Estimate of long-term dissolution rate of basaltic glass. A case study on Mt. Fuji area

International Nuclear Information System (INIS)

Shikazono, Naotatsu; Takino, Akitsugu

2002-01-01

Bulk compositional, mineralogical and physical properties of weathered basaltic ash soil ('Andisol') derived mainly from Mt. Fuji were studied. Mineralogical studies revealed that the dominant primary material and weathering products are volcanic glass, allophane and halloysite and the sequence of weathering is volcanic glass → allophane → 10A halloysite → 7A halloysite. X-ray fluorescence analysis indicates that the relative elemental mobilities during the weathering is Na, Ca>K>Mg>P>Si>Ti, Fe>Al>Mn. The trends of soilwater chemistry (H 4 SiO 4 concentration) with depth were calculated based on dissolution - precipitation kinetics - fluid flow coupling model. In order to calculate the trends, the data on present-day annual rainfall, solubility of basalt glass, porosity and specific weight of soil, deposition rate of volcanic ash and grain size of volcanic glass were used. The calculated results were compared with analytical trends of soilwater chemistry. From this comparison the dissolution rate constant of basalt glass was estimated to be 10 -9.4 - 10 -9.2 (mole Si m -2 s -1 ). This value is consistent with previous experimental dissolution rate constant of basalt glass reported in the literature. (author)

Affinity functions for modeling glass dissolution rates

Energy Technology Data Exchange (ETDEWEB)

Bourcier, W.L. [Lawrence Livermore National Lab., CA (United States)

1997-07-01

Glass dissolution rates decrease dramatically as glass approach ''saturation'' with respect to the leachate solution. Most repository sites are chosen where water fluxes are minimal, and therefore the waste glass is most likely to dissolve under conditions close to ''saturation''. The key term in the rate expression used to predict glass dissolution rates close to ''saturation'' is the affinity term, which accounts for saturation effects on dissolution rates. Interpretations of recent experimental data on the dissolution behaviour of silicate glasses and silicate minerals indicate the following: 1) simple affinity control does not explain the observed dissolution rate for silicate minerals or glasses; 2) dissolution rates can be significantly modified by dissolved cations even under conditions far from saturation where the affinity term is near unity; 3) the effects of dissolved species such as Al and Si on the dissolution rate vary with pH, temperature, and saturation state; and 4) as temperature is increased, the effect of both pH and temperature on glass and mineral dissolution rates decrease, which strongly suggests a switch in rate control from surface reaction-based to diffusion control. Borosilicate glass dissolution models need to be upgraded to account for these recent experimental observations. (A.C.)

Electronic states of SiO2-MxOy (MxOy=P205, TiO2 and ZrO2) glasses

Energy Technology Data Exchange (ETDEWEB)

Kowada, Y [Hyogo Univ. of Teacher Education, Hyogo (Japan); Adachi, H [Kyoto Univ. (Japan). Faculty of Engineering; Minami, T [Univ. of Osaka Prefecture, Osaka (Japan). Faculty of Engineering

1993-12-01

Using the sol-gel method the surface of metal and glass substrates can be modified. For example, stainless steel sheets coated with the SiO2-ZrO2 glass films have higher resistance to corrosion and oxidation. The coating films contain high concentration of alkali ions diffusing from the glass substrates. It suggests that the sodium ions are trapped strongly within the coating films and are blocked to further diffuse to the surface. This behavior must be associated with the chemical bonding around the sodium ions in the SiO2-TiO2 and SiO2-ZrO2 films. For better understanding of the chemical bonding in the glasses, the electronic states of the SiO2-MxOy glasses were calculated by means of the DV-Xa cluster method. In this paper, the calculation method is explained, the results are discussed and the conclusion is stated. 17 refs., 6 figs.

Structure-Dependent Spectroscopic Properties of Yb3+-Doped Phosphosilicate Glasses Modified by SiO2

Directory of Open Access Journals (Sweden)

Ling Wang

2017-02-01

Full Text Available Yb3+-doped phosphate glasses containing different amounts of SiO2 were successfully synthesized by the conventional melt-quenching method. The influence mechanism of SiO2 on the structural and spectroscopic properties was investigated systematically using the micro-Raman technique. It was worth noting that the glass with 26.7 mol % SiO2 possessed the longest fluorescence lifetime (1.51 ms, the highest gain coefficient (1.10 ms·pm2, the maximum Stark splitting manifold of 2F7/2 level (781 cm−1, and the largest scalar crystal-field NJ and Yb3+ asymmetry degree. Micro-Raman spectra revealed that introducing SiO2 promoted the formation of P=O linkages, but broke the P=O linkages when the SiO2 content was greater than 26.7 mol %. Based on the previous 29Si MAS NMR experimental results, these findings further demonstrated that the formation of [SiO6] may significantly affect the formation of P=O linkages, and thus influences the spectroscopic properties of the glass. These results indicate that phosphosilicate glasses may have potential applications as a Yb3+-doped gain medium for solid-state lasers and optical fiber amplifiers.

Structure-Dependent Spectroscopic Properties of Yb3+-Doped Phosphosilicate Glasses Modified by SiO2

Science.gov (United States)

Wang, Ling; Zeng, Huidan; Yang, Bin; Ye, Feng; Chen, Jianding; Chen, Guorong; Smith, Andew T.; Sun, Luyi

2017-01-01

Yb3+-doped phosphate glasses containing different amounts of SiO2 were successfully synthesized by the conventional melt-quenching method. The influence mechanism of SiO2 on the structural and spectroscopic properties was investigated systematically using the micro-Raman technique. It was worth noting that the glass with 26.7 mol % SiO2 possessed the longest fluorescence lifetime (1.51 ms), the highest gain coefficient (1.10 ms·pm2), the maximum Stark splitting manifold of 2F7/2 level (781 cm−1), and the largest scalar crystal-field NJ and Yb3+ asymmetry degree. Micro-Raman spectra revealed that introducing SiO2 promoted the formation of P=O linkages, but broke the P=O linkages when the SiO2 content was greater than 26.7 mol %. Based on the previous 29Si MAS NMR experimental results, these findings further demonstrated that the formation of [SiO6] may significantly affect the formation of P=O linkages, and thus influences the spectroscopic properties of the glass. These results indicate that phosphosilicate glasses may have potential applications as a Yb3+-doped gain medium for solid-state lasers and optical fiber amplifiers. PMID:28772601

Deep-UV Raman spectroscopic analysis of structure and dissolution rates of silica-rich sodium borosilicate glasses

Energy Technology Data Exchange (ETDEWEB)

Pierce, Eric M [ORNL; WindischJr., Charles F. [Pacific Northwest National Laboratory (PNNL); Burton, Sarah D. [Pacific Northwest National Laboratory (PNNL); Bovaird, Chase C. [Pacific Northwest National Laboratory (PNNL)

2010-01-01

As part of ongoing studies to evaluate relationships between structure and rates of dissolution of silicate glasses in aqueous media, sodium borosilicate glasses of composition Na2O xB2O3 (3 x)SiO2, with x 1 (Na2O/B2O3 ratio 1), were analyzed using deep-UV Raman spectroscopy. Results were quantified in terms of the fraction of SiO4 tetrahedra with one non-bridging oxygen (Q3) and then correlated with Na2O and B2O3 content. The Q3 fractionwas found to increase with increasing Na2O content, in agreement with studies on related glasses, and, as long as the value of x was not too high, this contributed to higher rates of dissolution in single pass flow-through testing. In contrast, dissolution rates were less strongly determined by the Q3 fraction when the value of x was near unity, and appeared to grow larger upon further reduction of the Q3 fraction. Results were interpreted to indicate the increasingly important role of network hydrolysis in the glass dissolution mechanism as the BO4 tetrahedron replaces the Q3 unit as the charge-compensating structure for Na+ ions. Finally, the use of deep-UV Raman spectroscopy was found to be advantageous in studying finely powdered glasses in cases where visible Raman spectroscopy suffered from weak Raman scattering and fluorescence interference.

Structure and crystallization of SiO2 and B2O3 doped lithium disilicate glasses from theory and experiment.

Science.gov (United States)

Erlebach, Andreas; Thieme, Katrin; Sierka, Marek; Rüssel, Christian

2017-09-27

Solid solutions of SiO 2 and B 2 O 3 in Li 2 O·2SiO 2 are synthesized and characterized for the first time. Their structure and crystallization mechanisms are investigated employing a combination of simulations at the density functional theory level and experiments on the crystallization of SiO 2 and B 2 O 3 doped lithium disilicate glasses. The remarkable agreement of calculated and experimentally determined cell parameters reveals the preferential, kinetically controlled incorporation of [SiO 4 ] and [BO 4 ] at the Li + lattice sites of the Li 2 O·2SiO 2 crystal structure. While the addition of SiO 2 increases the glass viscosity resulting in lower crystal growth velocities, glasses containing B 2 O 3 show a reduction of both viscosities and crystal growth velocities. These observations could be rationalized by a change of the chemical composition of the glass matrix surrounding the precipitated crystal phase during the course of crystallization, which leads to a deceleration of the attachment of building units required for further crystal growth at the liquid-crystal interface.

Alkali passivation mechanism of sol-gel derived TiO2-SiO2 films coated on soda-lime-silica glass substrates

Energy Technology Data Exchange (ETDEWEB)

Matsuda, A; Matsuno, Y; Katayama, S; Tsuno, T [Nippon Steel Glass Co. Ltd., Tokyo (Japan); Toge, N; Minami, T [University of Osaka Prefecture, Osaka (Japan). College of Engineering

1992-09-01

TiO2-SiO2 films prepared by the sol-gel method serves as an effective alkali passivation layer on a soda-lime-silica glass substrate and the film is superior to a sol-gel derived pure SiO2 film from the view point of weathering resistance improvement. To clarify the reason, alkali passivation mechanism of sol-gel derived TiO2-SiO2 glass films with different TiO2 contents coated on a soda-lime-silica glass substrate was studied by SIMS (secondary ion mass spectroscopy) and XPS (X-ray photoelectron spectroscopy) analyses, and compared with the results of a sol-gel derived pure SiO2 film. As a result, the following conclusions were obtained: An increase in TiO2 content in the TiO2 SiO2 film increases the sodium concentration in the film, which was induced by sodium migration from the glass substrate during the heat-treatment. Because of the presence of sodium the TiO2 -SiO2 films serve not as a barrier but as an effective getter of alkali ions and thereby effectively improve the weathering resistance Of the glass substrate. 10 refs., 6 figs.

