; Dixon, David R; Fong, Celesta; Drummond, Calum J

    2012-12-11

    Force-separation measurements between Giardia lamblia cysts and an inorganic oxide (silicate glass) have been obtained by using an atomic force microscope (AFM). The cysts are compressible on the scale of the loads applied during force measurement, with the surface compressibility expressed in terms of an interfacial spring constant (K(int)). The force of interaction prior to this Hookean region, on approach, is long-range and repulsive. The long-range force has been compared to models of the electrical double layer as well as an electrosteric layer. The comparison has led to the conclusion that the cyst surface can be described as a polyelectrolyte brush at intermediate separations (5-115 nm from linear compliance) with an electrical double layer often observed at larger separations. The dependence of the interaction force on surface retraction suggests that tethering between the cyst and siliceous surface can occur. The variation of the interaction with pH and upon variation with ionic strength has also been assessed. The information gained from the measurement of the interaction between G. lamblia and this model sandlike surface informs water treatment processes. Similar studies have been performed by us for the Cryptosporidium parvum (C. parvum) oocyst system to which this work is compared.

  1. Heat conductivity of LiF-NaF-Al(PO{sub 3}){sub 3} mixed-alkali glasses

    SciTech Connect

    Il`in, A.A.; Pronkin, A.A.

    1995-03-01

    Described is the heat conductivity of LiF-NaF-Al(PO{sub 3}){sub 3} mixed-alkali phosphate glasses. The percentage of NaF was varied to measure the density, mean sound velocity, Debye temperature, thermal oscillation frequency, and heat conductivity coefficient at different molar fractions. Correlation between the heat conductivity and the Debye temperature show the same regularity of variation in these parameters as for most crystalline substances.

  2. Contrasting sound velocity and intermediate-range structural order between polymerized and depolymerized silicate glasses under pressure

    NASA Astrophysics Data System (ADS)

    Sakamaki, Tatsuya; Kono, Yoshio; Wang, Yanbin; Park, Changyong; Yu, Tony; Jing, Zhicheng; Shen, Guoyin

    2014-04-01

    X-ray diffraction and ultrasonic velocity measurements of three silicate glasses (in jadeite, albite, and diopside compositions) show a sharp contrast in pressure-induced changes in structure and elasticity. With increasing pressure to around 6 GPa, polymerized glasses (jadeite and albite) display large shift in the first sharp diffraction peak (FSDP) in the structure factor, S(Q), to higher-Q values, indicating rapid shrinkage in the intermediate-range ordered (IRO) structure. Above 6 GPa, the shift of FSDP decelerates, suggesting that shrinkage in the IRO structure has been largely completed and the structure evolution is now dominated by the diminution of the interstitial volume in a more densely packed arrangement. Associated with this structural change, sound velocities increase with pressure above 6 GPa. In contrast, the depolymerized diopside glass exhibits smaller changes in the pressure dependence for both sound velocities and FSDP positions. Compared to the polymerized glasses, the velocities are faster and the positions of FSDP appear at higher-Q under the same experimental conditions. The results suggest that the depolymerized diopside glass has an initially denser IRO structure compared to that of the polymerized glasses, and there are no sufficient interstitial voids to shrink. The different behaviors between polymerized and depolymerized glasses are apparently related to the initial linkage of tetrahedra and the pressure-induced structural reactions. These results suggest that under compression up to 10 GPa, the degree of polymerization is a major factor affecting the IRO network structure and the sound velocity of silicate glasses.

  3. 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.

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

    PubMed

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

    2014-07-01

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

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

    PubMed

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

    2014-07-01

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

  6. Highly flexible, proton-conductive silicate glass electrolytes for medium-temperature/low-humidity proton exchange membrane fuel cells.

    PubMed

    Lee, Hyeon-Ji; Kim, Jung-Hwan; Won, Ji-Hye; Lim, Jun-Muk; Hong, Young Taik; Lee, Sang-Young

    2013-06-12

    We demonstrate highly flexible, proton-conductive silicate glass electrolytes integrated with polyimide (PI) nonwoven fabrics (referred to as "b-SS glass electrolytes") for potential use in medium-temperature/low-humidity proton exchange membrane fuel cells (PEMFCs). The b-SS glass electrolytes are fabricated via in situ sol-gel synthesis of 3-trihydroxysilyl-1-propanesulfonic acid (THPSA)/3-glycidyloxypropyl trimethoxysilane (GPTMS) mixtures inside PI nonwoven substrates that serve as a porous reinforcing framework. Owing to this structural uniqueness, the b-SS glass electrolytes provide noticeable improvements in mechanical bendability and membrane thickness, in comparison to typical bulk silicate glass electrolytes that are thick and easily fragile. Another salient feature of the b-SS glass electrolytes is the excellent proton conductivity at harsh measurement conditions of medium temperature/low humidity, which is highly important for PEMFC-powered electric vehicle applications. This beneficial performance is attributed to the presence of a highly interconnected, proton-conductive (THPSA/GPTMS-based) silicate glass matrix in the PI reinforcing framework. Notably, the b-SS glass electrolyte synthesized from THPSA/GPTMS = 9/1 (mol/mol) exhibits a higher proton conductivity than water-swollen sulfonated polymer electrolyte membranes (here, sulfonated poly(arylene ether sulfone) and Nafion are chosen as control samples). This intriguing behavior in the proton conductivity of the b-SS glass electrolytes is discussed in great detail by considering its structural novelty and Grotthuss mechanism-driven proton migration that is strongly affected by ion exchange capacity (IEC) values and also state of water.

  7. 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

  8. Corrosion of soda lime silicate glasses co-doped with Gd2O3 and Y2O3

    NASA Astrophysics Data System (ADS)

    Wang, Mitang; Li, Mei; Cheng, Jinshu; He, Feng; Liu, Zhaogang; Hu, Yanhong

    2014-01-01

    Corrosion behaviors of Gd2O3 and Y2O3 co-doped silicate glasses have been carried out at low reaction progress. The better enhance effect of co-doping with Gd2O3 and Y2O3 on the silicate glass resistance against attacking of neutral and acid media is observed, while the alkaline resistance is Y2O3 > Gd2O3 + Y2O3 > Gd2O3. Moreover, extreme value is also observed in variation of released ions concentration, pH value and mass loss of glass when substituting Y2O3 for Gd2O3.

  9. 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.

  10. Glass transition, freezing and melting of liquids confined in the mesoporous silicate MCM-41

    NASA Astrophysics Data System (ADS)

    Morineau, Denis; Dosseh, Gilberte; Alba-Simionesco, Christiane; Llewellyn, Philip

    1999-11-01

    MCM-41 is a recently discovered mesoporous silicate that consists of a hexagonal arrangement of cylindrical pores. Because the pores are very well defined in size and shape, MCM-41 can be considered as a model material in comparison with previous types of porous glass and has therefore been used in the present study. In particular, we have focused on the properties of confined liquids and related phase transitions using an MCM-41 with a pore diameter of 4nm. We discuss here the first stage of a study where the thermodynamics of a series of molecular liquids (water, cyclohexane, benzene, toluene, o-terphenyl and m toluidine) are analysed by differential scanning calorimetry. Only a moderate decrease in the melting point of organic liquids has been observed. Moreover, analysing the freezing process, we have established thermal treatments that provide temperature ranges where confined liquids can be studied below the melting temperatures of both the bulk and the confined phases. Surprisingly, no significant change in the glass transition temperature has been observed compared with the bulk.

  11. Ab initio molecular dynamics study of 45S5 bioactive silicate glass.

    PubMed

    Tilocca, Antonio; de Leeuw, Nora H

    2006-12-28

    Bioglass 45S5, the prototype of bioactive melt-quenched silicate glasses, was modeled by means of Car-Parrinello molecular dynamics (CPMD) simulations. Although long-range structural properties cannot be modeled by using this ab initio approach, the accuracy of CPMD simulations is exploited here to provide insight into the short-range structure and to analyze vibrational and electronic properties of this biomaterial. Detailed structural analysis in the short-range scale provided insight into the local environment of modifier Na and Ca ions: a possible key role of these cations in organizing the glass network by connecting different chains and fragments into specific, rather flexible geometries was proposed. The individual contributions of different species to the vibrational density of states were separated and discussed, allowing the identification of specific features in the vibrational spectrum, such as those related to phosphate groups. The components of the electronic density of states were also analyzed, enabling us to identify correlations between the electronic structure and the structural properties, such as the different bonding character of Si-O bonds involving bridging or nonbridging oxygen atoms.

  12. Helical core optical fibre made of Nd3+/Yb3+-doped oxyfluoride silicate glass

    NASA Astrophysics Data System (ADS)

    Dorosz, D.; Kochanowicz, M.; Zmojda, J.; Dorosz, J.

    2010-05-01

    The properties of helical-core optical fibre made by authors from Nd3+/Yb3+-doped oxyfluoride silicate glass are presented. The construction and forming conditions of the helical-core optical fibre enabled to obtain the helix pitch from several mm and the off-set ranging from 10 μm to 200 μm. The paper also presents optimisation of Nd3+/Yb3+ ratio to enhance the emission bandwidth at 1 μm. In consequence of matching the values of the emission cross-section σem(Nd)and the absorption cross-section σabs(Yb) in the glass doped with 0.15Nd3+:0.45Yb3+ a broad (Δλ = 100nm) luminescence band in the vicinity of 1μm was obtained, which was the result of overlapping emission transitions: 2F5/2-->2F7/2 in ytterbium and 4F3/2-->4I11/2 in neodymium.

  13. Use of depleted uranium silicate glass to minimize release of radionuclides from spent nuclear fuel waste packages

    SciTech Connect

    Forsberg, C.W.

    1996-01-20

    A Depleted Uranium Silicate Container Backfill System (DUSCOBS) is proposed that would use small, isotopically-depleted uranium silicate glass beads as a backfill material inside repository waste packages containing spent nuclear fuel (SNF). The uranium silicate glass beads would fill the void space inside the package including the coolant channels inside SNF assemblies. Based on preliminary analysis, the following benefits have been identified. DUSCOBS improves repository waste package performance by three mechanisms. First, it reduces the radionuclide releases from SNF when water enters the waste package by creating a local uranium silicate saturated groundwater environment that suppresses (a) the dissolution and/or transformation of uranium dioxide fuel pellets and, hence, (b) the release of radionuclides incorporated into the SNF pellets. Second, the potential for long-term nuclear criticality is reduced by isotopic exchange of enriched uranium in SNF with the depleted uranium (DU) in the glass. Third, the backfill reduces radiation interactions between SNF and the local environment (package and local geology) and thus reduces generation of hydrogen, acids, and other chemicals that degrade the waste package system. Finally, DUSCOBS provides a potential method to dispose of significant quantities of excess DU from uranium enrichment plants at potential economic savings. DUSCOBS is a new concept. Consequently, the concept has not been optimized or demonstrated in laboratory experiments.

  14. Stationary and nonstationary absorption in lead silicate glasses with short-range order inversion

    NASA Astrophysics Data System (ADS)

    Zatsepin, A. F.; Kukharenko, A. I.; Zatsepin, D. A.; Shchapova, Yu. V.; Yakovlev, V. Yu.; Cholakh, S. O.; Zhidkov, I. S.

    2011-02-01

    The methods of stationary and pulsed absorption spectroscopy were used to study the optical properties of xPbO·(1- x)SiO 2 glasses produced by cooling of a molten mixture of chemically pure oxides. The spectral dependence of the absorption in the range of the short-wavelength edge obeys the Urbach rule. As the PbO concentration increases, a red shift of the optical transparency cutoff is observed. At x = 0.45-0.50 the amorphous matrix undergoes a structural inversion, which is due to a transition from a silicate to a lead-oxygen glass-forming network. This transition shows up as an abrupt change in the type of optical transitions, the width of the optical gap Eg, and the Urbach energy EU. The short-range order inversion in the glass is accompanied by an increase in the atomic correlation radius R0 characterizing the size of the medium-range order in the system. It was found empirically that R0 has a linear relationship with a continuum-disorder parameter EU. It was found that pulsed electron irradiation produces short-lived color centers, which absorb at 1.65 and 2.30 eV. The relaxation of unstable absorption centers is characterized by microsecond kinetics. The nature of unstable absorption centers and their relationship with a short-range order inversion and the structure function of lead atoms have been discussed. The kinetic dependences have been interpreted in the context of a mechanism responsible for diffusion-controlled tunneling recombination of radiation-induced electronic and hole states of the matrix.

  15. Comparative investigation on the spectroscopic properties of Pr³⁺-doped boro-phosphate, boro-germo-silicate and tellurite glasses.

    PubMed

    Zhang, Liaolin; Dong, Guoping; Peng, Mingying; Qiu, Jianrong

    2012-07-01

    We report on the spectroscopic properties of Pr(3+)-doped boro-phosphate, boro-germo-silicate and tellurite glasses. The stimulated absorption and emission cross sections were estimated. Only one emission at 596 nm and 605 nm is observed in Pr(3+)-doped boro-phosphate and boro-germo-silicate glasses, respectively, while three emissions at 605 nm, 612 nm and 645 nm are observed in Pr(3+)-doped tellurite glass when excited at 467 nm. The fluorescence lifetime at 600 nm in Pr(3+)-doped boro-phosphate, boro-germo-silicate and tellurite glasses is 137 μs, 73 μs and 51 μs, respectively. The emissions from Pr(3+)-doped boro-phosphate, boro-germo-silicate and tellurite glasses show different decay behaviors and can be well explained by multiphonon relaxation theory.

  16. Thermal Expansion Calculation of Silicate Glasses at 210°C, Based on the Systematic Analysis of Global Databases

    SciTech Connect

    Fluegel, Alex

    2010-10-01

    Thermal expansion data for more than 5500 compositions of silicate glasses were analyzed statistically. These data were gathered from the scientific literature, summarized in SciGlass© 6.5, a new version of the well known glass property database and information system. The analysis resulted in a data reduction from 5500 glasses to a core of 900, where the majority of the published values is located within commercial glass composition ranges and obtained over the temperature range 20 to 500°C. A multiple regression model for the linear thermal expansivity at 210°C, including error formula and detailed application limits, was developed based on those 900 core data from over 100 publications. The accuracy of the model predictions is improved about twice compared to previous work because systematic errors from certain laboratories were investigated and corrected. The standard model error (precision) was 0.37 ppm/K, with R² = 0.985. The 95% confidence interval for individual predictions largely depends on the glass composition of interest and the composition uncertainty. The model is valid for commercial silicate glasses containing Na2O, CaO, Al2O3, K2O, MgO, B2O3, Li2O, BaO, ZrO2, TiO2, ZnO, PbO, SrO, Fe2O3, CeO2, fining agents, and coloring and de-coloring components. In addition, a special model for ultra-low expansion glasses in the system SiO2-TiO2 is presented. The calculations allow optimizing the time-temperature cooling schedule of glassware, the development of glass sealing materials, and the design of specialty glass products that are exposed to varying temperatures.

  17. 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.

  18. 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.

  19. Chemical durability of alkali-borosilicate glasses studied by analytical SEM, IBA, isotopic-tracing and SIMS

    NASA Astrophysics Data System (ADS)

    Trocellier, P.; Djanarthany, S.; Chêne, J.; Haddi, A.; Brass, A. M.; Poissonnet, S.; Farges, F.

    2005-10-01

    Simple and complex alkali-borosilicate glasses were submitted to aqueous corrosion at room temperature, 60 and 90 °C in solutions with pH ranging between 0 and 12. Analytical scanning electron microscopy (SEM), ion beam analysis (IBA) techniques, isotopic tracing and secondary ion mass-depth profiling (SIMS) have been used to investigate the variations of the surface composition of glass. In acidic medium, the glass surface is generally covered by a thick hydrated silica layer, mobile elements like Li, Na and B and transition elements (Fe, Zr, Mo, etc.) are strongly depleted. Near pH 7, relative enrichments of aluminium, iron and rare earths are shown together with strong Li, Na and B depletions. In basic medium, the glass surface exhibits relative enrichments of the major part of transition metals (from Cr to U) whereas mobile elements seem to be kept close to their nominal concentration level at the glass surface and Si is severely impoverished. Hydrogen incorporated at the glass surface after leaching is much more immobile in neutral and basic media than in acid medium.

  20. 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.

  1. 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.

  2. Effect of ZnO on the physical properties and optical band gap of soda lime silicate glass.

    PubMed

    Zaid, Mohd Hafiz Mohd; Matori, Khamirul Amin; Aziz, Sidek Hj Abdul; Zakaria, Azmi; Ghazali, Mohd Sabri Mohd

    2012-01-01

    This manuscript reports on the physical properties and optical band gap of five samples of soda lime silicate (SLS) glass combined with zinc oxide (ZnO) that were prepared by a melting and quenching process. To understand the role of ZnO in this glass structure, the density, molar volume and optical band gaps were investigated. The density and absorption spectra in the Ultra-Violet-Visible (UV-Visible) region were recorded at room temperature. The results show that the densities of the glass samples increased as the ZnO weight percentage increased. The molar volume of the glasses shows the same trend as the density: the molar volume increased as the ZnO content increased. The optical band gaps were calculated from the absorption edge, and it was found that the optical band gap decreased from 3.20 to 2.32 eV as the ZnO concentration increased.

  3. 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.

  4. Preliminary evaluation of therapeutic ion release from Sr-doped zinc-silicate glass ceramics.

    PubMed

    Looney, Mark; O'Shea, Helen; Boyd, Daniel

    2013-01-01

    Bioactive and degradable porous bioceramics play an important role in many clinical situations. Porosity is essential to the performance of a material that is proposed to be used as an implantable osseous scaffold. Scaffolds provide a three dimensional support and template to osseous integration and vascularization. Combining the porosity of a scaffold with the ability of the scaffold material to deliver therapeutic ions to the site of implantation goes some way towards developing an ideal bone graft. A series of strontium-doped zinc silicate (Ca-Sr-Na-Zn-Si) glass ceramics scaffoldswere developed, whose porosity was measured to be between 93% and 96%, which is advantageous in terms of osseous integration and vascularization. The levels of Zn(2+) and Sr(2+) detected as a result of degradation of the crystalline phases were found to be 1.4-600 parts per million (ppm) and 0-583 ppm, respectively. The levels detected correlate well with the levels of Sr(2+) and Zn(2+)ions typically associated with clinical benefits, including antibacterial efficacy, osteoblastic differentiation and impaired osteoclastic resorption.

  5. Dissolution mechanism of soda-lime silicate glass and of PNL 76-68 in the presence of dissolved Mg

    SciTech Connect

    Sang, J.C.; Guo, Y.; Barkatt, A.; Adel-Hadadi, M.A.; Marbury, G.S.; Barkatt, A.

    1994-12-31

    Leaching studies were performed on powdered PNL 76-68 glass in de-ionized water in the presence of Mg solute. The results showed that the presence of Mg in the leachant greatly reduced the rate of glass dissolution. The equation Q = kt{sup {alpha}} was used to express the experimental data. In the absence of Mg, {alpha} was about 1, i.e., the amount of glass dissolved was linear with time. In the presence of Mg, {alpha} was close to 0.5, i.e. the extracted amount was proportional to the square root of time. Therefore, the reduction of the dissolution rate of PNL 76-68 glass in the presence of Mg solute could be explained as a result of a change in the glass dissolution mechanism. Comparative leaching studies on bulk soda-lime silicate glass in a sodium borate buffered system (pH 8.1) showed the same results. The presence of Mg in the leachant reduced the rate of glass dissolution. In the absence of Mg, {alpha} was about 1, while in the presence of Mg, {alpha} was 0.5. This change in {alpha} was not caused by changes in pH, and it represents a real change in the glass dissolution mechanism.

  6. Bioactive Glass Shell Growth of a Si-Na-Ca-P Layer on Gold Nanoparticles Functionalized with Mercaptopropyltrimethyloxysilane-Silicate

    NASA Astrophysics Data System (ADS)

    Wang, Chih-Kuang; Chen, Szu-Hsien; Li, Wan-Yun; Lai, Chern-Hsiung; Chen, Wen-Cheng

    Calcium phosphate and silicate-modified gold surfaces have potential applications in orthopedic and dental reconstruction, especially when combined with bone cement or dental resins. The aim of this study was to evaluate the formation of a Si-Na-Ca-P glass system nanoshell on functionalized gold nanoparticles. Stable gold nanoparticle suspensions were prepared by controlled reduction of HAuCl4 using the sodium citrate method to obtain a nanogold-mercaptopropyltrimethyloxysilane (MPTS)-silicate-tetraethylothosilicate (TEOS)-capped particle solution. The nanoshells were formed when directly reacted with a 10-4 M calcium phosphate ion solution. The median nanoparticle diameter was observed to be 15 nm. The MPTS-silicate-TEOS-functionalized nanoshell more effectively formed a glass shell as compared with a nonsilicate nanoshell. The changes in the surface morphology and composition were observed by a scanning transmission electron microscope equipped with energy-dispersive X-ray spectroscopy. As seen using EDS, the nanoshell was in a glass phase with CaO-poor layers.

  7. Alkali exchange equilibria between a silicate melt and coexisting magmatic volatile phase: an experimental study at 800°C and 100 MPa

    NASA Astrophysics Data System (ADS)

    Frank, Mark R.; Candela, Philip A.; Piccoli, Philip M.

    2003-04-01

    Many experimental studies have been performed to evaluate the composition of coexisting silicate melts and magmatic volatile phases (MVP). However, few studies have attempted to define the relationship between melt chemistry and the acidity of a chloride-bearing fluid. Here we report data on melt composition as a function of the HCl concentration of coexisting brines. We performed 35 experimental runs with a NaCl-KCl-HCl-H 2O brine (70 wt% NaCl [equivalent])-silicate melt (starting composition of Qtz 0.38Ab 0.33Or 0.29, anhydrous) assemblage at 800°C and 100 MPa. We determined an apparent equilibrium constant K 'meas (K, Na) =( C Nam× C KClb)/( C NaClb× C Km) for the equilibrium NaCl b+Σ K m=Σ Na m+ KCl b, (where CKClb, CNaClb, CKm, and CNam are total concentrations of potassium and sodium chloride in the brine, and potassium and sodium in the melt, respectively) as a function of the HCl concentration in the brine (C HClb). Although K' meas (K, Na) was not affected by variations in KCl/NaCl of the brine, it did vary inversely with C HClb. The relationship is given by K 'meas (K, Na) = K 'ex (K, Na) + a/C HClb [where C HClb is in wt% and a = 0.03; K' ex (K, Na) = 0.40 ± 0.03 (1σ) and represents the exchange of model sodium and potassium between chloride components in the brine and the aluminate components (NaAlO 2 and KAlO 2) in the melt. This empirical result will be discussed in light of a structural hypothesis; however, validation of the model awaits determinations based on spectroscopy or transport properties-thermodynamic relations alone cannot be used as evidence of structure. The form of this equation is consistent with a model wherein sodium is present in the melt as both sodium aluminate and sodium hydroxide components, and HCl reacts with the NaOH component in the melt to produce NaCl and H 2O. The correlation between fugacity of H 2O ( fH 2Osys), model NaOH m/ΣNa m, aluminum saturation index (ASI), and the ratio (HCl/NaCl) b of an exsolving MVP is

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

    SciTech Connect

    Sato, K.; Hatta, T.

    2015-03-07

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

  9. Highly silicic compositions on the Moon.

    PubMed

    Glotch, Timothy D; Lucey, Paul G; Bandfield, Joshua L; Greenhagen, Benjamin T; Thomas, Ian R; Elphic, Richard C; Bowles, Neil; Wyatt, Michael B; Allen, Carlton C; Donaldson Hanna, Kerri; Paige, David A

    2010-09-17

    Using data from the Diviner Lunar Radiometer Experiment, we show that four regions of the Moon previously described as "red spots" exhibit mid-infrared spectra best explained by quartz, silica-rich glass, or alkali feldspar. These lithologies are consistent with evolved rocks similar to lunar granites in the Apollo samples. The spectral character of these spots is distinct from surrounding mare and highlands material and from regions composed of pure plagioclase feldspar. The variety of landforms associated with the silicic spectral character suggests that both extrusive and intrusive silicic magmatism occurred on the Moon. Basaltic underplating is the preferred mechanism for silicic magma generation, leading to the formation of extrusive landforms. This mechanism or silicate liquid immiscibility could lead to the formation of intrusive bodies.

  10. Highly silicic compositions on the Moon.

    PubMed

    Glotch, Timothy D; Lucey, Paul G; Bandfield, Joshua L; Greenhagen, Benjamin T; Thomas, Ian R; Elphic, Richard C; Bowles, Neil; Wyatt, Michael B; Allen, Carlton C; Donaldson Hanna, Kerri; Paige, David A

    2010-09-17

    Using data from the Diviner Lunar Radiometer Experiment, we show that four regions of the Moon previously described as "red spots" exhibit mid-infrared spectra best explained by quartz, silica-rich glass, or alkali feldspar. These lithologies are consistent with evolved rocks similar to lunar granites in the Apollo samples. The spectral character of these spots is distinct from surrounding mare and highlands material and from regions composed of pure plagioclase feldspar. The variety of landforms associated with the silicic spectral character suggests that both extrusive and intrusive silicic magmatism occurred on the Moon. Basaltic underplating is the preferred mechanism for silicic magma generation, leading to the formation of extrusive landforms. This mechanism or silicate liquid immiscibility could lead to the formation of intrusive bodies. PMID:20847267

  11. L-edge XANES measurements of the oxidation state of tungsten in iron bearing and iron free silicate glasses

    SciTech Connect

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

    2008-04-28

    W{sup 4+} is relevant to core formation but W{sup 6+} may also occur. Silicate glasses show W{sup 6+} above IW and mixed valence below IW. The transition to W{sup 4+} only, appears to happen at or below IW-2 for iron free systems, but below IW-3 for iron bearing systems. 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 (Fig. 1) are inconsistent on whether W occurs as W{sup 4+} or W{sup 6+}. It is assumed that W{sup 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 fO{sub 2} 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 fO{sub 2} most relevant to core formation, around IW-2.

  12. 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.

  13. 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.

  14. ALKALI/ AKALINE-EARTH CONTENT EFFECTS ON PROPERTIES OF HIGH-ALUMINA NUCLEAR WASTE GLASSES

    SciTech Connect

    McCloy, John S.; Rodriguez, Carmen P.; Windisch, Charles F.; Leslie, Clifford J.; Schweiger, Michael J.; Riley, Brian J.; Vienna, John D.

    2010-10-01

    A series of high alumina (>20 mass %) borosilicate glasses have been made and characterized based on the assumption that the primary modifier cation field strength plays a significant role in mediating glass structure of nuclear waste glasses. Any crystallization upon quenching or after heat treatment at 950 °C for 24 hours was identified and quantified by X-ray diffraction. Particular note was take of any aluminosilicates formed, such as those in the nepheline group (MAlSiO4 where M=K, Na, Li), as these remove multiple glass-formers from the network upon crystallization. The relative roles of potassium, sodium, lithium, calcium, and magnesium on glass structure and crystallization in high alumina glasses were explored using Raman and infrared vibrational spectroscopy. Strong evidence was found for the importance of 4 membered rings in glasses with 10 mol % alkaline earths (Ca, Mg).

  15. 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

  16. UV-curable silicate phosphor planar films printed on glass substrate for white light-emitting diodes.

    PubMed

    Jang, Jin Woo; Kim, Jun Sik; Kwon, Oh Hyeon; Lee, Tae Hyeon; Cho, Yong Soo

    2015-08-15

    We suggest a simple way of forming a nonconventional remote phosphor layer for white light-emitting diodes. A printing technology using a paste consisting of yellow (Ba,Sr,Ca)(2)SiO(4):Eu(2+) silicate phosphor and ultraviolet (UV)-curable polymer is applied to form solid planar films on a common soda lime silicate glass substrate through UV radiation. Relative content of the phosphor was adjusted for the best dispersion of the phosphor particles in the polymer matrix with better emission and luminescence performance. As a result, the 70 wt. % phosphor-embedded film has a luminous efficacy of ∼70.1  lm/W at 200 mA.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

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

    PubMed

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

    2013-10-01

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

  6. 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.

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

    SciTech Connect

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

    2011-12-31

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

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  10. 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.

  11. 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.

  12. 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.

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

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

  15. 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.

  16. 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.

  17. Liquid Crystals and Glasses in Binary Systems from Sodium and Alkali-Earth Metal Butyrates

    NASA Astrophysics Data System (ADS)

    Mirnaya, T. A.; Bereznitski, Y. V.; Volkov, S. V.

    1996-07-01

    The temperature and composition ranges of liquid crystal and glass formation have been established for the binary mixtures of mesogenic sodium butyrate with non-mesogenic magnesium, calcium and strontium butyrates by means of differential thermal analysis and hot stage polarization microscopy. The formation of a vitreous optically anisotropic mesophase has been found for binaries of sodium butyrate with calcium and strontium butyrates.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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. PMID:24759778

  4. Fe(3+) ions in alkali lead tetraborate glasses--an electron paramagnetic resonance and optical study.

    PubMed

    Chakradhar, R P Sreekanth; Sivaramaiah, G; Rao, J Lakshmana; Gopal, N O

    2005-11-01

    Glass systems of composition 90R(2)B(4)O(7)+9PbO+1Fe(2)O(3) (R=Li, Na and K) and 90Li(2)B(4)O(7)+(10-x)PbO+xFe(2)O(3) (x=0.5, 1, 3, 4, 5, 7 and 9 mol %) have been investigated by means of electron paramagnetic resonance (EPR) and optical absorption techniques. The EPR spectra exhibit three resonance signals at g approximately 6.0, 4.2 and 2.0. The resonances at g approximately 6.0 and 4.2 are attributed to Fe(3+) ions in rhombic and axial symmetry sites, respectively. The g approximately 2.0 resonance signal is due to two or more Fe(3+) ions coupled together with dipolar interaction. The EPR spectra of 1 mol % of Fe(2)O(3) doped in lithium lead tetraborate glass samples have been studied at different temperatures (123-433 K). The intensity of g approximately 4.2 resonance signal decreases and the intensity of g approximately 2.0 resonance signal increases with the increase of temperature. The line widths are found to be independent of temperature. The EPR spectra exhibit a marked concentration dependence on iron content. A decrease in intensity for the resonance signal at g approximately 4.2 with increase in iron content for more than 4 mol % has been observed in lithium lead tetraborate glass samples and this has been attributed to the formation of Fe(3+) ion clusters in the glass samples. The paramagnetic susceptibility (chi) is calculated from the EPR data at various temperatures and the Curie constant (C) has been evaluated from 1/chi versus T graph. The optical absorption spectrum of Fe(3+) ions in lithium lead tetraborate glasses exhibits three bands characteristic of Fe(3+) ions in an octahedral symmetry. The crystal field parameter D(q) and the Racah interelectronic repulsion parameters B and C have also been evaluated. The value of interelectronic repulsion parameter B (825 cm(-1)) obtained in the present work suggests that the bonding is moderately covalent.

  5. 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

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

    PubMed

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

    2013-01-15

    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.

  7. 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.

  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. Surface signatures of bioactivity: MD simulations of 45S and 65S silicate glasses.