Quantitative analysis of crystalline and remaining glass phases in CaO-B2O3-SiO2 ternary system glass ceramics

International Nuclear Information System (INIS)

He Ming; Wu Mengqiang; Zhang Shuren; Zhou Xiaohua; Zhang Ting; Chen Song

2010-01-01

Research highlights: → As for CBS ternary system glass ceramics, due to the complex phase compositions, many methods could be difficult to determine quantitatively the absolute amounts of crystalline and remaining oxides. In this study, an available method based on the Rietveld method was used to quantitatively analyze the relative weight fraction and densities of crystalline phases. These above data are used to obtain a table of both relative weight fraction of crystalline phases and densities of all phases including CBS LTCC. Using volume additivity rule, it is possible to analysis quantitatively the absolute weight fraction of crystalline phases and also the oxides molar content in the remaining glass. - Abstract: Based on Rietveld method of X-ray techniques and volume additivity rule, a new method was developed to quantitatively analyze the phase composition of CaO-B 2 O 3 -SiO 2 ternary system glass ceramics. Lattice parameters, densities and relative weight fractions of crystalline phases in CaO-B 2 O 3 -SiO 2 ternary system were obtained by X-ray diffraction (XRD) refinement. According to the relative weight fraction of crystalline phases and densities of various components, the volume additivity rule was revealed by calculating the absolute weight fraction of crystalline phases of CaO-B 2 O 3 -SiO 2 glass ceramics. In addition, molar contents of the oxides in the remaining glass can also be determined by this method. Comparing this method with internal standard method, it is found that the maximum deviations of the crystallinity and the absolute weight fraction of crystalline phases are less than 2.6% and 2.9%, respectively. As a result, quantitative evaluation of CaO-B 2 O 3 -SiO 2 ternary system glass ceramics can be achieved using this method.

B2O3/SiO2 substitution effect on structure and properties of Na2O-CaO-SrO-P2O5-SiO2 bioactive glasses from molecular dynamics simulations.

Science.gov (United States)

Ren, Mengguo; Lu, Xiaonan; Deng, Lu; Kuo, Po-Hsuen; Du, Jincheng

2018-05-23

The effect of B2O3/SiO2 substitution in SrO-containing 55S4.3 bioactive glasses on glass structure and properties, such as ionic diffusion and glass transition temperature, was investigated by combining experiments and molecular dynamics simulations with newly developed potentials. Both short-range (such as bond length and bond angle) and medium-range (such as polyhedral connection and ring size distribution) structures were determined as a function of glass composition. The simulation results were used to explain the experimental results for glass properties such as glass transition temperature and bioactivity. The fraction of bridging oxygen increased linearly with increasing B2O3 content, resulting in an increase in overall glass network connectivity. Ion diffusion behavior was found to be sensitive to changes in glass composition and the trend of the change with the level of substitution is also temperature dependent. The differential scanning calorimetry (DSC) results show a decrease in glass transition temperature (Tg) with increasing B2O3 content. This is explained by the increase in ion diffusion coefficient and decrease in ion diffusion energy barrier in glass melts, as suggested by high-temperature range (above Tg) ion diffusion calculations as B2O3/SiO2 substitution increases. In the low-temperature range (below Tg), the Ea for modifier ions increased with B2O3/SiO2 substitution, which can be explained by the increase in glass network connectivity. Vibrational density of states (VDOS) were calculated and show spectral feature changes as a result of the substitution. The change in bioactivity with B2O3/SiO2 substitution is discussed with the change in pH value and release of boric acid into the solution.

Overview of chemical modeling of nuclear waste glass dissolution

International Nuclear Information System (INIS)

Bourcier, W.L.

1991-02-01

Glass dissolution takes place through metal leaching and hydration of the glass surface accompanied by development of alternation layers of varying crystallinity. The reaction which controls the long-term glass dissolution rate appears to be surface layer dissolution. This reaction is reversible because the buildup of dissolved species in solution slows the dissolution rate due to a decreased dissolution affinity. Glass dissolution rates are therefore highly dependent on silica concentrations in solution because silica is the major component of the alteration layer. Chemical modeling of glass dissolution using reaction path computer codes has successfully been applied to short term experimental tests and used to predict long-term repository performance. Current problems and limitations of the models include a poorly defined long-term glass dissolution mechanism, the use of model parameters determined from the same experiments that the model is used to predict, and the lack of sufficient validation of key assumptions in the modeling approach. Work is in progress that addresses these issues. 41 refs., 7 figs., 2 tabs

Dissolution patterns of biocompatible glasses in 2-amino-2-hydroxymethyl-propane-1,3-diol (Tris) buffer.

Science.gov (United States)

Fagerlund, S; Hupa, L; Hupa, M

2013-02-01

A continuous flow measurement system with sensitive on-line ion analysis has been applied to study the initial dissolution behaviour of biocompatible glasses in Tris. Altogether 16 glasses with widely varying compositions were studied. The measurement system allowed for quantitative determination of the time-dependent rates of dissolution of sodium, potassium, calcium, magnesium, silicon and phosphorus during the first 10-15 min in contact with Tris solution. The dissolution rates of the different ions showed significant glass to glass variations, but all glasses studied showed one of four distinct dissolution patterns. The ion dissolution rates after an exposure of 1000 s, expressed as the normalized surface-specific mass loss rates, were compared with the in vitro and in vivo reactivity of the glasses as predicted by models in the literature. The results showed a clear correlation between the dissolution rates of the glasses in Tris and their reactivity as measured by other different methods. Consequently, the measured short-term dissolution patterns could be used to determine which glasses are suitable as bioactive, biodegradable, or inert biomaterials for medical devices. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effects of alteration product precipitation on glass dissolution

Energy Technology Data Exchange (ETDEWEB)

Strachan, Denis M.; Neeway, James J.

2014-06-01

Understanding the mechanisms that control the durability of nuclear waste glass is paramount if reliable models are to be constructed so that the glass dissolution rate in a given geological repository can be calculated. Presently, it is agreed that (boro)silicate glasses dissolve in water at a rate dependent on the solution concentration of orthosilicic acid (H₄SiO₄) with higher [H₄SiO₄] leading to lower dissolution rates. Once the reaction has slowed as a result of the buildup of H₄SiO₄, another increase in the rate has been observed that corresponds to the precipitation of certain silica-bearing alteration products. However, it has also been observed that the concentration of silica-bearing solution species does not significantly decrease, indicating saturation, while other glass tracer elements concentrations continue to increase, indicating that the glass is still dissolving. In this study, we have used the Geochemist’s Workbench code to investigate the relationship between glass dissolution rates and the precipitation rate of a representative zeolitic silica-bearing alteration product, analcime [Na(AlSi₂O₆)∙H₂O]. To simplify the calculations, we suppressed all alteration products except analcime, gibbsite (Al(OH)₃), and amorphous silica. The pseudo-equilibrium-constant matrix for amorphous silica was substituted for the glass pseudo-equilibrium-constant matrix because it has been shown that silicate glasses act as a silica-only solid with respect to kinetic considerations. In this article, we present the results of our calculations of the glass dissolution rate at different values for the analcime precipitation rate constant and the effects of varying the glass dissolution rate constant at a constant analcime precipitation rate constant. From the simulations we conclude, firstly, that the rate of glass dissolution is dependent on the kinetics of

Apatite formation on organic polymers by biomimetic process using Na2O-SiO2 glasses as nucleating agent

Energy Technology Data Exchange (ETDEWEB)

Tanahashi, M; Yao, t; Kokubo, T [Kyoto University, Kyoto (Japan). Faculty of Engineering; Minoda, M; Miyamoto, T [Kyoto University, Kyoto (Japan). Institute for Chemical Research; Nakamura, T [Kyoto University, Kyoto (Japan). Research Center for Biomedical Engineering; Yamamuro, T [Kyoto University, Kyoto (Japan). Faculty of Medicine

1994-09-01

In this investigation, CaO-SiO2-based glass, which was previously used as the nucleating agent, was replaced by Na2O-SiO2 glasses, SiO2 glass, and SiO2 gel. The induction period for the apatite nucleation on various organic polymer substrates and the adhesive strength of the apatite layer to the substrates were examined. It was considered that the short induction period for the glasses with high Na2O contents was attributed to high dissolution rates of sodium and silicate ions from them. It was also considered that highly polar carboxyl or sulfinyl groups were formed on the polymer surfaces by the hydrolysis of their ester, amide or sulfonyl group in simulated body fluid with its pH increased by the Na{sup +} dissolution from the glass, and that these polar groups formed a strong bond with the apatite. It is suggested that thus formed apatite-organic polymer composites are useful as the bone-repairing as well as soft tissue-repairing materials. 11 refs., 13 figs., 3 tabs.

Improvement of database on glass dissolution

International Nuclear Information System (INIS)

Hayashi, Maki; Sasamoto, Hiroshi; Yoshikawa, Hideki

2008-03-01

In geological disposal system, high-level radioactive waste (HLW) glass is expected to retain radionuclide for the long term as the first barrier to prevent radionuclide release. The advancement of its performance assessment technology leads to the reliability improvement of the safety assessment of entire geological disposal system. For this purpose, phenomenological studies for improvement of scientific understanding of dissolution/alteration mechanisms, and development of robust dissolution/alteration model based on the study outcomes are indispensable. The database on glass dissolution has been developed for supporting these studies. This report describes improvement of the prototype glass database. Also, this report gives an example of the application of the database for reliability assessment of glass dissolution model. (author)

Bending strength of glass-ceramics based on 3CaO.P2O5-SiO2-MgO glass system

International Nuclear Information System (INIS)

Daguano, J.K.M.F.; Suzuki, P.A.; Santos, C.; Fernandes, M.H.V.; Elias, C.N.

2009-01-01

In this work, the Modulus of Rupture of bioactive glass-ceramic based on 3CaO.P 2 O 5 -SiO 2 -MgO system was investigated, aiming its use in bone-restorations. The mechanical property was correlated with microstructural and crystallographic features of this material. High-purity starting-powders, CaCO 3 , SiO 2 , MgO, Ca (H 2 PO 4 ).H 2 O, were used in this study. The powders were mixed in a stoichiometric ratio, using planetary ball-mill. The suspensions were dried, sieved and melted at 1600 deg C, for 4h. The casting ones were cooled quickly until annealing temperature 700 deg C, in which remained for 2h, with controlled cooling-rate until ambient temperature. Bulks of glass were heat-treated with temperatures varying between 700 deg C and 1100 deg C, for 4h, being after that, cooled at 3 deg C/min. Bioactive glass and glass-ceramic were characterized by HRXRD (high resolution X-ray diffraction), where whitlockite was main phase. The microstructure was analyzed by scanning electronic microscopy. Modulus of Rupture was determined by four-point bending testing using specimens of 1.5 x 2 x 25 mm and glasses presented strength near to 70MPa, while glass ceramics treated at 975 deg C-4h, presented bending strength of 120MPa. (author)

Crystallization behavior of (1 - x)Li2O.xNa2O.Al2O3.4SiO2 glasses

International Nuclear Information System (INIS)

Wang, Moo-Chin; Cheng, Chih-Wei; Chang, Kuo-Ming; Hsi, Chi-Shiung

2010-01-01

The crystallization behavior of the (1 - x)Li 2 O.xNa 2 O.Al 2 O 3 .4SiO 2 glasses has been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron diffraction (ED) and energy dispersive spectroscopy (EDS). The crystalline phase was composed of β-spodumene. The isothermal crystallization kinetics of β-spodumene from the (1 - x)Li 2 O.xNa 2 O.Al 2 O 3 .4SiO 2 glasses has also been studied by a quantitative X-ray diffraction method. The activation energy of β-spodumene formation decreases from 359.2 to 317.8 kJ/mol when the Na 2 O content increases from 0 to 0.4 mol and it increases from 317.8 to 376.9 kJ/mol when the Na 2 O content increases from 0.4 to 0.6 mol. The surface nucleation and plate-like growth were dominant in the crystallization of the (1 - x)Li 2 O.xNa 2 O.Al 2 O 3 .4SiO 2 glasses.

Network rigidity and properties of SiO2 and GeO2 glasses under pressure.

Science.gov (United States)

Trachenko, Kostya; Dove, Martin T; Brazhkin, Vadim; El'kin, F S

2004-09-24

We report in situ studies of SiO2 glass under pressure and find that temperature-induced densification takes place in a pressure window. To explain this effect, we study how rigidity of glasses changes under pressure, with rigidity percolation affecting the dynamics of local relaxation events. We link rigidity percolation in glasses to other effects, including a large increase of crystallization temperature and logarithmic relaxation under pressure.

Microstructural dependence on relevant physical-mechanical properties on SiO2-Na2O-CaO-P2O5 biological glasses.

Science.gov (United States)

Rajendran, V; Begum, A Nishara; Azooz, M A; el Batal, F H

2002-11-01

Bioactive glasses of the system SiO2-Na2O-CaO-P2O5 have been prepared by the normal melting and annealing technique. The elastic moduli, attenuation, Vickers hardness, fracture toughness and fracture surface energy have been obtained using the known method at room temperature. The temperature dependence of elastic moduli and attenuation measurements have been extended over a wide range of temperature from 150 to 500 K. The SiO2 content dependence of velocities, attenuation, elastic moduli, and other parameters show an interesting observation at 45 wt% of SiO2 by exhibiting an anomalous behaviour. A linear relation is developed for Tg, which explores the influence of Na2O on SiO2-Na2O-CaO-P2O5 bioactive glasses. The measured hardness, fracture toughness and fracture surface energy show a linear relation with Young's modulus. It is also interesting to note that the observed results are functions of polymerisation and the number of non-bridging oxygens (NBO) prevailing in the network with change in SiO2 content. The temperature dependence of velocities, attenuation and elastic moduli show the existence of softening in the glass network structure as temperature increases.

Room Temperature Imprint Using Crack-Free Monolithic SiO2-PVA Nanocomposite for Fabricating Microhole Array on Silica Glass

Directory of Open Access Journals (Sweden)

Shigeru Fujino

2015-01-01

Full Text Available This paper aims to fabricate microhole arrays onto a silica glass via a room temperature imprint and subsequent sintering by using a monolithic SiO2-poly(vinyl alcohol (PVA nanocomposite as the silica glass precursor. The SiO2-PVA suspension was prepared from fumed silica particles and PVA, followed by drying to obtain tailored SiO2-PVA nanocomposites. The dependence of particle size of the fumed silica particles on pore size of the nanocomposite was examined. Nanocomposites prepared from 7 nm silica particles possessed suitable mesopores, whereas the corresponding nanocomposites prepared from 30 nm silica particles hardly possessed mesopores. The pore size of the nanocomposites increased as a function of decreasing pH of the SiO2-PVA suspension. As a consequence, the crack-free monolithic SiO2-PVA nanocomposite was obtained using 7 nm silica particles via the suspension at pH 3. Micropatterns were imprinted on the monolithic SiO2-PVA nanocomposite at room temperature. The imprinted nanocomposite was sintered to a transparent silica glass at 1200°C in air. The fabricated sintered glass possessed the microhole array on their surface with aspect ratios identical to the mold.

Photochemical process of divalent germanium responsible for photorefractive index change in GeO2-SiO2 glasses.

Science.gov (United States)

Sakoh, Akifumi; Takahashi, Masahide; Yoko, Toshinobu; Nishii, Junji; Nishiyama, Hiroaki; Miyamoto, Isamu

2003-10-20

The photoluminescence spectra of the divalent Ge (Ge2+) center in GeO2-SiO2 glasses with different photosensitivities were investigated by means of excitation-emission energy mapping. The ultraviolet light induced photorefractivity has been correlated with the local structure around the Ge2+ centers. The glasses with a larger photorefractivity tended to exhibit a greater band broadening of the singlet-singlet transition on the higher excitation energy side accompanied by an increase in the Stokes shifts. This strongly suggests the existence of highly photosensitive Ge2+ centers with higher excitation energies. It is also found that the introduction of a hydroxyl group or boron species in GeO2-SiO2 glasses under appropriate conditions modifies the local environment of Ge2+ leading to an enhanced photorefractivity.

Plutonium dioxide dissolution in glass

International Nuclear Information System (INIS)

Vienna, J.D.; Alexander, D.L.; Li, Hong

1996-09-01

In the aftermath of the Cold War, the U.S. Department of Energy's (DOE) Office of Fissile Materials Disposition (OFMD) is charged with providing technical support for evaluation of disposition options for excess fissile materials manufactured for the nation's defense. One option being considered for the disposition of excess plutonium (Pu) is immobilization by vitrification. The vitrification option entails immobilizing Pu in a host glass and waste package that are criticality-safe (immune to nuclear criticality), proliferation-resistant, and environmentally acceptable for long-term storage or disposal. To prove the technical and economic feasibility of candidate vitrification options it is necessary to demonstrate that PuO 2 feedstock can be dissolved in glass in sufficient quantity. The OFMD immobilization program has set a Pu solubility goal of 10 wt% in glass. The life cycle cost of the vitrification options are strongly influenced by the rate at which PUO 2 dissolves in glass. The total number of process lines needed for vitrification of 50 t of Pu in 10 years is directly dependent upon the time required for Pu dissolution in glass. The objective of this joint Pacific Northwest National Laboratory (PNNL) - Savannah River Technology Center (SRTC) study was to demonstrate a high Pu solubility in glass and to identify on a rough scale the time required for Pu dissolution in the glass. This study was conducted using a lanthanide borosilicate (LaBS) glass composition designed at the SRTC for the vitrification of actinides

Plutonium dioxide dissolution in glass

Energy Technology Data Exchange (ETDEWEB)

Vienna, J.D.; Alexander, D.L.; Li, Hong [and others

1996-09-01

In the aftermath of the Cold War, the U.S. Department of Energy`s (DOE) Office of Fissile Materials Disposition (OFMD) is charged with providing technical support for evaluation of disposition options for excess fissile materials manufactured for the nation`s defense. One option being considered for the disposition of excess plutonium (Pu) is immobilization by vitrification. The vitrification option entails immobilizing Pu in a host glass and waste package that are criticality-safe (immune to nuclear criticality), proliferation-resistant, and environmentally acceptable for long-term storage or disposal. To prove the technical and economic feasibility of candidate vitrification options it is necessary to demonstrate that PuO{sub 2} feedstock can be dissolved in glass in sufficient quantity. The OFMD immobilization program has set a Pu solubility goal of 10 wt% in glass. The life cycle cost of the vitrification options are strongly influenced by the rate at which PUO{sub 2} dissolves in glass. The total number of process lines needed for vitrification of 50 t of Pu in 10 years is directly dependent upon the time required for Pu dissolution in glass. The objective of this joint Pacific Northwest National Laboratory (PNNL) - Savannah River Technology Center (SRTC) study was to demonstrate a high Pu solubility in glass and to identify on a rough scale the time required for Pu dissolution in the glass. This study was conducted using a lanthanide borosilicate (LaBS) glass composition designed at the SRTC for the vitrification of actinides.

Adsorption of uranyl in SiO2 porous glass

International Nuclear Information System (INIS)

Benedetto, F. E.; Prado, M. O.