    PubMed

    Tilocca, Antonio; Cormack, Alastair N

    2010-01-01

    The surface of a bioactive (45S) and a bioinactive (65S) glass composition has been modeled using shell-model classical molecular dynamics simulations. Direct comparison of the two structures allowed us to identify the potential role of specific surface features in the processes leading to integration of a bioglass implant with the host tissues, focusing in particular on the initial dissolution of the glass network. The simulations highlight the critical role of network fragmentation and sodium enrichment of the surface in determining the rapid hydrolysis and release of silica fragments in solution, characteristic of highly bioactive compositions. On the other hand, no correlation has been found between the surface density of small (two- and three-membered) rings and bioactivity, thus suggesting that additional factors need to be taken into account to fully understand the role of these sites in the mechanism leading to calcium phosphate deposition on the glass surface. PMID:19725567

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  11. Effect of Ti(+4) on in vitro bioactivity and antibacterial activity of silicate glass-ceramics.

    PubMed

    Riaz, Madeeha; Zia, Rehana; Saleemi, Farhat; Hussain, Tousif; Bashir, Farooq; Ikhram, Hafeez

    2016-12-01

    A novel glass-ceramic series in (48-x) SiO2-36 CaO-4 P2O5-12 Na2O-xTiO2 (where x=0, 3.5, 7, 10.5 and 14mol %) system was synthesized by crystallization of glass powders, obtained by melt quenching technique. The differential scanning calorimetric analysis (DSC) was used to study the non-isothermal crystallization kinetics of the as prepared glasses. The crystallization behaviour of glasses was analyzed under non-isothermal conditions, and qualitative phase analysis of glass-ceramics was made by X-ray diffraction. The in vitro bioactivity of synthesized glass-ceramics was studied in stimulated body fluid at 37°C under static condition for 24days. The formation of hydroxyl-carbonated apatite layer; evident of bioactivity of the material, was elucidated by XRD, FTIR, AAS, SEM and EDX analysis. The result showed that partial substitution of TiO2 with SiO2 negatively influenced bioactivity; it decreased with increase in concentration of TiO2. As Ti(+4) having stronger field strength as compared to Si(+4) so its replacement became the cause for reduction in degradation that in turn improved the chemical stability. The compressive strength was also enhanced with progress addition of TiO2 in the system. The antibacterial properties were examined against Staphylococcus Epidermidis. Strong antibacterial efficacy was observed with the addition of TiO2 in the system. PMID:27612803

  12. Effect of Ti(+4) on in vitro bioactivity and antibacterial activity of silicate glass-ceramics.

    PubMed

    Riaz, Madeeha; Zia, Rehana; Saleemi, Farhat; Hussain, Tousif; Bashir, Farooq; Ikhram, Hafeez

    2016-12-01

    A novel glass-ceramic series in (48-x) SiO2-36 CaO-4 P2O5-12 Na2O-xTiO2 (where x=0, 3.5, 7, 10.5 and 14mol %) system was synthesized by crystallization of glass powders, obtained by melt quenching technique. The differential scanning calorimetric analysis (DSC) was used to study the non-isothermal crystallization kinetics of the as prepared glasses. The crystallization behaviour of glasses was analyzed under non-isothermal conditions, and qualitative phase analysis of glass-ceramics was made by X-ray diffraction. The in vitro bioactivity of synthesized glass-ceramics was studied in stimulated body fluid at 37°C under static condition for 24days. The formation of hydroxyl-carbonated apatite layer; evident of bioactivity of the material, was elucidated by XRD, FTIR, AAS, SEM and EDX analysis. The result showed that partial substitution of TiO2 with SiO2 negatively influenced bioactivity; it decreased with increase in concentration of TiO2. As Ti(+4) having stronger field strength as compared to Si(+4) so its replacement became the cause for reduction in degradation that in turn improved the chemical stability. The compressive strength was also enhanced with progress addition of TiO2 in the system. The antibacterial properties were examined against Staphylococcus Epidermidis. Strong antibacterial efficacy was observed with the addition of TiO2 in the system.

  13. 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.

  14. The influence of silver-ion doping using ion implantation on the luminescence properties of Er-Yb silicate glasses

    NASA Astrophysics Data System (ADS)

    Stanek, S.; Nekvindova, P.; Svecova, B.; Vytykacova, S.; Mika, M.; Oswald, J.; Mackova, A.; Malinsky, P.; Spirkova, J.

    2016-03-01

    A set of zinc-silicate glasses with different ratios of erbium and ytterbium was fabricated. To achieve Ag-rich thin films in a sub-surface layer, ion-implantation technique at an energy of 1.2 MeV and 1.7 MeV with a fluence of 1 × 1016 cm-2 was used. Post-implantation annealing was also applied. Changes in the spectroscopic and lasing properties of erbium ions as a function of implantation fluence of silver were studied with the aim to assess the positive effect of silver as a sensitiser of erbium luminescence. Therefore, absorption spectra in the visible range as well as luminescence spectra in the near-infrared range were measured and partially also the 4I11/2-4I15/2 transition of the erbium ion was studied. The results showed that silver positively influenced luminescence intensity at 1530 nm by increasing it almost three times. The biggest increase was achieved in glass with the highest concentration of erbium. Luminescence lifetime was not significantly influenced by the presence of silver and still remained around 10 ms.

  15. ∼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.

  16. Better Alternatives to "Astronomical Silicate": Laboratory-based Optical Functions of Chondritic/Solar Abundance Glass with Application to HD 161796

    NASA Astrophysics Data System (ADS)

    Speck, A. K.; Pitman, K. M.; Hofmeister, A. M.

    2015-08-01

    “Astronomical” or “circumstellar” silicate optical functions (real and imaginary indices of refraction n(λ ) and k(λ )) have previously been derived from compositionally and structurally disparate samples; past values were compiled from different sources in the literature, and are essentially kluges of observational, laboratory, and extrapolated or interpolated values. These synthetic optical functions were created because astronomers lack the quantitative data on amorphous silicates at all wavelengths needed for radiative transfer modeling. This paper provides optical functions that (1) are created with a consistent methodology, (2) use the same sample across all wavelengths, and (3) minimize interpolation and extrapolation wherever possible. We present electronic data tables of optical functions derived from mid-ultraviolet to far-infrared (FIR) laboratory transmission spectra for two materials: iron-free glass with chondritic/solar atmospheric abundances, and metallic iron. We compare these optical functions to other popular n, k data used to model amorphous silicates (e.g., “astronomical” or “circumstellar” silicate), both directly and in application to a simple system: the dust shell of the post-AGB star HD 161796. Using the new optical functions, we find that the FIR profile of model spectral energy distributions are significantly affected by the ratio of glass to iron. Our case study on HD 161796 shows that in modeling with our new optical functions, the mineralogy is markedly different from that derived using synthetic optical functions and suggests a new scenario of crystalline silicate formation.

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

    NASA Astrophysics Data System (ADS)

    Erdogan, S. T.

    2015-12-01

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

  18. On the Paramagnetic Impurity Concentration of Silicate Glasses from Low-Temperature Physics

    NASA Astrophysics Data System (ADS)

    Bonfanti, Silvia; Jug, Giancarlo

    2015-08-01

    The concentration of paramagnetic trace impurities in glasses can be determined via precise SQUID measurements of the sample's magnetization in a magnetic field. However, the existence of quasi-ordered structural inhomogeneities in the disordered solid causes correlated tunneling currents that can contribute to the magnetization, surprisingly, also at the higher temperatures. We show that taking into account such tunneling systems gives rise to a good agreement between the concentrations extracted from SQUID magnetization and those extracted from low-temperature heat capacity measurements. Without suitable inclusion of such magnetization contribution from the tunneling currents, we find that the concentration of paramagnetic impurities gets considerably over-estimated. This analysis represents a further positive test for the structural inhomogeneity theory of the magnetic effects in the cold glasses.

  19. Synthesis and structural studies of multi-component strontium zinc silicate glass-ceramics

    SciTech Connect

    Tiwari, Babita; Pandey, M.; Kothiyal, G. P.; Gadkari, S. C.

    2013-02-05

    Glass having composition 40SrO-10ZnO-40SiO{sub 2}-2B{sub 2}O{sub 3}-2Al{sub 2}O{sub 3}-2TiO{sub 2}-2Cr{sub 2}O{sub 3}-2Y{sub 2}O{sub 3}, (mol %) was prepared by melt-quench technique and converted into glass-ceramics by subjecting it to varying heat treatments. Thermal properties were measured by thermo-mechanical analyzer and differential thermal analyzer. The XRD revealed that initially Sr{sub 2}ZnSi{sub 2}O{sub 7} phase at lower temperature and later SrSiO{sub 3}/Sr{sub 3}Si{sub 3}O{sub 9} phase crystallized. The structural elucidation by Raman spectroscopy shows the presence of mainly Q{sup 1} structural units along with Q{sup 2} and Q{sup 0} units in the base glass. Raman spectra revealed that during crystallization initially crystalline phase having Q{sup 1} structural units (corresponding to Sr{sub 2}ZnSi{sub 2}O{sub 7} phase) are formed and later crystalline phase having Q{sup 2} structural units with 3 member ring type structure crystallizes. Thus, Raman spectroscopy and XRD together confirm that in early stage of crystallization, Sr{sub 2}ZnSi{sub 2}O{sub 7} phase and later Sr{sub 3}Si{sub 3}O{sub 9} phase formed in the glass-ceramics.

  20. 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

  1. Spectroscopic investigation of amber color silicate glasses and factors affecting the amber related absorption bands.

    PubMed

    Morsi, Morsi M; El-Sherbiny, Samya I; Mohamed, Karam M

    2015-06-15

    The effects of carbon, Fe2O3 and Na2SO4 contents on the amber color of glass with composition (wt%) 64.3 SiO2, 25.7 CaO, 10 Na2O were studied. The effect of some additives that could be found in glass batch or cullets on the amber related absorption band(s) was also studied. An amber related absorption band due to the chromophore Fe(3+)O3S(2-) was recorded at 420 nm with shoulder at 440 nm. A second amber related band recorded at 474 nm with shoulder at 483 nm was assigned to FeS. Increasing melting time at 1400°C up to 6h caused fainting of the amber color, decreases the intensities of the amber related bands and shifted the first band to 406 nm. Addition of ZnO, Cu2O and NaNO3 to the glass produced decolorizing effect and vanishing of the amber related bands. The effects of melting time and these additives were explained on the bases of destruction the amber chromophore and its conversion into Fe(3+) in tetrahedral sites or ZnS. Addition of Se intensifies the amber related bands and may cause dark coloration due to the formation of Se° and polyselenide. Amber color can be monitored through measuring the absorption in the range 406-420 nm.

  2. Spectroscopic investigation of amber color silicate glasses and factors affecting the amber related absorption bands

    NASA Astrophysics Data System (ADS)

    Morsi, Morsi M.; El-sherbiny, Samya I.; Mohamed, Karam M.

    2015-06-01

    The effects of carbon, Fe2O3 and Na2SO4 contents on the amber color of glass with composition (wt%) 64.3 SiO2, 25.7 CaO, 10 Na2O were studied. The effect of some additives that could be found in glass batch or cullets on the amber related absorption band(s) was also studied. An amber related absorption band due to the chromophore Fe3+O3S2- was recorded at 420 nm with shoulder at 440 nm. A second amber related band recorded at 474 nm with shoulder at 483 nm was assigned to FeS. Increasing melting time at 1400 °C up to 6 h caused fainting of the amber color, decreases the intensities of the amber related bands and shifted the first band to 406 nm. Addition of ZnO, Cu2O and NaNO3 to the glass produced decolorizing effect and vanishing of the amber related bands. The effects of melting time and these additives were explained on the bases of destruction the amber chromophore and its conversion into Fe3+ in tetrahedral sites or ZnS. Addition of Se intensifies the amber related bands and may cause dark coloration due to the formation of Se° and polyselenide. Amber color can be monitored through measuring the absorption in the range 406-420 nm.

  3. 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.

  4. 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.

  5. 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.

  6. Color center generation in sodium-calcium silicate glass by nanosecond and femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Siiman, Leo A.; Glebov, Leonid B.

    2005-12-01

    It was found that high purity soda lime glass shows a markedly different induced absorption spectra when exposed to different types of ionizing radiation such as UV lamp or femtosecond and nanosecond laser pulses. The following irradiation was used in the experiments: nanosecond pulses at the fundamental and harmonics of a Nd:YAG laser (λ = 1064, 532, 355, and 266 nm), femtosecond pulses of a Ti:sapphire laser operating at λ = 780 nm, ultraviolet rays from a high pressure Xe lamp, X-rays, and Gamma rays. Features of radiation defect generations are discussed.

  7. 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.

  8. Strontium environment transition in tin silicate glasses by neutron and x-ray diffraction.

    SciTech Connect

    Johnson, J. A.; Urquidi, D.; Holland, D.; Johnson, C. E.; Appelyard, P. G.; New Mexico State Univ.; LANL; Warwick Univ.; Northern Illinois Univ.; Cranfield Univ.

    2007-11-15

    The effect of Sr modifier atoms on the structure of stannosilicate glasses of composition (Sr0){sub x}(SnO){sub 0.5-x}(SiO{sub 2}){sub 0.5}, with 0 {le} x {le} 0.15, has been studied using Moessbauer spectroscopy and neutron and X-ray diffraction. The tin is mostly in the Sn{sup 2+} state. The Sr-O bond length undergoes a step decrease from (2.640 {+-} 0.005) {angstrom} to (2.585 {+-} 0.005) {angstrom} as x increases from 0.10 to 0.15, indicating a decrease in co-ordination number from 8 to 7. A Sn-Sn distance of 3.507 {+-} 0.005 {angstrom} is revealed by a first-order difference calculation from the x = 0 sample. This is too short to be consistent with significant edge sharing of [SnO{sub 3}] trigonal pyramids.

  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. Phospho-silicate glass gated 4H-SiC metal-oxide-semiconductor devices: Phosphorus concentration dependence

    NASA Astrophysics Data System (ADS)

    Jiao, C.; Ahyi, A. C.; Xu, C.; Morisette, D.; Feldman, L. C.; Dhar, S.

    2016-04-01

    The correlation between phosphorus concentration in phospho-silicate glass (PSG) gate dielectrics and electrical properties of 4H-SiC MOS devices has been investigated. Varying P uptake in PSG is achieved by changing the POCl3 post-oxidation annealing temperature. The density of interface traps (Dit) at the PSG/4H-SiC interface decreases as the amount of interfacial P increases. Most significantly, the MOSFET channel mobility does not correlate with Dit for all samples, which is highly unusual for SiC MOSFETs. Further analysis reveals two types of field-effect mobility (μfe) behavior, depending on the annealing temperature. Annealing at 1000 °C improves the channel mobility most effectively, with a peak value ˜105 cm2 V-1 s-1, and results in a surface phonon scattering limited mobility at high oxide field. On the other hand, PSG annealed at other temperatures results in a surface roughness scattering limited mobility at similar field.

  12. 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.

  13. 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.

  14. Micro-Brillouin spectroscopy mapping of the residual density field induced by Vickers indentation in a soda-lime silicate glass

    NASA Astrophysics Data System (ADS)

    Tran, H.; Clément, S.; Vialla, R.; Vandembroucq, D.; Rufflé, B.

    2012-06-01

    High-resolution Brillouin scattering is used to achieve 3-dimensional maps of the longitudinal acoustic mode frequency shift in soda-lime silicate glasses subject to Vickers indentations. Assuming that residual stress-induced effects are simply proportional to density changes, residual densification fields are obtained. The density gradient is nearly isotropic, confirming earlier optical observations made on a similar glass. The results show that Brillouin micro-spectroscopy opens the way to a fully quantitative comparison of experimental data with predictions of mechanical models for the identification of a constitutive law.

  15. 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.

  16. 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.