2013-01-01

Vitreous SiO 2 porous matrices can be used in many applications involving the uptake of chemical species on its solid surface. In this work, vitreous silica sponges were prepared from a sodium borosilicate glass manufactured in our laboratory. The product obtained was then separated into phases with subsequent leaching of the soluble phase rich in B and Na. The resulting porous matrices have a specific surface of 35 m2/gr. Adsorption of uranyl ions onto the SiO 2 porous surface was studied to evaluate the use of this material as a filter for treatment of uranium containing water. The effects of contact time, adsorbent mass and equilibrium concentration of solution were studied. The porous adsorbent exhibits a pseudo-second-order kinetic behavior. The sponges with adsorbed uranium were thermally sealed as a way of U immobilization. Retention of uranium was confirmed during the matrix sealing by TGA. Uranium concentration before and after adsorption tests were made by means of ICP-OES. For uranium concentration of 800 ppm, 72 hours contact time and pH of 3.5, the amount of uranium adsorbed was 21.06 ± 0.02 mg U per gram of vitreous porous SiO 2 . (author)

Super-bright and short-lived photoluminescence of textured Zn2SiO4:Mn2+ phosphor film on quartz glass

Science.gov (United States)

Park, Jehong; Park, Kwangwon; Lee, Jaebum; Kim, Jongsu; Seo, Kwangil; Kwon, Kevin; Kung, Patrick; Kim, Seongsin M.

2010-02-01

Green-emissive textured Zn2SiO4:Mn2+ phosphor film was fabricated by a thermal diffusion of ZnO:Mn on quartz glass. The characterization has been performed in terms of Mn2+ ions concentration (Mn/Zn=1~9 mol %). As an increase of Mn2+ ions concentration in the Zn2SiO4:Mn2+ phosphor film, the emission peak was red shifted from 519 nm to 526 nm, and the decay time to 10% of the maximum intensity was shorter from 20 ms to 0.5 ms. All annealed Zn2SiO4:Mn2+ phosphor films became textured along some hexagonal directions on the amorphous quartz glass. The brightest Zn2SiO4:Mn2+ film at optimal Mn2+ concentration of 5 % showed the photoluminescence brightness of 65 % and the shortened decay time of 4.4 ms in comparison with a commercially Zn2SiO4: Mn2+ powder phosphor screen. The excellencies can be attributed to a unique textured structure.

CoO-doped MgO-Al2O3-SiO2-colored transparent glass-ceramics with high crystallinity

Science.gov (United States)

Tang, Wufu; Zhang, Qian; Luo, Zhiwei; Yu, Jingbo; Gao, Xianglong; Li, Yunxing; Lu, Anxian

2018-02-01

To obtain CoO-doped MgO-Al2O3-SiO2 (MAS)-colored transparent glass-ceramics with high crystallinity, the glass with the composition 21MgO-21Al2O3-54SiO2-4B2O3-0.2CoO (in mol %) was prepared by conventional melt quenching technique and subsequently thermal treated at several temperatures. The crystallization behavior of the glass, the precipitated crystalline phases and crystallinity were analyzed by X-ray diffraction (XRD). The microstructure of the glass-ceramics was characterized by field emission scanning electron microscopy (FSEM). The transmittance of glass-ceramic was measured by UV spectrophotometer. The results show that a large amount of α-cordierite (indianite) with nano-size was precipitated from the glass matrix after treatment at 1020 °C for 3 h. The crystallinity of the transparent glass-ceramic reached up to 97%. Meanwhile, the transmittance of the glass-ceramic was 74% at 400 nm with a complex absorption band from 450 nm to 700 nm. In addition, this colored transparent glass-ceramic possessed lower density (2.469 g/cm3), lower thermal expansion coefficient (1.822 × 10-6 /℃), higher Vickers hardness (9.1 GPa) and higher bending strength (198 MPa) than parent glass.

A kinetic model for borosilicate glass dissolution based on the dissolution affinity of a surface alteration layer

International Nuclear Information System (INIS)

Bourcier, W.L.; Peiffer, D.W.; Knauss, K.G.; McKeegan, K.D.; Smith, D.K.

1989-11-01

A kinetic model for the dissolution of borosilicate glass is used to predict the dissolution rate of a nuclear waste glass. In the model, the glass dissolution rate is controlled by the rate of dissolution of an alkali-depleted amorphous surface (gel) layer. Our model predicts that all components concentrated in the surface layer, affect glass dissolution rates. The good agreement between predicted and observed elemental dissolution rates suggests that the dissolution rate of the gel layer limits the overall rate of glass dissolution. The model predicts that the long-term rate of glass dissolution will depend mainly on ion concentrations in solution, and therefore on the secondary phases which precipitate and control ion concentrations. 10 refs., 5 figs., 1 tab

Preparation and encapsulation performance of Al_2O_3-SiO_2-B_2O_3 glass-ceramic for high temperature thermal storage

International Nuclear Information System (INIS)

Li, Ruguang; Zhu, Jiaoqun; Zhou, Weibing; Cheng, Xiaomin; Liu, Fengli

2017-01-01

Highlights: • Al_2O_3-B_2O_3-SiO_2 has good chemical durability, corrosion resistance and dense structure. • The material rarely used in high temperature thermal storage. • The material was prepared and characterized in the paper. - Abstract: In this paper, Al_2O_3-SiO_2-B_2O_3 glass-ceramic was prepared and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), further, the porosity was detected by Archimedes principle, thermo physical properties were investigated by differential scanning calorimeter (DSC), respectively. The phase composition was detected by XRD, and the morphology was observed by SEM. The results indicated that the thermal conductivities of the Al_2O_3-SiO_2-B_2O_3 glass-ceramic were between 1.3 and 1.5 W·(m·K)"−"1, and the material had good thermal stability in the range of 300–900 °C. The porosity and apparent density were increased with the temperature. The porosity of Al_2O_3-SiO_2-B_2O_3 glass-ceramic in ranging from 1.2 to 9.6%, the apparent density were between 2.12 and 2.67 g·cm"−"3, and heat capacities were between 0.64 and 0.79 kJ/(kg·K). All the results indicated that the Al_2O_3-SiO_2-B_2O_3 glass-ceramic can be applied as encapsulation material in high temperature latent thermal energy storage.

Toward a consistent model for glass dissolution

International Nuclear Information System (INIS)

Strachan, D.M.; McGrail, B.P.; Bourcier, W.L.

1994-01-01

Understanding the process of glass dissolution in aqueous media has advanced significantly over the last 10 years through the efforts of many scientists around the world. Mathematical models describing the glass dissolution process have also advanced from simple empirical functions to structured models based on fundamental principles of physics, chemistry, and thermodynamics. Although borosilicate glass has been selected as the waste form for disposal of high-level wastes in at least 5 countries, there is no international consensus on the fundamental methodology for modeling glass dissolution that could be used in assessing the long term performance of waste glasses in a geologic repository setting. Each repository program is developing their own model and supporting experimental data. In this paper, we critically evaluate a selected set of these structured models and show that a consistent methodology for modeling glass dissolution processes is available. We also propose a strategy for a future coordinated effort to obtain the model input parameters that are needed for long-term performance assessments of glass in a geologic repository. (author) 4 figs., tabs., 75 refs

Dissolution rates of DWPF glasses from long-term PCT

International Nuclear Information System (INIS)

Ebert, W.L.; Tam, S.W.

1996-01-01

We have characterized the corrosion behavior of several Defense Waste Processing Facility (DWPF) reference waste glasses by conducting static dissolution tests with crushed glasses. Glass dissolution rates were calculated from measured B concentrations in tests conducted for up to five years. The dissolution rates of all glasses increased significantly after certain alteration phases precipitated. Calculation of the dissolution rates was complicated by the decrease in the available surface area as the glass dissolves. We took the loss of surface area into account by modeling the particles to be spheres, then extracting from the short-term test results the dissolution rate corresponding to a linear decrease in the radius of spherical particles. The measured extent of dissolution in tests conducted for longer times was less than predicted with this linear dissolution model. This indicates that advanced stages of corrosion are affected by another process besides dissolution, which we believe to be associated with a decrease in the precipitation rate of the alteration phases. These results show that the dissolution rate measured soon after the formation of certain alteration phases provides an upper limit for the long-term dissolution rate, and can be used to determine a bounding value for the source term for radionuclide release from waste glasses. The long-term dissolution rates measured in tests at 20,000 per m at 90 degrees C in tuff groundwater at pH values near 12 for the Environmental Assessment glass and glasses made with SRL 131 and SRL 202 frits, respectively

Optical Properties of Malachite Green Dye Doped SiO2 Glasses: Effect of Transition Metal (Fe-I Used as a Codopant

Directory of Open Access Journals (Sweden)

Dulen Bora

2014-01-01

Full Text Available Enhanced luminescence properties of Malachite Green (MG (oxalate in Fe-MG codoped SiO2 glasses compared to its values in MG doped SiO2 glasses are reported here. The enhancement is chiefly attributed to a resonance nonradiative energy transfer between Fe and MG. The quantum yield of Malachite Green (MG, in presence of Iron, trapped in sol-gel derived SiO2 glass increases by an order of ~103 compared to that in low viscous solvent while a lifetime of 3.29 ns is reported.

Effective role of CaO/P2O5 ratio on SiO2-CaO-P2O5 glass system

Directory of Open Access Journals (Sweden)

P. Kiran

2017-05-01

Full Text Available In the present work, the effect of the CaO/P2O5 ratio on the composition of sol-gel synthesized 58SiO2-(19 − xP2O5–(23 + xCaO (x = 0, 5, 10 and 15 mol% glass samples was studied. Further, the effect of NBO/BO ratio on hydroxy carbonated apatite layer (HCA forming ability based on dissolution behavior in simulated body fluid (SBF solution was also investigated. CaO/P2O5 ratios of synthesized glass samples were 1.2, 2, 3.6, and 9.5, respectively. NBO/BO ratios were obtained using Raman spectroscopic analysis as 0.58, 1.20, 1.46, and 1.78, respectively. All samples were soaked in the SBF solution for 7 days. The calculated weight losses of these samples were 58%, 64%, 83%, and 89% for corresponding NBO/BO ratios. The increase in CaO/P2O5 ratio increases the NBO/BO ratios. However, the increase in NBO/BO ratio increases HCA forming ability of SBF treated samples. The HCA crystalline layer formation was confirmed through X-ray Diffraction (XRD, Transmission Electron Microscopy (TEM, Scanning Electron Microscopy (SEM, Raman and Infrared spectroscopic analysis. Higher CaO/P2O5 ratio favors the increase in HCA formation for SBF treated calcium phospho silicate glasses.

Effect of alteration phase formation on the glass dissolution rate

International Nuclear Information System (INIS)

Ebert, W.L.

1997-01-01

The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. While simulations have predicted the accelerating effect of formation of certain phases, the phases predicted to form in computer simulations are usually different than those observed to form in experiments. This is because kinetically favored phases form first in experiments, while simulations predict the thermodynamically favored phases. Static dissolution tests with crushed glass have been used to measure the glass dissolution rate after alteration phases form. Because glass dissolution rates are calculated on a per area basis, an important effect in tests conducted with crushed glass is the decrease in the surface area of glass that is available for reaction as the glass dissolves. This loss of surface area must be taken into account when calculating the dissolution rate. The phases that form and their effect on the dissolution rate are probably related to the glass composition. The impact of phase formation on the glass dissolution rate also varies according to the solubility products of the alteration phases and how the orthocilicic acid activity is affected. Insight into the relationship between the glass dissolution rate, solution chemistry and alteration phase formation is provided by the results of accelerated dissolution tests

Effect of alteration phase formation on the glass dissolution rate

Energy Technology Data Exchange (ETDEWEB)

Ebert, W L [Argonne National Laboratory, Chemical Technology Div. (United States)

1997-07-01

The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. While simulations have predicted the accelerating effect of formation of certain phases, the phases predicted to form in computer simulations are usually different than those observed to form in experiments. This is because kinetically favored phases form first in experiments, while simulations predict the thermodynamically favored phases. Static dissolution tests with crushed glass have been used to measure the glass dissolution rate after alteration phases form. Because glass dissolution rates are calculated on a per area basis, an important effect in tests conducted with crushed glass is the decrease in the surface area of glass that is available for reaction as the glass dissolves. This loss of surface area must be taken into account when calculating the dissolution rate. The phases that form and their effect on the dissolution rate are probably related to the glass composition. The impact of phase formation on the glass dissolution rate also varies according to the solubility products of the alteration phases and how the orthocilicic acid activity is affected. Insight into the relationship between the glass dissolution rate, solution chemistry and alteration phase formation is provided by the results of accelerated dissolution tests.

Hydrothermal alteration of the glass R7T7. Glass dissolution kinetics at 150 and 2500, role of neo-formed phases

International Nuclear Information System (INIS)

Caurel, J.

1990-01-01

The glass R7T7 is chosen in France for vitrification of solution from reprocessing. Safety requires the knowledge of R7T7 long term behavior in deep geologic formations. Temperature dependence of leaching between 50 and 300 0 C is studied by static tests for 7 days. An activation energy of 30kJ/Mole is calculated between 50; 75 or 100 0 C and 250 0 C. Results suggest similar corrosion mechanisms between 90-100 and 250 0 C by a complete change between 250 and 275 0 C. Glass corrosion kinetics at 150 0 C and 250 0 C between 1 day and 1 year evidence the precipitation of aluminosilicates and formation of thick amorphous gels progressively enriched with silica. Glass dissolution at 150 0 C and 250 0 C is simulated with the geochemical DISSOL code. Results suggest that dissolution kinetics are controlled by activity of H 4 SiO 4 in solution only. Silica contained into the gel controls corrosion kinetics different from 0. Even if the nature of dissolution mechanisms does not seem modified between 150 and 250 0 C, sample cracking at 250 0 C induces an increase of dissolved glass that does not allow a direct comparison of corrosion kinetics between 150 and 250 0 C [fr

First Measurements of Time-Dependent Nucleation as a Function of Composition in Na2O.2CaO.3SiO2 Glasses

Science.gov (United States)

Kelton, K. F.; Narayan, K. Lakshmi

1996-01-01

The first measurements in any system of the composition dependence of the time-dependent nucleation rate are presented Nucleation rates of the stoichiometric crystalline phase, Na2O.2CaO.3SiO2, from quenched glasses made with different SiO2 concentrations were determined as a function of temperature and glass composition. A strong compositional dependence of the nucleation rates and a weak dependence for the induction times are observed. Using measured values of the liquidus temperatures and growth velocities as a function of glass composition, these data are shown to be consistent with predictions from the classical theory of nucleation, assuming a composition-dependent interfacial energy.

Structure of Mg2SiO4 glass up to 140 GPa

Science.gov (United States)

Prescher, C.; Prakapenka, V.; Wang, Y.; Skinner, L. B.

2014-12-01

The physical properties of melts at temperature and pressure conditions of the Earth's mantle have a fundamental influence on the chemical and thermal evolution of the Earth. However, direct investigations of melt structures at these conditions are experimentally very difficult or even impossible with current capabilities. In order to still be able to obtain an estimate of the structural behavior of melts at high pressures and temperatures, amorphous materials have been widely used as analogue materials. In particular the investigation of sound wave velocities of amorphous SiO2 and MgSiO3 as analogues for silicate melts indicate structural changes at about ~30-40 GPa and ~130-140 GPa [1]. The transition pressures are lower for MgSiO3 than for SiO2 indicating that these transitions are affected by the degree of polymerization of the SiO2 network of the glasses. Nevertheless, these measurements only give a hint about the occurrence of structural transitions but lack information on the actual structural changes accompanied by the sound wave velocity discontinuities. The pressure of the second structural transition at ~130-140 GPa is of vital importance for geophysics. If it causes silicate melts to become denser than the surrounding solid material, it would result in negatively buoyant melts close to the core-mantle boundary, which could be a major factor affecting the chemical stratification of the Earth's mantle during an early magma ocean after the moon forming impact. In order to resolve the structural transition and estimate the effect of a different degree of polymerization further, we studied the structural behavior of Mg2SiO4 glass up to 140 GPa using X-ray total scattering and pair distribution function analysis. The measurements were performed at the GSECARS 13-IDD beamline at the APS employing the newly developed multichannel collimator (MCC) setup. The MCC effectively removes unwanted Compton scattering of the diamond anvils and enables easy extraction of

Surface chemistry and durability of borosilicate glass

International Nuclear Information System (INIS)

Carroll, S.A.; Bourcier, W.L.; Phillips, B.L.

1994-01-01

Important glass-water interactions are poorly understood for borosilicate glass radioactive waste forms. Preliminary results show that glass durability is dependent on reactions occurring at the glass-solution interface. CSG glass (18.2 wt. % Na 2 O, 5.97 wt. % CaO, 11.68 wt. % Al 2 O 3 , 8.43 wt. % B 2 O 3 , and 55.73 wt. % SiO 2 ) dissolution and net surface H + and OH - adsorption are minimal at near neutral pH. In the acid and alkaline pH regions, CSG glass dissolution rates are proportional to [H + ] adsorbed 2 and [OH - ] adsorbed 0.8 , respectively. In contrast, silica gel dissolution and net H + and OH - adsorption are minimal and independent of pH in acid to neutral solutions. In the alkaline pH region, silica gel dissolution is proportional to [OH - ] adsorbed 0.9 adsorbed . Although Na adsorption is significant for CSG glass and silica gel in the alkaline pH regions, it is not clear if it enhances dissolution, or is an artifact of depolymerization of the framework bonds

Preparation and characterization of new glasses from the TeO2-CdO-Al2O3-SiO2 system

OpenAIRE

Zayas, Mª. E.; Espinoza-Beltrán, F. J.; Romero, Maximina; Rincón López, Jesús María

1998-01-01

A new family of glasses from the TeO2-CdO-Al2O3-SiO2 system obtained from CdS-TeO2 mixtures melted in fireclay crucibles have been prepared and characterized. The density values of these glasses are in the 3.30-3.46 gcm-3 range. The viscosity-temperature variation shows that glasses with high TeO2 content depict the typical variation of `short glasses' for a molding operation. Microstructural observations by TEM (replica method) and SEM microscopies have shown that these glasses contain very ...

Phytic acid derived bioactive CaO-P2O5-SiO2 gel-glasses.

Science.gov (United States)

Li, Ailing; Qiu, Dong

2011-12-01

The possibility of using phytic acid as a precursor to synthesize CaO-P(2)O(5)-SiO(2) glasses by sol-gel method has been explored and the pseudo ternary phase diagram has been established. It was shown that gel-glasses over a broader range of compositions could be prepared compared to other phosphorus precursors or melt-quenching method. Furthermore, phytic acid was found to assist calcium being incorporated into glass networks. In vitro tests in simulated body fluid (SBF) were performed on the above gel-glasses and it was found that they were bioactive over a much broader compositional range especially at high phosphate content, thus enabling one to design bioactive materials with various degradation rates by adjusting the phosphate content.