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

    SciTech Connect

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

    1997-10-01

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

  18. 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

  19. 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

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-11-01

    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 (Li2O.2SiO2) over a wide temperature range, from above Tm to 0.98Tg where Tg ≈ 727 K is the calorimetric glass transition temperature and Tm = 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, O2-, and Si4+ 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 Li2Si2O5 "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 Tm. 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 nucleation time-lags) but at a

  2. Na/Ca Intermixing around Silicate and Phosphate Groups in Bioactive Phosphosilicate Glasses Revealed by Heteronuclear Solid-State NMR and Molecular Dynamics Simulations.

    PubMed

    Mathew, Renny; Stevensson, Baltzar; Edén, Mattias

    2015-04-30

    We characterize the intermixing of network-modifying Na(+)/Ca(2+) ions around the silicate (QSi(n)) and phosphate (QP(n)) tetrahedra in a series of 16 Na2O–CaO–SiO2–P2O5 glasses, whose P content and silicate network connectivity were varied independently. The set includes both bioactive and bioinactive compositions and also encompasses two soda-lime-silicate members devoid of P, as well as two CaO–SiO2 glasses and one Na2O–SiO2–P2O5 glass. The various Si/P↔Na/Ca contacts were probed by molecular dynamics (MD) simulations together with heteronuclear magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) experimentation utilizing (23)Na{(31)P} and (23)Na{(29)Si} REDOR, as well as (31)P{ (23)Na} and (29)Si{(23)Na} REAPDOR. We introduce an approach for quantifying the extent of Na(+)/Ca(2+) ordering around a given QP(n) or QSi(n) group, encoded by the preference factor 0⩽ PM ⩽ 1 conveying the relative weights of a random cation intermixing (PM = 0) and complete preference/ordering (PM = 1) for one of the species M, which represents either Na(+) or Ca(2+). The MD-derived preference factors reveal phosphate and silicate species surrounded by Na(+)/Ca(2+) ions intermixed nearly randomly (PM ≲ 0.15), except for the QSi(4) and QSi(1) groups, which manifest more significant cation ordering with preference for Na+ and Ca2+, respectively. The overall weak preferences are essentially independent of the Si and P contents of the glass, whereas PM primarily correlates with the total amount of network modifiers: as the latter is increased, the Na/Ca distribution around the {QP(0), QSi(1), QSi(2)} groups with preference for Ca2(+ )tend to randomize (i.e., PCa decreases), while the PNa-values grow slightly for the {QP(1), QSi(3), QSi(4)} species already preferring coordination of Na. The set of experimental preference factors {PCa} for the orthophosphate (QP(0)) groups extracted from (31)P{(23)Na} REAPDOR NMR-derived M2(P–Na) dipolar second moments agrees

  3. 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

  4. Borosilicate glass alteration driven by magnesium carbonates

    NASA Astrophysics Data System (ADS)

    Debure, M.; Frugier, P.; De Windt, L.; Gin, S.

    2012-01-01

    The alteration of simplified synthetic glass, representative of the French reference nuclear glass R7T7, in presence of hydromagnesite has been experimentally investigated and modeled. Magnesium in solution is known to potentially enhance glass alteration; nuclear glass clayed host rocks contain magnesium and can dissolve to maintain the concentration of magnesium in solution. For modeling purposes, it was suitable to study a simple system. Hydromagnesite was therefore chosen as a simple model mineral in order to check the influence of an Mg-rich mineral on glass alteration. Since the models use thermodynamic and kinetic parameters measured in pure water and pH-buffered solutions, changing the solution composition or adding minerals is a key step towards the validation of the modeling assumptions before using the model for predictive purposes. Experiments revealed that glass alteration is enhanced in presence of hydromagnesite. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC reactive transport code. Modeling proved useful both for explaining the mechanisms involved and quantifying the impact on glass alteration: Mg coming from hydromagnesite dissolution reacts with Si provided by the glass in order to form magnesium silicates. This reaction decreases the pH down to neutral conditions where magnesium silicates are more soluble than at the natural alkali pH imposed by glass or hydromagnesite dissolution. The driving force of the magnesium silicate precipitation is eventually the interdiffusion of alkali within the altered amorphous glass layer as this mechanism consumes protons. The model's ability to describe the concentrations of elements in solution and formed solids whatever the glass/hydromagnesite ratio strongly supports the basic modeling hypothesis.

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

    SciTech Connect

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

    1981-01-01

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

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Comparative study of the strength of Er indirect optical pumping in silicate glasses codoped with Si clusters and Er 3+ ions

    NASA Astrophysics Data System (ADS)

    Lebour, Youcef; Pellegrino, Paolo; García, Cristina; Moreno, José A.; Garrido, Blas

    2006-04-01

    Erbium-doped silicon-rich dielectrics are expected to lead to compact and scalable cost-effective optical amplifiers due to the high sensing of Er via nano-silicon. Different silicates glasses, namely: Aluminum-silicates, soda-lime glasses and fused silica codoped with Si and Er were used in order to explore the mechanism of energy transfer from Si nanoclusters (Si nc) to Er. Si excess of 5 and 15 at.% and different Er doses, so that the resulting Er peak concentration could vary from 2x10 19 up to 6x10 20 cm -3, were introduced in the wafers by ion implantation technique. Thermal treatments in a rapid thermal process were carried out before and after Er implantation in order to precipitate Si nc, and to find the accurate temperature to obtain the best Er emission around 1540 nm. Very intense emission, comparing to structures only doped with Er, has been detected in all co-implanted glasses. By time resolved photoluminescence experiments we measured lifetimes of the exited state of Er 3+ ions ranging from 2.5 to 12 ms and an effective excitation cross-section about 1x10 -17 - 6 x10 -17 cm2 (depending on the Er dose and Si excess). This is orders of magnitude higher than the Er direct absorption cross-section (about 10-21 cm2). By quantifying Er emission we found only 10% of the total Er concentration was effectively excited through Si nc.

  12. 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.

  13. Highly thermally stable single-component white-emitting silicate glass for organic-resin-free white-light-emitting diodes.

    PubMed

    Zhang, Xuejie; Huang, Lin; Pan, Fengjuan; Wu, Mingmei; Wang, Jing; Chen, Yan; Su, Qiang

    2014-02-26

    Thermal management is still a great challenge for high-power phosphor-converted white-light-emitting diodes (pc-WLEDs) intended for future general lighting. In this paper, a series of single-component white-emitting silicate SiO2-Li2O-SrO-Al2O3-K2O-P2O5: Ce(3+), Tb(3+), Mn(2+) (SLSAKP: Ce(3+), Tb(3+), Mn(2+)) glasses that simultaneously play key roles as a luminescent convertor and an encapsulating material for WLEDs were prepared via the conventional melt-quenching method, and systematically studied using their absorption spectra, transmittance spectra, photoluminescence excitation and emission spectra in the temperature range 296-498 K, decay curves, and quantum efficiency. The glasses show strong and broad absorption in 250-380 nm region and exhibit intense white emission, produced by in situ mixing of blue-violet, green, and orange-red light from Ce(3+), Tb(3+), and Mn(2+) ions, respectively, in a single glass component. The quantum efficiency of SLSAKP: 0.3%Ce(3+), 2.0%Tb(3+), 2.0%Mn(2+) glass is determined to be 19%. More importantly, this glass shows good thermal stability, exhibiting at 373 and 423 K about 84.56 and 71.02%, respectively, of the observed room temperature (298 K) emission intensity. The chromaticity shift of SLSAKP: 0.3%Ce(3+), 2.0%Tb(3+), 2.0%Mn(2+) is 2.94 × 10(-2) at 498 K, only 57% of the commercial triple-color white-emitting phosphor mixture. Additionally, this glass shows no transmittance loss at the 370 nm emission of a UV-Chip-On-Board (UV-COB) after thermal aging for 240 h, compared with the 82% transmittance loss of epoxy resin. The thermal conductivity of the glass is about 1.07 W/mK, much larger than the 0.17 W/mK of epoxy resin. An organic-resin-free WLEDs device based on SLSAKP: 0.3%Ce(3+), 2.0%Tb(3+), 2.0%Mn(2+) glass and UV-COB is successfully demonstrated. All of our results demonstrate that the presented Ce(3+)/Tb(3+)/Mn(2+) tridoped lithium-strontium-silicate glass may serve as a promising candidate for high-power WLEDs

  14. Highly thermally stable single-component white-emitting silicate glass for organic-resin-free white-light-emitting diodes.

    PubMed

    Zhang, Xuejie; Huang, Lin; Pan, Fengjuan; Wu, Mingmei; Wang, Jing; Chen, Yan; Su, Qiang

    2014-02-26

    Thermal management is still a great challenge for high-power phosphor-converted white-light-emitting diodes (pc-WLEDs) intended for future general lighting. In this paper, a series of single-component white-emitting silicate SiO2-Li2O-SrO-Al2O3-K2O-P2O5: Ce(3+), Tb(3+), Mn(2+) (SLSAKP: Ce(3+), Tb(3+), Mn(2+)) glasses that simultaneously play key roles as a luminescent convertor and an encapsulating material for WLEDs were prepared via the conventional melt-quenching method, and systematically studied using their absorption spectra, transmittance spectra, photoluminescence excitation and emission spectra in the temperature range 296-498 K, decay curves, and quantum efficiency. The glasses show strong and broad absorption in 250-380 nm region and exhibit intense white emission, produced by in situ mixing of blue-violet, green, and orange-red light from Ce(3+), Tb(3+), and Mn(2+) ions, respectively, in a single glass component. The quantum efficiency of SLSAKP: 0.3%Ce(3+), 2.0%Tb(3+), 2.0%Mn(2+) glass is determined to be 19%. More importantly, this glass shows good thermal stability, exhibiting at 373 and 423 K about 84.56 and 71.02%, respectively, of the observed room temperature (298 K) emission intensity. The chromaticity shift of SLSAKP: 0.3%Ce(3+), 2.0%Tb(3+), 2.0%Mn(2+) is 2.94 × 10(-2) at 498 K, only 57% of the commercial triple-color white-emitting phosphor mixture. Additionally, this glass shows no transmittance loss at the 370 nm emission of a UV-Chip-On-Board (UV-COB) after thermal aging for 240 h, compared with the 82% transmittance loss of epoxy resin. The thermal conductivity of the glass is about 1.07 W/mK, much larger than the 0.17 W/mK of epoxy resin. An organic-resin-free WLEDs device based on SLSAKP: 0.3%Ce(3+), 2.0%Tb(3+), 2.0%Mn(2+) glass and UV-COB is successfully demonstrated. All of our results demonstrate that the presented Ce(3+)/Tb(3+)/Mn(2+) tridoped lithium-strontium-silicate glass may serve as a promising candidate for high-power WLEDs.

  15. 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.

  16. Through the volcanic-looking glass: using pyroclastic obsidian to image magma degassing and flow in shallow silicic conduits

    NASA Astrophysics Data System (ADS)

    Castro, J. M.; Tuffen, H.; Schipper, C.

    2012-12-01

    Obsidian pyroclasts have been widely used to understand magma degassing processes and conduit flow during Plinian eruptions of silicic magma. Recent observations of active rhyolite volcanoes show that obsidian pyroclasts may also erupt during dominantly effusive activity and this raises the question of how might the crystallization, degassing, and cooling histories differ between parcels of magma that become pyroclastic versus effusive obsidian? As the two disparate, yet coeval eruptive styles require different magma ascent conditions, it follows that glassy pyroclasts should record these differences. Here we report on chemical and textural evidence of degassing and crystallization in glassy bombs, pyroclastic lapilli and obsidian lava collected from the recently active Cordón Caulle and Chaitén volcanoes in southern Chile. Coarse obsidian bombs are abundant at both volcanoes and were erupted during large blasts that accompanied lava effusion. Obsidian lapilli are equally ubiquitous in fall deposits and near-vent tuff cones formed during the initial Plinian phases of activity. Total H2O contents and hydrous speciation was measured on these glassy materials by FTIR. The data show two distinct trends, one corresponding to bombs and glassy lavas and characterized by a relative abundance of molecular water and the other associated with the lapilli glasses having relatively elevated OH-. These speciation patterns can be explained by different cooling histories in parcels of magma that had different ascent speeds and residence times in the conduit. The bomb and lava obsidians appear to form of a single Pressure-Temperature-time (P-T-t) path, one that is offset from the Plinian lapilli to lower ascent and cooling rates. These relations suggest that flow in the volcanic conduit is bifurcated and this allows parcels of magma to rise up quickly and fuel sustained pyroclastic columns while other magma can follow more relaxed ascent trajectories allowing it to become proto

  17. Estimation of excited-state absorption and photobleaching in Fe²⁺-doped lithium sodium silicate glass under exposure to high-power nanosecond laser pulses.

    PubMed

    Demos, Stavros G; Ehrmann, Paul R; Qiu, S Roger; Schaffers, Kathleen I; Suratwala, Tayyab I

    2015-04-01

    Fe-doped lithium sodium silicate glasses codoped with Sn and C to promote the Fe²⁺ redox state are investigated under simultaneous excitation at the first and third harmonics of a nanosecond Nd:YAG laser. The aim is to evaluate critical parameters associated with the potential use of this material as an optical filter that transmits the third harmonic but blocks the fundamental frequency. Estimations of the excited-state absorption coefficient and photobleaching (reduction of absorption at the fundamental) are provided. The results provide insight on the design and expected operational parameters of this type of Fe-doped materials. PMID:25967187

  18. Tunable Luminescent Properties and Concentration-Dependent, Site-Preferable Distribution of Eu(2+) Ions in Silicate Glass for White LEDs Applications.

    PubMed

    Zhang, Xuejie; Wang, Jing; Huang, Lin; Pan, Fengjuan; Chen, Yan; Lei, Bingfu; Peng, Mingying; Wu, Mingmei

    2015-05-13

    The design of luminescent materials with widely and continuously tunable excitation and emission is still a challenge in the field of advanced optical applications. In this paper, we reported a Eu(2+)-doped SiO2-Li2O-SrO-Al2O3-K2O-P2O5 (abbreviated as SLSAKP:Eu(2+)) silicate luminescent glass. Interestingly, it can give an intense tunable emission from cyan (474 nm) to yellowish-green (538 nm) simply by changing excitation wavelength and adjusting the concentration of Eu(2+) ions. The absorption spectra, photoluminescence excitation (PLE) and emission (PL) spectra, and decay curves reveal that there are rich and distinguishable local cation sites in SLSAKP glasses and that Eu(2+) ions show preferable site distribution at different concentrations, which offer the possibility to engineer the local site environment available for Eu(2+) ions. Luminescent glasses based color and white LED devices were successfully fabricated by combining the as-synthesized glass and a 385 nm n-UV LED or 450 nm blue LED chip, which demonstrates the potential application of the site engineering of luminescent glasses in advanced solid-state lighting in the future. PMID:25897869

  19. Tunable Luminescent Properties and Concentration-Dependent, Site-Preferable Distribution of Eu(2+) Ions in Silicate Glass for White LEDs Applications.

    PubMed

    Zhang, Xuejie; Wang, Jing; Huang, Lin; Pan, Fengjuan; Chen, Yan; Lei, Bingfu; Peng, Mingying; Wu, Mingmei

    2015-05-13

    The design of luminescent materials with widely and continuously tunable excitation and emission is still a challenge in the field of advanced optical applications. In this paper, we reported a Eu(2+)-doped SiO2-Li2O-SrO-Al2O3-K2O-P2O5 (abbreviated as SLSAKP:Eu(2+)) silicate luminescent glass. Interestingly, it can give an intense tunable emission from cyan (474 nm) to yellowish-green (538 nm) simply by changing excitation wavelength and adjusting the concentration of Eu(2+) ions. The absorption spectra, photoluminescence excitation (PLE) and emission (PL) spectra, and decay curves reveal that there are rich and distinguishable local cation sites in SLSAKP glasses and that Eu(2+) ions show preferable site distribution at different concentrations, which offer the possibility to engineer the local site environment available for Eu(2+) ions. Luminescent glasses based color and white LED devices were successfully fabricated by combining the as-synthesized glass and a 385 nm n-UV LED or 450 nm blue LED chip, which demonstrates the potential application of the site engineering of luminescent glasses in advanced solid-state lighting in the future.

  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. 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.

  2. Mechanical and microstructural properties of alkali-activated fly ash geopolymers.

    PubMed

    Komljenović, M; Bascarević, Z; Bradić, V

    2010-09-15

    This paper investigates the properties of geopolymer obtained by alkali-activation of fly ash (FA), i.e. the influence of characteristics of the representative group of FA (class F) from Serbia, as well as that of the nature and concentration of various activators on mechanical and microstructural properties of geopolymers. Aqueous solutions of Ca(OH)(2), NaOH, NaOH+Na(2)CO(3), KOH and sodium silicate (water glass) of various concentrations were used as alkali activators. It was established that the nature and concentration of the activator was the most dominant parameter in the alkali-activation process. In respect of physical characteristics of FA, the key parameter was fineness. The geopolymer based on FA with the highest content of fine particles (<43 microm), showed the highest compressive strength in all cases. Regardless of FA characteristics, nature and concentration of the activator, the alkali-activation products were mainly amorphous. The formation of crystalline phases (zeolites) occurred in some cases, depending on the reaction conditions. The highest compressive strength was obtained using sodium silicate. Together with the increase of sodium silicate SiO(2)/Na(2)O mass ratio, the atomic Si/Al ratio in the reaction products was also increased. Under the experimental conditions of this investigation, high strength was directly related to the high Si/Al ratio. PMID:20554110

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

    SciTech Connect

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

    2012-05-28

    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/cm{sup 2}) leads to a characteristic shift of {approx}1.0 eV in the K-edge revealing a reduced ({approx}3%) mean magnesium bond length to the ligated oxygen ions (Mg-O) along with a reduced average coordination number of the Mg ions.

  4. 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.

  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. 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.

    2016-10-01

    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 (ΔE) have been evaluated. The values of E opt and ΔE 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.

  8. Evidence of denser MgSiO3 glass above 133 gigapascal (GPa) and implications for remnants of ultradense silicate melt from a deep magma ocean.

    PubMed

    Murakami, Motohiko; Bass, Jay D

    2011-10-18

    Ultralow velocity zones are the largest seismic anomalies in the mantle, with 10-30% seismic velocity reduction observed in thin layers less than 20-40 km thick, just above the Earth's core-mantle boundary (CMB). The presence of silicate melts, possibly a remnant of a deep magma ocean in the early Earth, have been proposed to explain ultralow velocity zones. It is, however, still an open question as to whether such silicate melts are gravitationally stable at the pressure conditions above the CMB. Fe enrichment is usually invoked to explain why melts would remain at the CMB, but this has not been substantiated experimentally. Here we report in situ high-pressure acoustic velocity measurements that suggest a new transformation to a denser structure of MgSiO(3) glass at pressures close to those of the CMB. The result suggests that MgSiO(3) melt is likely to become denser than crystalline MgSiO(3) above the CMB. The presence of negatively buoyant and gravitationally stable silicate melts at the bottom of the mantle, would provide a mechanism for observed ultralow seismic velocities above the CMB without enrichment of Fe in the melt. An ultradense melt phase and its geochemical inventory would be isolated from overlying convective flow over geologic time. PMID:21969547

  9. Evidence of denser MgSiO3 glass above 133 gigapascal (GPa) and implications for remnants of ultradense silicate melt from a deep magma ocean.

    PubMed

    Murakami, Motohiko; Bass, Jay D

    2011-10-18

    Ultralow velocity zones are the largest seismic anomalies in the mantle, with 10-30% seismic velocity reduction observed in thin layers less than 20-40 km thick, just above the Earth's core-mantle boundary (CMB). The presence of silicate melts, possibly a remnant of a deep magma ocean in the early Earth, have been proposed to explain ultralow velocity zones. It is, however, still an open question as to whether such silicate melts are gravitationally stable at the pressure conditions above the CMB. Fe enrichment is usually invoked to explain why melts would remain at the CMB, but this has not been substantiated experimentally. Here we report in situ high-pressure acoustic velocity measurements that suggest a new transformation to a denser structure of MgSiO(3) glass at pressures close to those of the CMB. The result suggests that MgSiO(3) melt is likely to become denser than crystalline MgSiO(3) above the CMB. The presence of negatively buoyant and gravitationally stable silicate melts at the bottom of the mantle, would provide a mechanism for observed ultralow seismic velocities above the CMB without enrichment of Fe in the melt. An ultradense melt phase and its geochemical inventory would be isolated from overlying convective flow over geologic time.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. Measurements of alkali concentrations in an oxygen-natural gas-fired soda-lime-silica glass furnace

    SciTech Connect

    S. G. Buckley; P. M. Walsh; D. w. Hahn; R. J. Gallagher; M. K. Misra; J. T. Brown; F. Quan; K. Bhatia; V. I. Henry; R. D. Moore

    1999-10-18

    Sodium species vaporized from melting batch and molten glass in tank furnaces are the principal agents of corrosion of superstructure refractory and main contributors to emissions of particulate matter from glass melting. The use of oxygen in place of air for combustion of natural gas reduces particulate emissions, but is thought to accelerate corrosion in some melting tanks. Methods for measuring sodium are under investigation as means for identifying the volatilization, transport, and deposition mechanisms and developing strategies for control. Three separate methods were used to measure the concentrations of sodium species at various locations in an oxygen-natural gas-fired soda-lime-silica glass melting tank. Measurements were made inside the furnace using the absorption of visible light and in the flue duct using Laser-Induced Breakdown Spectroscopy (LIBS). Measurements in both the furnace and flue were also made by withdrawing and analyzing samples of the furnace gas.

  15. 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)

  16. 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.

  17. 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

  18. Investigation on broadband near-infrared emission in Yb3+/Ho3+ co-doped antimony-silicate glass and optical fiber

    NASA Astrophysics Data System (ADS)

    Dorosz, D.; Zmojda, J.; Kochanowicz, M.

    2013-10-01

    In the paper antimony-silicate glass and double-clad optical fiber co-doped with ytterbium and holmium ions were investigated. Absorption spectra in infrared (FT-IR) showed characteristic bands: 445, 605, 1037, 1168 cm-1 coming from the vibration of chemical bonds of SbO3 and SiO4, respectively. The combination of relatively low phonon energy with a capability for greater separation (avoiding clustering) of optically active centers in the fabricated glasses should allow an effective expansion of spontaneous emission band. The highest intensity of emission at the wavelength of λe = 1950 nm resulting from energy transfer between Yb3+ → Ho3+ ions was observed in the glass co-doped with 1 mol% Yb2O3:0.5 mol% Ho2O3. As a result of the optical pumping at the wavelength of 976 nm in the produced optical fiber, strong and narrow band of amplified spontaneous emission (ASE) around 2.1 μm, corresponds to the 5I7 → 5I8 transition, were obtained.

  19. 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.

  20. 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.

  1. 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.

  2. Glass substrates crosslinked with tetracycline-imprinted polymeric silicate and CdTe quantum dots as fluorescent sensors.

    PubMed

    Chao, Mu-Rong; Hu, Chiung-Wen; Chen, Jian-Lian

    2016-06-21

    A fluorescence-based sensor that combines the merits of quantum dots (QDs) and molecularly imprinted polymers (MIPs) was first fabricated on a glass substrate via a sol-gel route. Some of the key performance factors, including silane selection, substrate etching, the reaction times of glass silanization and sol-gel polymerization, and the times and methods used for template stripping and loading, were discussed and determined. After fabricating the sensor on either a 3-aminopropyltriethoxysilane (APS) or a 3-mercaptopropyltriethoxysilane (MPS) modified glass substrate, APS showed a much better performance than MPS as both the capping reagent of QDs and the functional monomer of tetracycline-templated MIPs. The APS-QDs on APS-modified glass had a higher imprinted factor (IF = 5.6), a lower LOD (2.1 μM, 3σ), and a more stable signal (2.8%, n = 10 at 70 μM) than those on the MPS-modified glass (IF = 5.2, LOD = 6.5 μM, stability = 6.2%). Furthermore, the recoveries of tetracycline (70 μM) from BSA (133 μg/mL) and FBS (0.66 ppt) by the APS-modified glass were 98% (RSD = 3.5%, n = 5) and 97% (RSD = 5.7%), respectively. For the MPS-modified glass, recoveries of 95% (RSD = 7.2%) and 89% (RSD = 8.7%) were observed at 67 μg/mL of BSA and 0.33 ppt of FBS, respectively. PMID:27188318

  3. Glass substrates crosslinked with tetracycline-imprinted polymeric silicate and CdTe quantum dots as fluorescent sensors.

    PubMed

    Chao, Mu-Rong; Hu, Chiung-Wen; Chen, Jian-Lian

    2016-06-21

    A fluorescence-based sensor that combines the merits of quantum dots (QDs) and molecularly imprinted polymers (MIPs) was first fabricated on a glass substrate via a sol-gel route. Some of the key performance factors, including silane selection, substrate etching, the reaction times of glass silanization and sol-gel polymerization, and the times and methods used for template stripping and loading, were discussed and determined. After fabricating the sensor on either a 3-aminopropyltriethoxysilane (APS) or a 3-mercaptopropyltriethoxysilane (MPS) modified glass substrate, APS showed a much better performance than MPS as both the capping reagent of QDs and the functional monomer of tetracycline-templated MIPs. The APS-QDs on APS-modified glass had a higher imprinted factor (IF = 5.6), a lower LOD (2.1 μM, 3σ), and a more stable signal (2.8%, n = 10 at 70 μM) than those on the MPS-modified glass (IF = 5.2, LOD = 6.5 μM, stability = 6.2%). Furthermore, the recoveries of tetracycline (70 μM) from BSA (133 μg/mL) and FBS (0.66 ppt) by the APS-modified glass were 98% (RSD = 3.5%, n = 5) and 97% (RSD = 5.7%), respectively. For the MPS-modified glass, recoveries of 95% (RSD = 7.2%) and 89% (RSD = 8.7%) were observed at 67 μg/mL of BSA and 0.33 ppt of FBS, respectively.

  4. 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

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

    PubMed

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

    2012-09-21

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

  6. 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.

  7. 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.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  10. Optical and thermal properties of phosphors based on lead-silicate glass for high-power white LEDs

    NASA Astrophysics Data System (ADS)

    Shvaleva, M. A.; Tuzova, Yu. V.; Romanov, A. E.; Aseev, V. A.; Nikonorov, N. V.; Mynbaev, K. D.; Bugrov, V. E.

    2015-11-01

    A study is reported of the properties of a new phosphor material based on a highly refractive leadsilicate glass and microparticles of yttrium-aluminum garnet doped with cerium ions (YAG: Ce3+). The mass percentage fraction of YAG: Ce3+ microparticles in the material was varied from 50 to 90%. The optical properties of the phosphor were examined, as well as its thermal properties when used as a primary optical material in high-power light-emitting diode (LED) units. The results obtained reveal problems of excess heat removal from an LED structure, which appear on passing from phosphor binders based on silicone elastomers to glasses, and demonstrate that the phosphor developed in the study is promising for obtaining warm white light.

  11. Characterizing the hierarchical structures of bioactive sol-gel silicate glass and hybrid scaffolds for bone regeneration.

    PubMed

    Martin, R A; Yue, S; Hanna, J V; Lee, P D; Newport, R J; Smith, M E; Jones, J R

    2012-03-28

    Bone is the second most widely transplanted tissue after blood. Synthetic alternatives are needed that can reduce the need for transplants and regenerate bone by acting as active temporary templates for bone growth. Bioactive glasses are one of the most promising bone replacement/regeneration materials because they bond to existing bone, are degradable and stimulate new bone growth by the action of their dissolution products on cells. Sol-gel-derived bioactive glasses can be foamed to produce interconnected macropores suitable for tissue ingrowth, particularly cell migration and vascularization and cell penetration. The scaffolds fulfil many of the criteria of an ideal synthetic bone graft, but are not suitable for all bone defect sites because they are brittle. One strategy for improving toughness of the scaffolds without losing their other beneficial properties is to synthesize inorganic/organic hybrids. These hybrids have polymers introduced into the sol-gel process so that the organic and inorganic components interact at the molecular level, providing control over mechanical properties and degradation rates. However, a full understanding of how each feature or property of the glass and hybrid scaffolds affects cellular response is needed to optimize the materials and ensure long-term success and clinical products. This review focuses on the techniques that have been developed for characterizing the hierarchical structures of sol-gel glasses and hybrids, from atomic-scale amorphous networks, through the covalent bonding between components in hybrids and nanoporosity, to quantifying open macroporous networks of the scaffolds. Methods for non-destructive in situ monitoring of degradation and bioactivity mechanisms of the materials are also included.

  12. 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

  13. 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

  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. 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

  16. 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.

  17. 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.

  18. Calcium silicate cement-induced remineralisation of totally demineralised dentine in comparison with glass ionomer cement: tetracycline labelling and two-photon fluorescence microscopy.

    PubMed

    Atmeh, A R; Chong, E Z; Richard, G; Boyde, A; Festy, F; Watson, T F

    2015-02-01

    Two-photon fluorescence microscopy, in combination with tetracycline labelling, was used to observe the remineralising potentials of a calcium silicate-based restorative material (Biodentine(TM) ) and a glass ionomer cement (GIC:​Fuji​IX) on totally demineralised dentine. Forty demineralised dentine discs were stored with either cement in three different solutions: phosphate buffered saline (PBS) with tetracycline, phosphate-free tetracycline, and tetracycline-free PBS. Additional samples of demineralised dentine were stored alone in the first solution. After 8-week storage at 37 °C, dentine samples were imaged using two-photon fluorescence microscopy and Raman spectroscopy. Samples were later embedded in PMMA and polished block surfaces studied by 20 kV BSE imaging in an SEM to study variations in mineral concentration. The highest fluorescence intensity was exhibited by the dentine stored with Biodentine(TM) in the PBS/tetracycline solution. These samples also showed microscopic features of matrix remineralisation including a mineralisation front and intra- and intertubular mineralisation. In the other solutions, dentine exhibited much weaker fluorescence with none of these features detectable. Raman spectra confirmed the formation of calcium phosphate mineral with Raman peaks similar to apatite, while no mineral formation was detected in the dentine stored in cement-free or PBS-free media, or with GIC. It could therefore be concluded that Biodentine(TM) induced calcium phosphate mineral formation within the dentine matrix when stored in phosphate-rich media, which was selectively detectable using the tetracycline labelling.

  19. The oxidation state of tungsten in iron bearing and iron free silicate glasses: Initial results from W L-edge XANES measurements

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

    (XANES) microprobe at the Advanced Photon Source (GeoSoilEnviroCARS), Argonne National Laboratory. A monochromatic X-ray beam from a Si(111) double crystal monochromator was focused onto the sample and the fluorescent X-ray yield was plotted as a function of incident X-ray energy (more detail can be found in Sutton et al., 2002). The oxidation state of tungsten was inferred from the energy of the first peak in the LIII-edge derivative spectrum. WO2, WO3, FeWO4, CaWO4, were used as standards. Results for the CMAS starting materials suggest that only W^{6+} is present from the most oxidized conditions to IW (log fO2 -10.75). At IW-1, W starts to exhibit mixed valence but is still dominated by W^{6+}. At IW-2, W^{4+} becomes more abundant, with the most reduced state observed being equal proportions of W^{4+} and W^{6+}. These preliminary results suggest that W^{6+} may still be present, even below IW-5. At IW-2 and below, metal exsolves from the silicate, complicating the analyses. For ankaramite, only W^{6+} is present down to IW-1, with mixed valence beginning at IW-2, similar behavior to the Fe-free samples. As in the CMAS samples, "the nugget effect" is also observed for the ankaramite glasses below IW-2 and W^{6+} appears to be present below IW-5. Thus, the effect of iron appears to be small, if present at all.