Fluorescence of Pentavalent Chromium in SiO2 Sol-Gel Glasses

Science.gov (United States)

Jia, Weiyi; Castro, Lymari; Wang, Yanyun; Liu, Huimin

1998-01-01

Chromium ions are very attractive to optical spectroscopy and laser physics. It is well known that the first laser in the history is a ruby laser activated with Cr(3+). It was found in early nineties that Cr(4+) was also an interesting lasing ion in the near infrared, and various Cr(4+) lasers have been developed. Very recently, it was reported that Cr(2+) doped in CdSe crystals showed lasing action in the infrared. The above achievement have stimulated an interest in searching for Cr(5+) and investigating its optical properties. Cr(5+) is isoelectronic with Ti(3+) and V(4+), having electron configuration 3d1. Ti(3+) is the active center of commercial cw and femtosecond sapphire lasers, tunable in the range 680-1100 nm. V(4+) doped in YAlO3 and Al2O3 showed broad band emission near 635 nm. Although EPR results of Cr(5+) were reported, the optical properties were less studied. Herren et al. reported an observation of luminescence from Cr doped in SiO2 sol-gel glass. The luminescence spectrum was assigned to pentavalent ions in their first paper, and later it was identified to be the emission from the charge transfer transition of Cr(6+). The first observation of photoluminescence from octahedrally coordinated Cr(5+) in BaCaMg aluminate glasses was reported very recently. In this work, we report luminescence results of Cr doped SiO2 sol-gel glasses. The fluorescence spectra are very different from Herrens' results, and we believe it originates from pentavalent Cr.

Cesium Hydroxide Fusion Dissolution of Analytical Reference Glass-1 in Both Powder and Shard Form

International Nuclear Information System (INIS)

Coleman, C.J.; Spencer, W.A.

1998-04-01

CsOH has been shown to be an effective and convenient dissolution reagent for Analytical Reference Glass-1 (ARG-1). This glass standard was prepared from nonradioactive DWPF Start-up Glass. Therefore, its composition is similar to DWPF product glass and many of the glass matrices prepared at SRTC.The principal advantage of the CsOH fusion dissolution is that the reagent does not add the alkali metals Li, Na, and K usually needed by SRS customers. Commercially available CsOH is quite pure so that alkali metals can be measured accurately, often without blank corrections. CsOH fusions provide a single dissolution method for applicable glass to replace multiple dissolution schemes used by most laboratories. For example, SRTC glass samples are most commonly dissolved with a Na 2 O 2 -NaOH fusion (ref.1) and a microwave- assisted acid dissolution with HNO 3 -HF-H 3 BO 3 -HCl (ref.2). Othe laboratories use fusion methods based on KOH, LiBO 2 , and Na 2 CO 3 CsOH fusion approach reduces by half not only the work in the dissolution laboratory, but also in the spectroscopy laboratories that must analyze each solution.Experiments also revealed that glass shards or pellets are rapidly attacked if the flux temperature is raised considerably above the glass softening point. The softening point of ARG-1 glass is near 650 degrees C. Fusions performed at 750 degrees C provided complete dissolutions and accurate elemental analyses of shards. Successful dissolution of glass shards was demonstrated with CsOH, Na 2 O 2 , NaOH, KOH, and RbOH. Ability to dissolve glass shards is of considerable practical importance. Crushing glass to a fine powder is a slow and tedious task, especially for radioactive glasses dissolved in shielded cells. CsOH fusion of glass powder or shards is a convenient, cost-effective dissolution scheme applicable in SRTC, the DWPF, and the commercial glass industry

A statistical approach to determine the effects of nuclear glass components on the short and long term glass alteration

International Nuclear Information System (INIS)

Advocat, Th.; Tovena, I.; Vernaz, E.; Larche, F.; Phan Tan Luu, R.

1997-01-01

The experimentation plan methodology may be a powerful tool to design statistical models able to calculate quantitative leach rates as a function of glass compositions. The investigation discussed here implemented an experimentation plan methodology covering a wide range of glass composition variations with two major objectives: - identify the effects of the main component oxides of R7T7 glass (SiO 2 , B 2 O 3 , Al 2 O 3 , Na 2 O+Li 2 O, additive oxides, Fission Products oxides, actinide oxides) on the dissolution rates far and close to equilibrium; - and develop a statistical model relating the measured initial dissolution rate with the selected oxide compositions. A second-degree silica-based model was developed to express the initial dissolution rates at 100 deg C according to the oxide weight percentage of 6 major oxides or oxide groups. The model is qualified by comparison with independent experimental results. For the short term, far from saturation conditions (confined media), plotting the effects of the oxides clearly showed that SiO 2 , Al 2 O 3 and the additive oxides enhanced glass durability at 100 deg C, while B 2 O 3 and Na 2 O+Li 2 O diminished the initial corrosion resistance. For the long term, plotting the effects of the oxides showed that additive oxides, Al 2 O 3 and SiO 2 enhanced glass durability at 90 deg C, in that order, while Na 2 O+Li 2 O still diminished the corrosion resistance. The fission products and actinide oxides and ZrO 2 have apparently a slight beneficial effect on the glass durability, under saturation conditions (long term). (author)

Glass-ceramic materials of system MgO-Al2O3-SiO2 from rice husk ash

OpenAIRE

Martín Hernández, María Isabel; Rincón López, Jesús María; Andreola, F.; Barbieri, L.; Bondioli, F.; Lancellotti, I.; Romero, Maximina

2011-01-01

This wok shows the results of a valorisation study to use rice husk ash as raw material to develop glass-ceramic materials. An original glass has been formulated in the base system MgO-Al2O3-SiO2 with addition of B2O3 and Na2O to facilitate the melting and poring processes. Glass characterization was carried out by determining its chemical composition. Sintering behaviour has been examined by Hot Stage Microscopy (HSM). Thermal stability and crystallization mechanism have been studied by Diff...

Scratch resistance of SiO2 and SiO2 - ZrO2 sol-gel coatings on glass-ceramic obtained by sintering

International Nuclear Information System (INIS)

Soares, V. O.; Soares, P.; Peitl, O.; Zanotto, E. D.; Duran, A.; Castro, Y.

2013-01-01

The sol-gel process is widely used to obtain coatings on glass-ceramic substrates in order to improve the scratch and abrasion resistance, also providing a bright and homogeneous appearance of a glaze avoiding expensive final polishing treatments. This paper describes the preparation of silica and silica / zirconia coatings by sol-gel method on Li 2 O-Al 2 O3-SiO 2 (LAS) glassceramic substrates produced by sintering. The coatings were deposited by dip-coating on LAS substrates and characterized by optical microscopy and spectral ellipsometry. On the other hand, hardness and elastic modulus, coefficient of friction and abrasion and scratch resistance of the coatings were determined and compared with the substrate properties. Coatings deposited on LAS glass-ceramic confere the substrate a bright and homogeneous aspect, similar to a glaze, improving the appearance and avoiding the final polishing. However these coatings do not increase the scratch resistance of the substrate only equaling the properties of the glass-ceramic. (Author)

Kinetic Rate Law Parameter Measurements on a Borosilicate Waste Glass: Effect of Temperature, pH, and Solution Composition on Alkali Ion Exchange

International Nuclear Information System (INIS)

Pierce, Eric M.; McGrail, B PETER.; Icenhower, J P.; Rodriguez, Elsa A.; Steele, Jackie L.; Baum, Steven R.

2004-01-01

The reaction kinetics of glass is controlled by matrix dissolution and ion exchange (IEX). Dissolution of an alkali-rich simulated borosilicate waste glass was investigated using single-pass flow-through (SPFT) experiments. Experiments were conducted as a function of temperature, pH, and solution composition by varying the SiO 2 (aq) activity in the influent solution. Results showed that under dilute conditions matrix dissolution increased with increasing pH and temperature, and decreased with increasing SiO 2 (aq) activity. IEX rates decreased with increasing pH and temperature, and increased with increasing SiO 2 (aq) activity. Over the solution composition range interrogated in this study the dominant dissolution mechanism changed from matrix dissolution to IEX. These results suggest that ''secondary'' reactions may become dominant under certain environmental conditions and emphasize the need to incorporate these reactions into dissolution rate models

Dissolution rate enhancement of the poorly water-soluble drug Tibolone using PVP, SiO2, and their nanocomposites as appropriate drug carriers.

Science.gov (United States)

Papadimitriou, Sofia; Bikiaris, Dimitrios

2009-09-01

Creation of immediate release formulations for the poorly water-soluble drug Tibolone through the use of solid dispersions (SDs). SD systems of Tibolone (Tibo) with poly(vinylpyrrolidone) (PVP), fumed SiO(2) nanoparticles, and their corresponding ternary systems (PVP/SiO(2)/Tibo) were prepared and studied in order to produce formulations with enhanced drug dissolution rates. The prepared SDs were characterized by the use of differential scanning calorimetry and wide-angle X-ray diffractometry techniques. Also dissolution experiments were performed. From the results it was concluded that PVP as well as SiO(2) can be used as appropriate carriers for the amorphization of Tibo, even when the drug is used at high concentrations (20-30%, w/w). This is due to the evolved interactions taking place between the drug and the used carriers, as was verified by Fourier transform infrared spectroscopy. At higher concentrations the drug was recrystallized. Similar are the observations on the ternary PVP/SiO(2)/Tibo SDs. The dissolution profiles of the drug in PVP/Tibo and SiO(2)/Tibo SDs are directly dependent on the physical state of the drug. Immediately release rates are observed in SD with low drug concentrations, in which Tibo was in amorphous state. However, these release profiles are drastically changed in the ternary PVP/SiO(2)/Tibo SDs. An immediate release profile is observed for low drug concentrations and an almost sustained release as the concentration of Tibo increases. This is due to the weak interactions that take place between PVP and SiO(2), which result in alterations of the characteristics of the carrier (PVP/SiO(2) nanocomposites). Immediate release formulation was created for Tibolone as well as new nanocomposite matrices of PVP/SiO((2)), which drastically change the release profile of the drug to a sustained delivery.