  20. Zero-field signal in the electron paramagnetic resonance spectrum of Mn{sup +2} in silicate glasses

    SciTech Connect

    Rakhimov, Rakhim R.; Jones, David E.

    2000-07-22

    A 9.4-9.8 GHz electron paramagnetic resonance (EPR) study of Mn{sup +2}-doped Na{sub 2}O-CaO-MgO-SiO{sub 2} glasses has revealed a nonresonant microwave magneto-absorption near zero magnetic field in addition to normal paramagnetic absorption due to Mn{sup +2} ions, electron spin S=5/2. The low-field response has an opposite phase relative to paramagnetic signal and is independent of the mutual orientation of the magnetic field of the microwave H{sub 1} and static magnetic field H. In contrast, the paramagnetic signal is different for perpendicular H{sub 1}(perpendicular sign)H and parallel H{sub 1}(parallel sign)H polarization of the microwave field, which is attributed to enhancement of forbidden magnetic dipolar transitions and suppression of the allowed transitions for parallel polarization. The low-field response is described in terms of microwave dielectric losses that derive from the magneto-induced charge migration in the first coordination sphere of Mn{sup +2}. As opposed to the spin-polarized tunneling that was described in ferromagnets between different valence forms of Mn, the observed effect is due to spin-dependent tunneling that occurs in the vicinity of Mn{sup +2} in a diluted paramagnetic system. (c) 2000 American Institute of Physics.

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

    DOEpatents

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

    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).

  2. 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).

  3. Structure and rheological properties in alkali aluminosilicate melts

    NASA Astrophysics Data System (ADS)

    Le Losq, Charles; Neuville, Daniel

    2010-05-01

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

  4. 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

  5. Method of handling radioactive alkali metal waste

    DOEpatents

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

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

  6. 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.

  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. 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

  9. Influence of mixed alkali on the spectral properties of vanadyl ions doped xNa{sub 2}O-(30 - x)K{sub 2}O-60B{sub 2}O{sub 3} glasses-an EPR and optical study

    SciTech Connect

    Sreekanth Chakradhar, R.P. . E-mail: chakra72@physics.iisc.ernet.in; Ramesh, K.P.; Rao, J.L.; Ramakrishna, J.

    2005-06-15

    Electron paramagnetic resonance (EPR) and optical investigations have been performed in the mixed alkali borate xNa{sub 2}O-(30 - x)K{sub 2}O-60B{sub 2}O{sub 3} (5 {<=} x {<=} 25) glasses doped with 10 mol% of vanadyl ions in order to look for the effect of 'mixed alkalis' on the spectral properties of the glasses. The observed EPR spectra have structures for x > 5 mol% which are characteristic of a hyperfine interaction arising from an unpaired electron with the {sup 51}V nucleus and it builds up in intensity as x increases. It is observed that the mixed alkali play a significant role in accommodating the vanadyl ions in these mixed alkali glasses and for x > 5 mol%, shows a well resolved hyperfine structure typical for isolated VO{sup 2+} ions. The spin-Hamiltonian parameters (g and A), the dipolar hyperfine coupling parameter (P) and Fermi contact interaction parameter (k) have been evaluated. It is observed that the spin-Hamiltonian parameters do not vary much with the change in composition. It is observed that with increase of x, an increase occurs in tetragonal distortion for VO{sup 2+}. The number of spins (N) participating in resonance and the paramagnetic susceptibility ({chi}) have been calculated. It is observed that N and {chi} increase with x. The optical bandgap energies evaluated for these glasses slightly increase with x and reach a maximum around x = 20 and thereafter decrease showing the mixed alkali effect. Optical band gap energies obtained in the present work vary from 2.73 to 3.10 eV for both the direct and indirect transitions. The physical parameters of the glasses are also determined with respect to the composition.

  10. 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+).

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. Raman spectra of Martian glass analogues: a tool to approximate their chemical composition

    NASA Astrophysics Data System (ADS)

    Di Genova, Danilo; Kolzenburg, Stephan; Vona, Alessandro; Chevrel, Magdalena O.; Hess, Kai-Uwe; Neuville, Daniel R.; Ertel-Ingrisch, Werner; Romano, Claudia; Dingwell, Donald B.

    2016-04-01

    We present a study on the systematic changes of Raman spectra of a series of glasses as a function of their chemistry. These glass compositions are considered as analogues for rock materials identified on Mars. We performed a diffusion experiment between an iron-rich basaltic and a rhyolitic melt under reducing conditions to produce a wide range of intermediate chemical compositions. We then systematically acquired Raman spectra of the intermediate composition glasses across the diffusion interface and correlate them with the corresponding chemical compositions derived by electron microprobe analysis. Using a linear mixing model for the spectral evolution as a function of chemistry, we fitted a Raman parameter to each spectrum to estimate the chemical composition of each glass. The Raman model was verified using external natural and synthetic samples. This study: 1) expands the Raman database of silicate glasses including alkali and iron-rich compositions as expected to be found on Mars; and 2) contributes to develop Raman spectroscopy as a quantitative tool in geological and planetary science to estimate the chemistry of glasses on a microscopic level. Moreover, as Raman spectrometers have been developed for two forthcoming Mars missions [ExoMars program (2016-2018) and Mars 2020], with the benefit of this calibration, Raman spectroscopy will allow rapid, in-situ and remotely controlled identification and investigation of silicate glasses on future extraterrestrial rover missions.

  16. Cation Diffusivity and the Mixed Network Former Effect in Borosilicate Glasses.

    PubMed

    Smedskjaer, Morten M; Mauro, John C; Yue, Yuanzheng

    2015-06-11

    Understanding the structural origins of cationic diffusion processes in silicate glasses is important for high-tech applications of silicate glasses. For glasses with more than one network former, transport properties such as diffusivity are often nonlinear functions of the particular distribution of these network formers, a phenomenon known as the mixed network former effect. Here, we investigate the sodium-potassium interdiffusion (D̅Na-K) and the calcium inward diffusion (DCa) in soda lime borosilicate glasses with varying silica/borate ratio but constant modifier content. Indeed, the structural organization of borosilicate glasses results in a pronounced nonlinear composition dependence of D̅Na-K and DCa (i.e., the mixed network former effect). Initial addition of B2O3 to the glass system results in a significant decrease in both diffusivities, whereas the change in diffusivity per mole of added B2O3 decreases with increasing B2O3 concentration. Besides the influences of water content and atomic packing degree, we find that 99% of the composition dependence of log D̅Na-K can be ascribed to the change in concentration of tetrahedral boron groups. This indicates that the formation of BO4/2 groups slows down diffusion processes of alkali and alkaline earth ions. Therefore, the mixed network former effect of the studied glass series is linked with the change of the concentration of tetrahedral boron groups, which is caused by the interactions between the different types of network formers.

  17. An integrated experimental-modeling approach to study the acid leaching behavior of lead from sub-micrometer lead silicate glass particles.

    PubMed

    van Elteren, Johannes T; Grilc, Miha; Beeston, Michael P; Reig, Milagros Santacatalina; Grgić, Irena

    2013-11-15

    This work focuses on the development of a procedure to study the mechanism of leaching of lead from sub-micrometer lead glass particles using 0.3 mo ll(-1) HNO3 as a leachant. Glass particles with an effective size distribution range from 0.05 to 1.4 μm were generated by laser ablation (213 nm Nd:YAG laser) and collected on an inline 0.2 μm syringe filter. Subsequently, the glass particles on the filter were subjected to online leaching and continuous monitoring of lead (Pb-208) in the leachate by quadrupole ICP-MS. The lead leaching profile, aided by the particle size distribution information from cascade impaction, was numerically fitted to a mathematical model based on the glass intraparticle diffusion, liquid film distribution and thermodynamic glass-leachant distribution equilibrium. The findings of the modeling show that the rate-limiting step of leaching is the migration of lead from the core to the surface of the glass particle by an ion-exchange mechanism, governed by the apparent intraparticle lead diffusivity in glass which was calculated to be 3.1 × 10(-18) m(2)s(-1). Lead leaching is illustrated in the form of graphs and animations of intraparticle lead release (in time and intraparticle position) from particles with sizes of 0.1 and 0.3 μm.

  18. The effect of composition on the viscosity, crystallization and dissolution of simple borate glasses and compositional design of borate based bioactive glasses

    NASA Astrophysics Data System (ADS)

    Goetschius, Kathryn Lynn

    Borate glasses have recently been developed for a variety of medical applications, but much less is known about their structures and properties than more common silicate glasses. Melt properties and crystallization tendency for compositions in the Na2O-CaO-B2O3 system were characterized using differential thermal analysis and viscosity measurements. Characteristic viscosity (isokom) temperatures varied with the ratio between the modifier content (Na2O+CaO) and B2O3, particularly at lower temperatures, consistent with the changes in the relative concentrations of tetrahedral borons in the glass structure. Similar glasses were used to study dissolution processes in water. These alkali-alkaline earth glasses dissolve congruently and follow linear dissolution kinetics. The dissolution rates were dependent on the glass structure, with slower rates associated with greater fractions of four-coordinated boron. For glasses with a fixed alkaline earth identity, the dissolution rates increased in the order Liglasses with a constant alkali identity, the dissolution rates increased in the order Caalkali and alkaline earth oxides on dissolution rates are discussed in terms of competing effects of four-coordinated boron and the field strength of the modifying cation. Finally, a seven component (Na2O, K2O, MgO, CaO, B2O3, SiO2, and P2O5) mixture model design was used to predict composition-property relationships to optimize the properties of new borate-based bioactive compositions for specific applications. Melt viscosity, thermal expansion coefficient, liquidus temperature and crystallization tendency were determined, as were dissolution rates in simulated body fluid (SBF).

  19. 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.

  20. The Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses: Results from W L-Edge XANES Measurements

    SciTech Connect

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

    2007-03-06

    Knowledge of the oxidation state of W over a wide range of fO{sub 2} is critical to understanding the oxidation state of the mantle and core formation processes. W occurs as W6+ above {approx}IW-1. The transition between W{sup 4+} and W{sup 6+} occurs just below IW-1. 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 (Fig. 1) are inconsistent on whether W occurs as W4+ or W{sup 6+}. It is assumed that W{sup 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 fO{sub 2} 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 fO{sub 2} most relevant to core formation, around IW-2.

  1. Atomic-scale models of early-stage alkali depletion and SiO2-rich gel formation in bioactive glasses.

    PubMed

    Tilocca, Antonio

    2015-01-28

    Molecular dynamics simulations of Na(+)/H(+)-exchanged 45S5 Bioglass® models reveal that a large fraction of the hydroxyl groups introduced into the proton-exchanged, hydrated glass structure do not initially form covalent bonds with Si and P network formers but remain free and stabilised by the modifier metal cations, whereas substantial Si-OH and P-OH bonding is observed only at higher Na(+)/H(+) exchange levels. The strong affinity between free OH groups and modifier cations in the highly fragmented 45S5 glass structure appears to represent the main driving force for this effect. This suggests an alternative direct route for the formation of a repolymerised silica-rich gel in the early stages of the bioactive mechanism, not considered before, which does not require sequential repeated breakings of Si-O-Si bonds and silanol condensations.

  2. 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)

  3. 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.

  4. 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.

  5. 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.

  6. High temperature alkali corrosion of ceramics in coal gas

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-02-24

    The high temperature alkali corrosion kinetics of SiC have been systematically investigated from 950 to 1100[degrees]C at 0.63 vol % alkali vapor concentration. The corrosion rate in the presence of alkaliis approximately 10[sup 4] to 10[sup 5] times faster than the oxidation rate of SiC in air. The activation energy associated with the alkali corrosion is 406 kJ/mol, indicating a highly temperature-dependent reaction rate. The rate-controlling step of the overall reaction is likely to be the dissolution of silica in the sodium silicate liquid, based on the oxygen diffusivity data.

  7. 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

  8. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates.

    PubMed

    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 (29)Si-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

  9. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates.

    PubMed

    Pustovgar, Elizaveta; Sangodkar, Rahul P; Andreev, Andrey S; Palacios, Marta; Chmelka, Bradley F; Flatt, Robert J; d'Espinose de Lacaillerie, Jean-Baptiste

    2016-03-24

    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 (29)Si-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. 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.

  12. High temperature alkali corrosion of ceramics in coal gas

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-05-27

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  13. High temperature alkali corrosion of ceramics in coal gas

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1991-11-30

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this program is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  14. High temperature alkali corrosion of ceramics in coal gas

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-08-29

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  15. 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.

  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. The speciation of carbon dioxide in silicate melts

    NASA Astrophysics Data System (ADS)

    Konschak, Alexander; Keppler, Hans

    2014-05-01

    The speciation of CO2 in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO2 into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO2 re-appeared. Infrared extinction coefficients of both carbonate and molecular CO2 decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/ t = 0.98) and basaltic andesite (NBO/ t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/ t = 0.09) and phonolite melts (NBO/ t = 0.14), the equilibrium CO2 + O2- = CO3 2- in the melt shifts toward CO2 with increasing temperature, with ln K = -4.57 (±1.68) + 5.05 (±1.44) 103 T -1 for dacite melt (Δ H = -42 kJ mol-1) and ln K = -6.13 (±2.41) + 7.82 (±2.41) 103 T -1 for phonolite melt (Δ H = -65 kJ mol-1), where K is the molar ratio of carbonate over molecular CO2 and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that Δ S and Δ H are linear functions of NBO/ t. Based on this relationship, a general model for CO2 speciation in silicate melts is developed, with ln K = a + b/ T, where T is temperature in Kelvin and a = -2.69 - 21.38 (NBO/ t), b = 1,480 + 38,810 (NBO/ t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO2, and therefore, the diffusion coefficient of CO2 is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO2 solubility and speciation on melt composition, in accordance with available solubility data.

  18. Collisional energy deposition threshold for extended damage depths in ion-implanted silicates

    SciTech Connect

    Arnold, G.W.; Battaglin, G.; Boscolo-Boscoletto, A.; Caccavalle, F.; De Marchi, G.; Mazzoldi, P.; Miotello, A.

    1991-12-31

    Many properties of implanted fused silica (e.g., surface stress, hardness) exhibit maximum implantation-induced changes for collisional energy deposition values of {approximately}10{sup 20} keV/cm{sup 3}. We have observed a second critical energy deposition threshold value of about 10{sup 22} keV/cm{sup 3} in stress and hardness measurements as well as in many other experiments on silicate glasses (leaching, alkali depletion, etching rate, gaseous implant redistribution). The latter show evidence for damage depths exceeding TRIM ranges by about a factor of 2. For crystalline quartz, a similar threshold value has been found for extended damage depths (greater than TRIM) for 250 kev ions (H-Au) as measured by RBS and interference fringes. This phenomenon at high damage deposition energy may involve the large stress gradients between damaged and undamaged regions and the much increased diffusion coefficient for defect transport. 13 refs., 6 figs.

  19. Collisional energy deposition threshold for extended damage depths in ion-implanted silicates

    SciTech Connect

    Arnold, G.W. ); Battaglin, G. ); Boscolo-Boscoletto, A. ); Caccavalle, F.; De Marchi, G.; Mazzoldi, P. ); Miotello, A. (Consorzio INFM, Dipartiment

    1991-01-01

    Many properties of implanted fused silica (e.g., surface stress, hardness) exhibit maximum implantation-induced changes for collisional energy deposition values of {approximately}10{sup 20} keV/cm{sup 3}. We have observed a second critical energy deposition threshold value of about 10{sup 22} keV/cm{sup 3} in stress and hardness measurements as well as in many other experiments on silicate glasses (leaching, alkali depletion, etching rate, gaseous implant redistribution). The latter show evidence for damage depths exceeding TRIM ranges by about a factor of 2. For crystalline quartz, a similar threshold value has been found for extended damage depths (greater than TRIM) for 250 kev ions (H-Au) as measured by RBS and interference fringes. This phenomenon at high damage deposition energy may involve the large stress gradients between damaged and undamaged regions and the much increased diffusion coefficient for defect transport. 13 refs., 6 figs.

  20. 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. PMID:19929965

  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. Influence of Ga{sup 3+} ions on spectroscopic and dielectric features of multi component lithium lead boro bismuth silicate glasses doped with manganese ions

    SciTech Connect

    Ramesh Babu, P.; Vijay, R.; Nageswara Rao, P.; Veeraiah, N.; Krishna Rao, D.

    2013-11-15

    Graphical abstract: The plots between ε″(ω)ω vs. ε′(ω) and ε″(ω)/ω vs. ε′(ω) yield straight lines with slope 1/τ and τ, respectively. Considerable deviation from the straight line is observed in the high frequency region. Such deviation suggests spreading of relaxation times and this is attributed to the presence of multiple type of dipoles in the glass matrix. Variation of the parameters ωε″(ω) and ε″(ω)/ω with ε′(ω) of glass Li{sub 2}O–PbO–B{sub 2}O{sub 3}–SiO{sub 2}–Bi{sub 2}O{sub 3}–MnO multi-component glasses mixed with 2.0 mol% of Ga{sub 2}O{sub 3} measured at 373 K. - Highlights: • A series of Li{sub 2}O–PbO–B{sub 2}O{sub 3}–SiO{sub 2}–Bi{sub 2}O{sub 3}–MnO:Ga{sub 2}O{sub 3} glasses have been synthesized. • A variety of spectroscopic and dielectric properties have been investigated. • Analysis of the results indicated that glasses with below 3.0 mol% Ga{sub 2}O{sub 3} are good conducting materials. - Abstract: Multi-component glasses of the chemical composition 19.5Li{sub 2}O–20PbO–20B{sub 2}O{sub 3}–30SiO–(10 − x)Bi{sub 2}O{sub 3}–0.5MnO:xGa{sub 2}O{sub 3} with 0 ≤ x ≤ 5.0 have been synthesized. Spectroscopic (optical absorption, IR, Raman and ESR) and dielectric properties were investigated. Optical absorption and ESR spectral studies have indicated that managanese ions do exist in Mn{sup 3+} state in addition to Mn{sup 2+} state in the samples containing low concentration of Ga{sub 2}O{sub 3}. The IR and Raman studies indicated increasing degree of disorder in the glass network with the concentration of Ga{sub 2}O{sub 3} up to 3.0 mol%. The dielectric constant, loss and ac conductivity are observed to increase with the concentration of Ga{sub 2}O{sub 3} up to 3.0 mol%. The quantitative analysis of the results of dielectric properties has indicated an increase in the insulating strength of the glasses as the concentration of Ga{sub 2}O{sub 3} is raised beyond 3.0 mol%. This has

  3. DFT modeling of 45S5 and 77S soda-lime phospho-silicate glass surfaces: clues on different bioactivity mechanism.

    PubMed

    Berardo, Enrico; Pedone, Alfonso; Ugliengo, Piero; Corno, Marta

    2013-05-14

    The reactivity of bioglasses, which is related to the dissolution of cations and orthosilicate groups in the physiological fluid, strongly depends on the key structural features present at the glass surfaces. On the basis of the composition and the synthetic routes employed to make the glass, surfaces with very different characteristics and thus presenting different mechanisms of dissolution can be observed. In this paper, the surface structures of two very different bioglass compositions, namely 45S5 (46.1 SiO2, 24.4 Na2O, 26.9 CaO, and 2.6 P2O5 mol %) and 77S (80.0 SiO2, 16.0 CaO, and 4.0 P2O5 mol %), have been investigated by means of periodic DFT calculations based on a PBE functional and localized Gaussian basis set as encoded in the CRYSTAL code. Our calculations show that the two glass surfaces differ by the relative amount of key structural sites such as NBOs, exposed ions, orthosilicate units, and small rings. We have demonstrated how the number of these sites affects the surface stability and reactivity (bioactivity).

  4. DFT modeling of 45S5 and 77S soda-lime phospho-silicate glass surfaces: clues on different bioactivity mechanism.

    PubMed

    Berardo, Enrico; Pedone, Alfonso; Ugliengo, Piero; Corno, Marta

    2013-05-14

    The reactivity of bioglasses, which is related to the dissolution of cations and orthosilicate groups in the physiological fluid, strongly depends on the key structural features present at the glass surfaces. On the basis of the composition and the synthetic routes employed to make the glass, surfaces with very different characteristics and thus presenting different mechanisms of dissolution can be observed. In this paper, the surface structures of two very different bioglass compositions, namely 45S5 (46.1 SiO2, 24.4 Na2O, 26.9 CaO, and 2.6 P2O5 mol %) and 77S (80.0 SiO2, 16.0 CaO, and 4.0 P2O5 mol %), have been investigated by means of periodic DFT calculations based on a PBE functional and localized Gaussian basis set as encoded in the CRYSTAL code. Our calculations show that the two glass surfaces differ by the relative amount of key structural sites such as NBOs, exposed ions, orthosilicate units, and small rings. We have demonstrated how the number of these sites affects the surface stability and reactivity (bioactivity). PMID:23594027

  5. 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

  6. 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.

  7. 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.

  8. 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

  9. Low-loss planar and stripe waveguides in Nd{sup 3+}-doped silicate glass produced by oxygen-ion implantation

    SciTech Connect

    Wang, Lei; Chen, Feng; Wang, Xue-Lin; Wang, Ke-Ming; Jiao, Yang; Wang, Liang-Ling; Li, Xi-Shan; Lu, Qing-Ming; Ma, Hong-Ji; Nie, Rui

    2007-03-01

    We report on the fabrication and characterization of low-loss planar and stripe waveguides in a Nd{sup 3+}-doped glass by 6 MeV oxygen-ion implantation at a dose of 1x10{sup 15} ions/cm{sup 2}. The dark mode spectroscopy of the planar waveguide was measured using a prism coupling arrangement. The refractive index profile of the planar waveguide was reconstructed from a code based on the reflectivity calculation method. The results indicate that a refractive index enhanced region as well as an optical barrier have been created after the ion beam processing. The near-field mode profiles of the stripe waveguide were obtained by an end-fire coupling arrangement, by which three quasitransverse electric modes were observed. After annealing, the propagation losses of the planar and stripe waveguides were reduced to be {approx}0.5 and {approx}1.8 dB/cm, respectively.

  10. 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.

  11. 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.

  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. Magnesium silicates adsorbents of organic compounds

    NASA Astrophysics Data System (ADS)

    Ciesielczyk, Filip; Krysztafkiewicz, Andrzej; Jesionowski, Teofil

    2007-08-01

    Studies were presented on production of highly dispersed magnesium silicate at a pilote scale. The process of silicate adsorbent production involved precipitation reaction using water glass (sodium metasilicate) solution and appropriate magnesium salt, preceded by an appropriate optimization stage. Samples of best physicochemical parameters were in addition modified (in order to introduce to silica surface of several functional groups) using the dry technique and various amounts of 3-isocyanatepropyltrimethoxysilane, 3-thiocyanatepropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane. The so prepared samples were subjected to a comprehensive physicochemical analysis. At the terminal stage of studies attempts were made to adsorb phenol from its aqueous solutions on the surface of unmodified and modified magnesium silicates. Particle size distributions were determined using the ZetaSizer Nano ZS apparatus. In order to define adsorptive properties of studied magnesium silicates isotherms of nitrogen adsorption/desorption on their surfaces were established. Efficiency of phenol adsorption was tested employing analysis of post-adsorption solution.

  15. Alkali-activated cementitious materials: Mechanisms, microstructure and properties

    NASA Astrophysics Data System (ADS)

    Jiang, Weimin

    The goal of this study was to examine the activation reaction, microstructure, properties, identify the mechanisms of activation, and achieve an enhanced understanding of activation processes occurring during the synthesis of alkali activated cementitious materials (AAC). The discussions classify the following categories. (1) alkali activated slag cement; (2) alkali activated portland-slag cement; (3) alkali activated fly ash-slag cement; (4) alkali activated pozzolana-lime cement; (5) alkali activated pozzolana cement. The activators involved are NaOH, KOH; Nasb2SOsb4;\\ Nasb2COsb3;\\ CaSOsb4, and soluble silicate of sodium and potassium. The effect of alkali activation on the microstructure of these materials were analyzed at the micro-nanometer scale by SEM, EDS, ESEM, and TEM. Also sp{29}Si and sp{27}Al MAS-NMR, IR, Raman, TGA, and DTA were performed to characterize the phase in these systems. Slag, fly ash, silica fume, as well as blended cements containing mixtures of these and other components were characterized. A set of ordinary portland cement paste samples served as a control. This study confirmed that AAC materials have great potential because they could generate very early high strength, greater durability and high performance. Among the benefits to be derived from this research is a better understanding of the factors that control concrete properties when using AAC materials, and by controlling the chemistry and processing to produce desired microstructures and properties, as well as their durability.

  16. Nanophase glass ceramics for capacitive energy storage

    NASA Astrophysics Data System (ADS)

    Rangarajan, Badri

    Glass ceramics are candidate dielectric materials for high energy storage capacitors. Since energy density depends primarily on dielectric permittivity and breakdown strength, glass ceramics with interconnected nano-crystalline particles and low porosity, which leads to high breakdown strength, are expected to have high energy density values. Three glass ceramic systems were investigated. Barium/lead sodium niobate glass ceramics, designated as PNNS (PbO-Na 2O-Nb2O5-SiO2) and BNNS (BaONa 2O- Nb2O5-SiO2), and barium titanate silicate glass ceramic, designated as BTS (BaOTiO2-SiO2), belonging to medium (epsilonr ~ 400-700) and low (epsilon r ~ 20) permittivity regimes, respectively, were fabricated by roller quenching and controlled crystallization. The overall properties of the glass ceramics were controlled by connectivity and volume fraction of crystallites. PNNS and BNNS developed perovskite and tungsten-bronze phases during crystallization with permittivity values between 400 and 700. Microstructural analysis of PNNS glass ceramic revealed grain sizes of the order of 50 nm. The calculated breakdown strengths were ~0.7 and ~075 MV/cm for PNNS and BNNS respectively. The resulting energy densities at breakdown were ~4.5 and ~6.5 J/cm3 for PNNS and BNNS respectively. However, the disadvantages, such as difficult glass formability, less control over crystallization due to multiphase formation and low dielectric breakdown strength values due to high dielectric contrast between the glass and crystal phases, associated with PNNS and BNNS glass ceramics served as the motivating factor for exploring BTS glass ceramic. The major advantage of studying BTS glass ceramic over the other systems is that a single crystalline phase, fresnoite (Ba2TiSi2O 8), grows from the quenched glass and properties can be explored over the whole spectrum ranging from fully amorphous to fully crystalline. Crystallization kinetics of the BTS glass is explored to control the relative volume

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. Effects of radiation exposure on glass alteration in a steam environment

    SciTech Connect

    Wronkiewicz, D.J.; Bates, J.K.; Tani, B.S.; Wang, L.M.

    1992-12-31

    Several Savannah River Plant (SRL) glass compositions were reacted in steam at temperatures of 150 to 200{degrees}C. Half of the tests utilized actinide-doped monoliths and were exposed to an external ionizing gamma source, while the remainder were doped only with U and reacted without gamma exposure. All glass samples readily reacted to form secondary mineral phases within the first week of testing. An in situ layer of smectite initially developed on nonirradiated SRL 202 glass test samples. After 21 days, a thin layer of illite was precipitated from solution onto the smectite layer. A number of alteration products including zeolite, Casilicate, and alkali or alkaline earth uranyl silicate phases were also distributed over most sample surfaces. In the irradiated SRL 202 glass tests, up to three layers enveloped rounded, and sometimes fractured, glass cores. After 35 to 56 days these remnant cores were replaced by a mottled or banded Fe- and Si-rich material. The formation of some secondary mineral phases also has been accelerated in the irradiated tests, and in some instances, the irradiated environment may have led to the precipitation of a different suite of minerals. The alteration layer(s) developed at rates of 2.3 and 32 {mu}m/day for the nonirradiated and irradiated SRL 202 glasses, respectively, indicating that layer development is accelerated by a factor of {approximately} 10 to 15X due to radiation exposure under the test conditions.

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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)

  7. Silicate volcanism on Io

    NASA Astrophysics Data System (ADS)

    Carr, M. H.

    1986-03-01

    This paper is mainly concerned with the nature of volcanic eruptions on Io, taking into account questions regarding the presence of silicates or sulfur as principal component. Attention is given to the generation of silicate magma, the viscous dissipation in the melt zone, thermal anomalies at eruption sites, and Ionian volcanism. According to the information available about Io, it appears that its volcanism and hence its surface materials are dominantly silicic. Several percent of volatile materials such as sulfur, but also including sodium- and potassium-rich materials, may also be present. The volatile materials at the surface are continually vaporized and melted as a result of the high rates of silicate volcanism.

  8. 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.

  9. 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.

  10. 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

  11. 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.; 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 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

  12. 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.

  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. 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.

  15. Alkali metal ion battery with bimetallic electrode

    SciTech Connect

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

    2015-04-07

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

  16. 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.

  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. 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)

  19. 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.

  20. DISORDERED SILICATES IN SPACE: A STUDY OF LABORATORY SPECTRA OF 'AMORPHOUS' SILICATES

    SciTech Connect

    Speck, Angela K.; Whittington, Alan G.; Hofmeister, Anne M.

    2011-10-20

    We present a laboratory study of silicate glasses of astrophysically relevant compositions including olivines, pyroxenes, and melilites. With emphasis on the classic Si-O stretching feature near 10 {mu}m, we compare infrared spectra of our new samples with laboratory spectra on ostensibly similar compositions, and also with synthetic silicate spectral data commonly used in dust modeling. Several different factors affect spectral features including sample chemistry (e.g., polymerization, Mg/Fe ratio, oxidation state, and Al-content) whereas different sample preparation techniques lead to variations in porosity, density, and water content. The convolution of chemical and physical effects makes it difficult to attribute changes in spectral parameters to any given variable. It is important that detailed chemical and structural characterization be provided along with laboratory spectra. In addition to composition and density, we measured the glass transition temperatures for the samples which place upper limits on the formation and/or processing temperatures of these solids in space. Popular synthetically generated optical functions do not have spectral features that match any of our glass samples. However, the {approx}10 {mu}m feature generated by the synthetic data rarely exactly matches the shape and peak position of astronomically observed silicate features. Our comparison with the synthetic spectra allows astronomers to determine likely candidates among our glass samples for matching astronomical observations.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  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. 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.

  4. 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

  5. P- T phase relations of silicic, alkaline, aluminous liquids: new results and applications to mantle melting and metasomatism

    NASA Astrophysics Data System (ADS)

    Draper, David S.; Green, Trevor H.