Excellent Brightness with Shortening Lifetime of Textured Zn2SiO4:Mn2+ Phosphor Films on Quartz Glass

Science.gov (United States)

Park, Jehong; Park, Kwangwon; Lee, Jaebum; Kim, Jongsu; Kim, Seongsin Margaret; Kung, Patrick

2010-04-01

Green-emissive textured Zn2SiO4:Mn2+ phosphor films were fabricated by the thermal diffusion of ZnO:Mn on quartz glass. The Zn2SiO4:Mn2+ phosphor films became textured along several hexagonal directions and their chemical composition was continuously graded at the interface. The decay time of Mn2+ was as short as 4.4 ms, and the optical transition probability of the films defined as the inverse of decay time showed a strong correlation with film texture degree as a function of annealing temperature. The brightest Zn2SiO4:Mn2+ film showed a photoluminescent brightness as high as 65% compared with a commercial Zn2SiO4:Mn2+ phosphor powder screen and a maximum absolute transparency of 70%. These excellent optical properties are explained by the combination of the unique textured structure and continuous grading of the Zn2SiO4:Mn2+ chemical composition at the interface.

A comparison of the performance of nuclear waste glasses by modeling

International Nuclear Information System (INIS)

Grambow, B.; Strachan, D.M.

1988-12-01

Through a combination of data collection and computer modeling, the dissolution mechanism of nuclear waste glasses has been investigated and more clearly defined. Glass dissolution can be described as a dissolution/precipitation process in which glass dissolves in aqueous solution and solids precipitate as the solubility products are exceeded. The dissolution process is controlled by activity of the rate-limiting specie H 4 SiO 4 . As a concentration of H 4 SiO 4 increases, the rate of dissolution decreases until a final reaction rate is reached. Between the forward reaction rate (early time) and final reaction rate (very long time), glasses may exhibit an intermediate root time dependence caused by a transport resistance for the diffusion of H 4 SiO 4 within the gel layer on the glass surface. In this report, three glasses are studied: JSS-A, PNL 76-68, and SRL-131. Data from static and dynamic leach tests are assembled, plotted, and successfully modeled. The kinetic parameters for these glasses are reported. With four parameters derived from experiments for each glass, the model can be used to calculate the effects of changes in the initial composition of the water contacting the glass. The effects of convective flow can also be modeled. Furthermore, glasses of different compositions can be readily compared. 49 refs., 27 figs., 5 tabs

Characterizing the residual glass in a MgO/Al2O3/SiO2/ZrO2/Y2O3 glass-ceramic

Science.gov (United States)

Seidel, Sabrina; Patzig, Christian; Wisniewski, Wolfgang; Gawronski, Antje; Hu, Yongfeng; Höche, Thomas; Rüssel, Christian

2016-01-01

The non-isochemical crystallization of glasses leads to glass-ceramics in which the chemical composition of the amorphous matrix differs from that of the parent glass. It is challenging to solely analyse the properties of these residual glassy phases because they frequently contain finely dispersed crystals. In this study, the composition of the residual glass matrix after the crystallization of a glass with the mol% composition 50.6 SiO2 · 20.7 MgO · 20.7 Al2O3 · 5.6 ZrO2 · 2.4 Y2O3 is analysed by scanning transmission electron microscopy (STEM) including energy dispersive X-ray analysis (EDXS). A batch of the residual glass with the determined composition is subsequently melted and selected properties are analysed. Furthermore, the crystallization behaviour of this residual glass is studied by X-ray diffraction, scanning electron microscopy including electron backscatter diffraction and STEM-EDXS analyses. The residual glass shows sole surface crystallization of indialite and multiple yttrium silicates while bulk nucleation does not occur. This is in contrast to the crystallization behaviour of the parent glass, in which a predominant bulk nucleation of spinel and ZrO2 is observed. The crystallization of the residual glass probably leads to different crystalline phases when it is in contact to air, rather than when it is enclosed within the microstructure of the parent glass-ceramics. PMID:27734918

Internal Friction of (SiO2)1-x (GeO2)x Glasses

OpenAIRE

Kosugi , T.; Kobayashi , H.; Kogure , Y.

1996-01-01

Internal friction of (SiO2)1-x (GeO2)x glasses (x = 0, 5, 10, 24 and 100 mole%) is measured at temperatures between 1.6 and 280 K. The data are filted with the equations for thermally activated relaxation with distributing activation energies in symmetrical double-well potentials. From the determined relaxation strength spectra for each sample, the contributions from each type of microscopic structural units are calculated assuming that transverse motion of the bridging O atom in Si-O-Si, Si-...

Antibacterial effects and dissolution behavior of six bioactive glasses.

Science.gov (United States)

Zhang, Di; Leppäranta, Outi; Munukka, Eveliina; Ylänen, Heimo; Viljanen, Matti K; Eerola, Erkki; Hupa, Mikko; Hupa, Leena

2010-05-01

Dissolution behavior of six bioactive glasses was correlated with the antibacterial effects of the same glasses against sixteen clinically important bacterial species. Powdered glasses (<45 microm) were immersed in simulated body fluid (SBF) for 48 h. The pH in the solution inside the glass powder was measured in situ with a microelectrode. After 2, 4, 27, and 48 h, the pH and concentration of ions after removing the particles and mixing the SBF were measured with a normal glass pH electrode and ICP-OES. The bacteria were cultured in broth with the glass powder for up to 4 days, after which the viability of the bacteria was determined. The antibacterial effect of the glasses increased with increasing pH and concentration of alkali ions and thus with increased dissolution tendency of the glasses, but it also depended on the bacterium type. The changes in the concentrations of Si, Ca, Mg, P, and B ions in SBF did not show statistically significant influence on the antibacterial property. Bioactive glasses showed strong antibacterial effects for a wide selection of aerobic bacteria at a high sample concentration (100 mg/mL). The antibacterial effects increased with glass concentration and a concentration of 50 mg/mL (SA/V 185 cm(-1)) was required to generate the bactericidal effects. Understanding the dissolution mechanisms of bioactive glasses is essential when assessing their antibacterial effects. Copyright 2009 Wiley Periodicals, Inc.

Crystallization and characterization of Y2O3-SiO2 glasses

Science.gov (United States)

Drummond, Charles H., III; Lee, William E.; Sanders, W. A.; Kiser, J. D.

1991-01-01

Glasses in the yttria-silica system with 20 to 40 mol pct Y2O3 were subjected to recrystallization studies after melting at 1900 to 2100 C in W crucibles in 1 and 50 atm N2. The TEM and XRD results obtained indicate the presence of the delta, gamma, gamma prime, and beta-Y2Si2O7 crystalline phases, depending on melting and quenching conditions. Heat treatment in air at 1100 to 1600 C increased the amount of crystallization, and led to the formation of Y2SiO5, cristabalite, and polymorphs of Y2Si2O7. Also investigated were the effects of 5 and 10 wt pct zirconia additions.

Characterisation and Properties of Lithium Disilicate Glass Ceramics in the SiO2-Li2O-K2O-Al2O3 System for Dental Applications

Directory of Open Access Journals (Sweden)

Naruporn Monmaturapoj

2013-01-01

Full Text Available This work proposes four different glass formulas derived from the SiO2-Li2O-K2O-Al2O3 system to investigate the effect of glass composition on their crystal formations and properties. Glass LD1 was SiO2-Li2O-K2O-Al2O3 system with the addition of P2O5 and CaF2 as nucleating agents. In Glass LD2, a slight amount of MgO was mixed in order to increase the viscosity of the melting glass. Finally, the important factor of Si : Li ratio was increased in Glasses LD3 and LD4 with compositions otherwise the same as LD1 and LD2. The results found that P2O5 and CaF2 served as a nucleating site for lithium phosphate and fluorapatite to encourage heterogenous nucleation and produce a fine-grained interlocking microstructure of lithium disilicate glass ceramics. MgO content in this system seemed to increase the viscosity of the melting glass and thermal expansion coefficient including the chemical solubility. Increasing the Si : Li ratio in glass compositions resulted in the change of the microstructure of Li2Si2O5 crystals.

Luminescence and energy transfer of Tb3+-doped BaO-Gd2O3-Al2O3-B2O3-SiO2 glasses.

Science.gov (United States)

Zuo, Chenggang; Huang, Jinze; Liu, Shaoyou; Xiao, Anguo; Shen, Youming; Zhang, Xiangyang; Zhou, Zhihua; Zhu, Ligang

2017-12-05

Transparent Tb 3+ -doped BaO-Gd 2 O 3 -Al 2 O 3 -B 2 O 3 -SiO 2 glasses with the greater than 4g/cm 3 were prepared by high temperature melting method and its luminescent properties have been investigated by measured UV-vis transmission, excitation, emission and luminescence decay spectra. The transmission spectrum shows there are three weak absorption bands locate at about 312, 378 and 484nm in the glasses and it has good transmittance in the visible spectrum region. Intense green emission can be observed under UV excitation. The effective energy transfer from Gd 3+ ion to Tb 3+ ion could occur and sensitize the luminescence of Tb 3+ ion. The green emission intensity of Tb 3+ ion could change with the increasing SiO 2 /B 2 O 3 ratio in the borosilicate glass matrix. With the increasing concentration of Tb 3+ ion, 5 D 4 → 7 F J transitions could be enhanced through the cross relaxation between the two nearby Tb 3+ ions. Luminescence decay time of 2.12ms from 546nm emission is obtained. The results indicate that Tb 3+ -doped BaO-Gd 2 O 3 -Al 2 O 3 -B 2 O 3 -SiO 2 glasses would be potential scintillating material for applications in X-ray imaging. Copyright © 2017 Elsevier B.V. All rights reserved.

Dissolution of basaltic glass in seawater: Mechanism and rate

International Nuclear Information System (INIS)

Crovisier, J.L.; Honnorez, J.; Eberhart, J.P.