    1999-07-01

    We report new experimental results obtained under nominally anhydrous conditions at 1.0-1.5 GPa on a synthetic melt whose composition is typical of extreme-composition xenolith glasses. These results demonstrate that part of this extreme compositional range is in equilibrium with a lherzolitic assemblage (olivine, orthopyroxene, and clinopyroxene on the liquidus), extending our earlier findings [D.S. Draper, T.H. Green P- T phase relations of silicic, alkaline, aluminous mantle-xenolith glasses under anhydrous and C-O-H fluid-saturated conditions, J. Petrol. 38 (1997) 1187-1224] showing saturation with harzburgite minerals (olivine and orthopyroxene on the liquidus). The new results strengthen the view that such liquids can readily coexist with upper mantle rocks. Our results also bear on the current debate regarding the nature of low-degree mantle melts between proponents of the diamond-aggregate technique [who argue for comparatively silica- and alkali-rich low-degree melts; e.g., M.B. Baker, M.M. Hirschmann, M.S. Ghiorso, E.M. Stolper, Compositions of near-solidus peridotite melts from experiments and thermodynamic calculations, Nature 375 (1995) 308-311; M.B. Baker, M.M. Hirschmann, L.E. Wasylenki, E.M. Stolper, M.S. Ghiorso, Quest for low-degree mantle melts, Nature 381 (1996) 286] and those favoring the sandwich technique [who question the value of the diamond-aggregate work and argue that near-solidus melts must be nepheline- and olivine-normative; T.J. Falloon, D.H. Green, H.St.C. O'Neill, C.G. Ballhaus, Quest for low-degree mantle melts, Nature 381 (1996) 285; T.J. Falloon, D.H. Green, H.St.C. O'Neill, W.O. Hibberson, Experimental tests of low degree peridotite partial melt compositions: implications for the nature of anhydrous near-solidus peridotite melts at 1 GPa, Earth Planet. Sci. Lett. 152 (1997) 149-162]. Our results support aspects of both views. The sandwich-technique view is supported, for example, because all our liquids coexisting with mantle

  6. Silicate-carbonate-salt liquid immiscibility and origin of the sodalite-haüyne rocks: study of melt inclusions in olivine foidite from Vulture volcano, S. Italy

    NASA Astrophysics Data System (ADS)

    Panina, Liya I.; Stoppa, Francesco

    2009-12-01

    Melt inclusions in clinopyroxenes of olivine foidite bombs from Serra di Constantinopoli pyroclastic flows of the Vulture volcano (Southern Italy) were studied in detail. The rocks contain abundant zoned phenocrysts and xenocrysts of clinopyroxene, scarce grains of olivine, leucite, haüyne, glass with microlites of plagioclase and K-feldspar. The composition of clinopyroxene in xenocrysts (Cpx I), cores (Cpx II), and in rims (Cpx III) of phenocrysts differs in the content of Mg, Fe, Ti, and Al. All clinopyroxenes contain two types of primary inclusion-pure silicate and of silicate-carbonate-salt composition. This fact suggests that the phenomena of silicate-carbonate immiscibility took place prior to crystallization of clinopyroxene. Homogenization of pure silicate inclusions proceeded at 1 225 - 1 190°C. The composition of conserved melts corresponded to that of olivine foidite in Cpx I, to tephrite-phonolite in Cpx II, and phonolite-nepheline trachyte in Cpx III. The amount of water in them was no more than 0.9 wt.%. Silicate-carbonate inclusions decrepitated on heating. Salt globules contained salts of alkali-sulphate, alkali-carbonate, and Ca-carbonate composition somewhat enriched in Ba and Sr. This composition is typical of carbonatite melts when decomposed into immiscible fractions. The formation of sodalite-haüyne rocks from Vulture is related to the presence of carbonate-salt melts in magma chamber. The melts conserved in clinopyroxenes were enriched in incompatible elements, especially in Cpx III. High ratios of La, Nb, and Ta in melts on crystallization of Cpx I and Cpx II suggest the influence of a carbonatite melt as carbonatites have extremely high La/Nb and Nb/Ta and this is confirmed by the appearance of carbonatite melts in magma chamber. Some anomalies in the concentrations and relatives values of Eu and especially Ga seems typical of Italian carbonatite related melts. The mantle source for initial melts was, most likely, rather uniform

  7. Decalcification resistance of alkali-activated slag.

    PubMed

    Komljenović, Miroslav M; Baščarević, Zvezdana; Marjanović, Nataša; Nikolić, Violeta

    2012-09-30

    This paper analyses the effects of decalcification in concentrated 6M NH(4)NO(3) solution on mechanical and microstructural properties of alkali-activated slag (AAS). Portland-slag cement (CEM II/A-S 42.5 N) was used as a benchmark material. Decalcification process led to a decrease in strength, both in AAS and in CEM II, and this effect was more pronounced in CEM II. The decrease in strength was explicitly related to the decrease in Ca/Si atomic ratio of C-S-H gel. A very low ratio of Ca/Si ~0.3 in AAS was the consequence of coexistence of C-S-H(I) gel and silica gel. During decalcification of AAS almost complete leaching of sodium and tetrahedral aluminum from C-S-H(I) gel also took place. AAS showed significantly higher resistance to decalcification in relation to the benchmark CEM II due to the absence of portlandite, high level of polymerization of silicate chains, low level of aluminum for silicon substitution in the structure of C-S-H(I), and the formation of protective layer of polymerized silica gel during decalcification process. In stabilization/solidification processes alkali-activated slag represents a more promising solution than Portland-slag cement due to significantly higher resistance to decalcification. PMID:22818592

  8. Noble gas diffusion in silicate liquids

    NASA Astrophysics Data System (ADS)

    Amalberti, J.; Burnard, P.; Laporte, D.

    2013-12-01

    Fractionated noble gas relative abundances (Ne/Ar, Kr/Ar and Xe/Ar) and isotopic compositions (40Ar/36Ar, 38Ar/36Ar, 20Ne/22Ne, 21Ne/22Ne) are found in volcanic materials, notably in pumices (1-3). This has generally been interpreted as fractionation resulting from diffusion. However, there is some disagreement as to whether this fractionation occurs during high temperature magmatic processes (3) or due to diffusion of air into solidified pyroclastic deposits (2). We show that differences in relative noble gas diffusivities (e.g. D4He vs D40Ar, where D is the diffusivity) and isotopic diffusivities (e.g. D40Ar vs D36Ar) reduce at high temperatures (Fig). These results predict minimal fractionation of noble gases during magmatic processes. However, it is important to note that these diffusivities were measured in silicate glasses; the relative noble diffusivities in silicate liquids are poorly known. We have developed a new experimental protocol which will to determine the diffusivities of the noble gases and their isotopes in the liquid state. A graphite crucible c. 0.3 mm diameter and c. 20mm deep is filled with powdered glass of the desired composition, heated to 1773 K for 15 minutes and quenched to form a glass cylinder within the crucible. The crucible is then placed in a low pressure (1 bar) controlled atmosphere vertical furnace and heated at high temperatures (1673-1773K) for 2 hours in a pure N2 atmosphere. At this point noble gases (He and Ar) are introduced into the furnace and allowed to diffuse into the cylinder of liquid for durations of between 30 and 90. After quenching, the glass cylinder, preserving its' diffusion profile, is sawed into c. 1mm thick discs which are measured by conventional noble gas mass spectrometry for noble gas abundances (He, Ar) and isotopes (40,38,36Ar). The results will be presented at the conference. References 1 Kaneoka, I. Earth Planet Sci Letts 48, 284-292 (1980). 2 Pinti, D. L., Wada, N. & Matsuda, J. J. Volcan

  9. 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.

  10. 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.

  11. 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,…

  12. 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

  13. 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.

  14. 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.

  15. Leaching behavior of glass ceramic nuclear waste forms

    NASA Astrophysics Data System (ADS)

    Lokken, R. O.

    1981-11-01

    Glass ceramic waste forms were investigated as alternatives to borosilicate glasses for the immobilization of high-level radioactive waste. Three glass ceramic systems were investigated, including basalt, celsian, and fresnoite, each containing 20 wt percent simulated high-level waste calcine. Static leach tests were performed on seven glass ceramic materials and one parent glass (before recrystallization). Samples were leached at 90 C for 3 to 28 days in deionized water and silicate water. The results, expressed in normalized elemental mass loss, show comparable releases from celsian and fresnoite glass ceramics. Basalt glass ceramics demonstrated the lowest normalized elemental losses with a nominal release less than 2 grams per square meter when leached in polypropylene containers. The releases from basalt glass ceramics when leached in silicate water were nearly identical with those in deionized water. The overall leachability of celsian and fresnoite glass ceramics was improved when silicate water was used as the leachant.

  16. Volatile-rich silicate melts from Oldoinyo Lengai volcano (Tanzania): Implications for carbonatite genesis and eruptive behavior

    NASA Astrophysics Data System (ADS)

    de Moor, J. Maarten; Fischer, Tobias P.; King, Penelope L.; Botcharnikov, Roman E.; Hervig, Richard L.; Hilton, David R.; Barry, Peter H.; Mangasini, Frederick; Ramirez, Carlos

    2013-01-01

    This study presents volatile, trace, and major element compositions of silicate glasses (nepheline-hosted melt inclusions and matrix glass) from the 2007-2008 explosive eruption at Oldoinyo Lengai volcano, Tanzania. The bulk compositions of the heterogeneous ash erupted in 2007-2008 are consistent with physical mixing between juvenile nephelinite magma and natrocarbonatite emplaced during the preceding ˜25 years of effusive carbonatite eruption. The melt inclusions and matrix glasses span a wide range of silica-undersaturated compositions, from ˜46 wt% SiO2 and (Na+K)/Al˜3 in the least evolved melt inclusions to 38 wt% SiO2 and (Na+K)/Al up to 12 in the matrix glass. The depletion in SiO2 between melt inclusions and matrix glass is accompanied by strong enrichment in all of the incompatible trace elements measured (Ba, Nb, La, Ce, Sr, Zr, Y), which is consistent with fractional crystallization of a bulk mineral assemblage with SiO2 higher than that of the melt inclusions but inconsistent with silicate melt evolution by assimilation of carbonatite. The melt inclusions are volatile-rich with 2.7 wt% to 8.7 wt% CO2 and 0.7 wt% to 10.1 wt% H2O, indicating that Oldoinyo Lengai is a hydrous system. This is contrary to the long-held assumption that Oldoinyo Lengai is relatively anhydrous, which is based on the observation that natrocarbonatite lavas are water-poor. We argue that natrocarbonatites are derived from hydrous carbonate liquid that degas H2O at low pressure. The silicate glass data show that H2O concentration is negatively correlated with incompatible element enrichment, which we attribute to crystallization of the melt in response to decompression degassing of H2O. The eruptive cycle at Oldoinyo Lengai reflects changes in bulk silicate magma viscosity due to extensive H2O-driven crystallization and explosive eruptions occur when volatiles (i.e. H2O>CO2 gas, and carbonate liquid) cannot separate from the crystal-rich nephelinite magma. Melt H2O content

  17. Lead silicate microstructured optical fibres for electro-optical applications.

    PubMed

    Zhang, Wen Qi; Manning, Sean; Ebendorff-Heidepriem, Heike; Monro, Tanya M

    2013-12-16

    We report progress towards the realization of optical modulators based on electro-optic effects in soft glass fibres. A hybrid fabrication procedure was developed for producing microstructured lead silicate glass fibres with internal electrodes. Electro-optical characterization confirms experimentally that the enhanced nonlinear properties and superior isolation between the optical field and the electrodes make these fibres an ideal candidate platform for efficient electro-optical devices.

  18. 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.

  19. 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

  20. 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

  1. Dehydration enthalpy of alkali-cations-exchanged montmorillonite from thermogravimetric analysis.

    PubMed

    Kharroubi, M; Balme, S; Henn, F; Giuntini, J C; Belarbi, H; Haouzi, A

    2009-01-15

    Dehydration of a series of homoionic alkali-exchanged montmorillonites is studied at different treatment temperatures by means of thermogravimetric analysis. More specifically, we investigate the last stages of dehydration when the number of adsorbed water molecules corresponds, at maximum, to a monolayer. Weight losses are measured at several constant temperatures as a function of time. Application of Van't Hoff's law yields the dehydration enthalpy. Trends and data similar to those reported from other experimental conditions are found. Comparison with X-ray data and with the dissociation enthalpy of alkali cation/water complexes shows that dehydration of weakly hydrated homoionic alkali montmorillonites results from the competition between opposite energy contributions due to (i) the cation solvation, (ii) the hydration of the silicate interlayer surface, and (iii) the structural swelling. So, depending on the balance between these various energy contributions, different behaviors are observed according to the nature of the alkali cations. PMID:18973904

  2. 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.

  3. 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

  4. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 6, December 1, 1992--February 28, 1993

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-02-24

    The high temperature alkali corrosion kinetics of SiC have been systematically investigated from 950 to 1100{degrees}C at 0.63 vol % alkali vapor concentration. The corrosion rate in the presence of alkaliis approximately 10{sup 4} to 10{sup 5} times faster than the oxidation rate of SiC in air. The activation energy associated with the alkali corrosion is 406 kJ/mol, indicating a highly temperature-dependent reaction rate. The rate-controlling step of the overall reaction is likely to be the dissolution of silica in the sodium silicate liquid, based on the oxygen diffusivity data.

  5. 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.

  6. Workability and mechanical properties of alkali activated slag concrete

    SciTech Connect

    Collins, F.G.; Sanjayan, J.G.

    1999-03-01

    This paper reports the results of an investigation on concrete containing alkali activated slag (AAS) as the binder, with emphasis on achievement of reasonable workability and equivalent one-day strength to portland cement concrete at normal curing temperatures. Two types of activators were used: sodium hydroxide in combination with sodium carbonate and sodium silicate in combination with hydrated lime. The fresh concrete properties reported include slump and slump loss, air content, and bleed. Mechanical properties of AAS concrete, including compressive strength, elastic modulus, flexural strength, drying shrinkage, and creep are contrasted with those of portland cement concrete.

  7. PROCESS OF RECOVERING ALKALI METALS

    DOEpatents

    Wolkoff, J.

    1961-08-15

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

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

    SciTech Connect

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

    2005-09-08

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

  9. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 12, June 1--August 31, 1994

    SciTech Connect

    Pickrell, G.R.; Brown, J.J.

    1994-09-01

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions.

  10. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 3, March 1, 1992--May 31, 1992

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-05-27

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  11. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 1, September 1, 1991--November 31, 1991

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1991-11-30

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this program is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  12. High temperature alkali corrosion of ceramics in coal gas. Quarterly progress report No. 4, June 1, 1992--August 31, 1992

    SciTech Connect

    Pickrell, G.R.; Sun, T.; Brown, J.J.

    1992-08-29

    High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and high efficiency heat engines. The objective of this research is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, zirconia, and fireclay glass. The study consists of identification of the alkali reaction products (phase equilibria) and the kinetics of the alkali reactions as a function of temperature and time.

  13. 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.

  14. 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.

  15. 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.

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

    NASA Astrophysics Data System (ADS)

    Lee, Martin R.; Chatzitheodoridis, Elias

    2016-07-01

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

  17. 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.

  18. 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.

  19. 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.

  20. Lithium alumino-silicate ion source development

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

    We report experimental progress on Li+ source development in preparation for warm dense matter heating experiments. To uniformly heat targets to electron-volt temperatures for the study of warm dense matter, we are pursuing the use of a low (E < 5 MeV) kinetic energy singly ionized lithium beam and a thin target. Two kinds of lithium (Li+) alumino-silicate ion sources, β-spodumene and β-eucryptite, each of area 0.31 cm2, have been fabricated for ion emission measurements. These surface ionization sources are heated to 1200 to 1300 C where they preferentially emit singly ionized alkali ions. Tight process controls were necessary in preparing and sintering the alumino-silicate to the porous tungsten substrate to produce an emitter that gives uniform ion emission, sufficient current density and low beam emittance. Current density limit of the two kinds have been measured, and ion species identification of possible contaminants has been verified with a Wien (E x B) filter.