1987-01-01

Basaltic glasses are considered as natural analogues for nuclear waste glasses. Thermodynamic computer codes used to evaluate long term behavior of both nuclear waste and basaltic glasses require the knowledge of the dissolution mechanism of the glass network. The paper presents the results of a series of experiments designed to study the structure and chemical composition of alteration layers formed on the surface of artificial tholeiitic glass altered in artificial seawater. Experiments were performed at 60 degree C, 1 bar and 350 bars in non-renewed conditions. A natural sample from Palagonia (Sicily) has been studied by electron microscopy and comparison between natural and experimental palagonitic layers is made. The behavior of dissolved silica during experiments, and both the structure and the chemical composition of the palagonitic layers, indicate that they form by precipitation of secondary minerals from solution after a total breakdown of the glassy network, i.e., congruent dissolution of the glass. Hence the dissolution equation necessary for thermodynamic modelling of basaltic glass dissolution in seawater at low temperature must be written as a simple stoichiometric process. These experiments indicate that the transformation of glass to palagonitic material is not isovolumetric. Hence it is preferable to use Fe or Ti as conservative elements for chemical budget calculations

Numerical modelling of glass dissolution: gel layer morphology

Energy Technology Data Exchange (ETDEWEB)

Devreux, F. E-mail: fd@pmc.polytechnique.fr; Barboux, P

2001-09-01

Numerical simulations of glass dissolution are presented. The glass is modelized as a random binary mixture composed of two species representing silica and soluble oxides, such as boron and alkali oxides. The soluble species are dissolved immediately when they are in contact with the solution. For the species which represents silica, one introduces dissolution and condensation probabilities. It is shown that the morphology and the thickness of the surface hydration layer (the gel) are highly dependent on the dissolution model, especially on the parameter which controls the surface tension. Simulations with different glass surface area to solution volume ratio (S/V) show that this experimental parameter has important effects on both the shrinkage and the gel layer thickness.

The effect of clay on the dissolution of nuclear waste glass

Science.gov (United States)

Lemmens, K.

2001-09-01

In a nuclear waste repository, the waste glass can interact with metals, backfill materials (if present) and natural host rock. Of the various host rocks considered, clays are often reported to delay the onset of the apparent glass saturation, where the glass dissolution rate becomes very small. This effect is ascribed to the sorption of silica or other glass components on the clay. This can have two consequences: (1) the decrease of the silica concentration in solution increases the driving force for further dissolution of glass silica, and (2) the transfer of relatively insoluble glass components (mainly silica) from the glass surface to the clay makes the alteration layer less protective. In recent literature, the latter explanation has gained credibility. The impact of the environmental materials on the glass surface layers is however not well understood. Although the glass dissolution can initially be enhanced by clay, there are arguments to assume that it will decrease to very low values after a long time. Whether this will indeed be the case, depends on the fate of the released glass components in the clay. If they are sorbed on specific sites, it is likely that saturation of the clay will occur. If however the released glass components are removed by precipitation (growth of pre-existing or new secondary phases), saturation of the clay is less likely, and the process can continue until exhaustion of one of the system components. There are indications that the latter mechanism can occur for varying glass compositions in Boom Clay and FoCa clay. If sorption or precipitation prevents the formation of protective surface layers, the glass dissolution can in principle proceed at a high rate. High silica concentrations are assumed to decrease the dissolution rate (by a solution saturation effect or by the impact on the properties of the glass alteration layer). In glass corrosion tests at high clay concentrations, silica concentrations are, however, often higher

The effect of clay on the dissolution of nuclear waste glass

International Nuclear Information System (INIS)

Lemmens, K.

2001-01-01

In a nuclear waste repository, the waste glass can interact with metals, backfill materials (if present) and natural host rock. Of the various host rocks considered, clays are often reported to delay the onset of the apparent glass saturation, where the glass dissolution rate becomes very small. This effect is ascribed to the sorption of silica or other glass components on the clay. This can have two consequences: (1) the decrease of the silica concentration in solution increases the driving force for further dissolution of glass silica, and (2) the transfer of relatively insoluble glass components (mainly silica) from the glass surface to the clay makes the alteration layer less protective. In recent literature, the latter explanation has gained credibility. The impact of the environmental materials on the glass surface layers is however not well understood. Although the glass dissolution can initially be enhanced by clay, there are arguments to assume that it will decrease to very low values after a long time. Whether this will indeed be the case, depends on the fate of the released glass components in the clay. If they are sorbed on specific sites, it is likely that saturation of the clay will occur. If however the released glass components are removed by precipitation (growth of pre-existing or new secondary phases), saturation of the clay is less likely, and the process can continue until exhaustion of one of the system components. There are indications that the latter mechanism can occur for varying glass compositions in Boom Clay and FoCa clay. If sorption or precipitation prevents the formation of protective surface layers, the glass dissolution can in principle proceed at a high rate. High silica concentrations are assumed to decrease the dissolution rate (by a solution saturation effect or by the impact on the properties of the glass alteration layer). In glass corrosion tests at high clay concentrations, silica concentrations are, however, often higher

The far infrared radiation characteristics for Li2O.Al2O3.4SiO2(LAS) glass-ceramics and transition-metal oxide

International Nuclear Information System (INIS)

Huh, Nam Jung; Yang, Joong Sik

1991-01-01

The far infrared radiation characteristic for Li 2 O.Al 2 O 3 .4SiO 2 (LAS) glass, the LAS glass-ceramic and sintered transition metal oxides such as CuO, Fe 2 O 3 and Co 3 O 4 , were investigated. LAS glass and LAS glass-ceramic was higher than that of the LAS glass. Heat-treated CuO and Co 3 o 4 had radiation characteristic of high efficiency infrared radiant, and heat-treated Fe 2 O 3 had radiation characteristic that infrared emissivity decreased in higher was length above 15μm. (Author)

Influence of CeO2 on structural properties of glasses by using ultrasonic technique: comparison between the local sand and SiO2.

Science.gov (United States)

Laopaiboon, Raewat; Bootjomchai, Cherdsak

2013-04-01

Comparison between the local sand and SiO2 with different compositions of CeO2 on the structural properties of glasses was carried out by using ultrasonic technique. The ultrasonic velocities were measured by the pulse echo technique with a frequency of 4 MHz and at room temperature. From these obtained velocities and densities, various elastic moduli, micro-hardness and Poisson's ratio were calculated. The interesting point of the bulk modulus (SiO2 glass system) decreases at x = 1.25 mol.% initially before it turns to increase between x = 3.75 and x = 5.00 mol.%. While the bulk modulus of the local sand glass system is near constant. FTIR spectra were used to study the structural properties of the prepared glass system. The results supported our discussion of the formation of non-bridging oxygens (NBO) and bridging oxygens (BO). Copyright © 2013 Elsevier B.V. All rights reserved.

Effect of alumina on the dissolution rate of glasses

International Nuclear Information System (INIS)

Palavit, G.; Montagne, L.

1997-01-01

Small alumina addition to silicate glasses improves their chemical durability, but a large amount of alumina can also be beneficial to obtain a high dissolution rate. This paper describes the effect of Al 3+ on the early stage of glass alteration, in relation with its coordination in the glass and also with the reactions involved (hydrolysis and ionic exchange). We describe briefly nuclear magnetic resonance tools available to characterize the aluminum environments in the glasses. The rote of alumina on the dissolution rate of phosphate glasses is also discussed in order to show that the effect of Al 3+ is dependant upon the nature of the glass matrix. (author)

Glass dissolution rate measurement and calculation revisited

Energy Technology Data Exchange (ETDEWEB)

Fournier, Maxime, E-mail: maxime.fournier@cea.fr [CEA, DEN, DTCD, SECM, F-30207, Bagnols sur Cèze (France); Ull, Aurélien; Nicoleau, Elodie [CEA, DEN, DTCD, SECM, F-30207, Bagnols sur Cèze (France); Inagaki, Yaohiro [Department of Applied Quantum Physics & Nuclear Engineering, Kyushu University, Fukuoka, 819-0395 (Japan); Odorico, Michaël [ICSM-UMR5257 CEA/CNRS/UM2/ENSCM, Site de Marcoule, BP17171, F-30207, Bagnols sur Cèze (France); Frugier, Pierre; Gin, Stéphane [CEA, DEN, DTCD, SECM, F-30207, Bagnols sur Cèze (France)

2016-08-01

Aqueous dissolution rate measurements of nuclear glasses are a key step in the long-term behavior study of such waste forms. These rates are routinely normalized to the glass surface area in contact with solution, and experiments are very often carried out using crushed materials. Various methods have been implemented to determine the surface area of such glass powders, leading to differing values, with the notion of the reactive surface area of crushed glass remaining vague. In this study, around forty initial dissolution rate measurements were conducted following static and flow rate (SPFT, MCFT) measurement protocols at 90 °C, pH 10. The international reference glass (ISG), in the forms of powders with different particle sizes and polished monoliths, and soda-lime glass beads were examined. Although crushed glass grains clearly cannot be assimilated with spheres, it is when using the samples geometric surface (S{sub geo}) that the rates measured on powders are closest to those found for monoliths. Overestimation of the reactive surface when using the BET model (S{sub BET}) may be due to small physical features at the atomic scale—contributing to BET surface area but not to AFM surface area. Such features are very small compared with the thickness of water ingress in glass (a few hundred nanometers) and should not be considered in rate calculations. With a S{sub BET}/S{sub geo} ratio of 2.5 ± 0.2 for ISG powders, it is shown here that rates measured on powders and normalized to S{sub geo} should be divided by 1.3 and rates normalized to S{sub BET} should be multiplied by 1.9 in order to be compared with rates measured on a monolith. The use of glass beads indicates that the geometric surface gives a good estimation of glass reactive surface if sample geometry can be precisely described. Although data clearly shows the repeatability of measurements, results must be given with a high uncertainty of approximately ±25%. - Highlights: • Initial dissolution

Gels and gel-derived glasses in the system Na2O-B2O3-SiO2

Science.gov (United States)

Mukherjee, S. P.

1983-01-01

The containerless melting of high-purity multicomponent homogeneous gels and gel monoliths offers a unique approach to making ultrapure multicomponent optical glasses in the reduced gravity environment of space. Procedures for preparing and characterizing gels and gel-derived glasses in the system Na2O-B2O3-SiO2 are described. Preparation is based on the polymerization reactions of alkoxysilane with trimethyl borate or boric acid and a suitable sodium compound. The chemistry of the gelling process is discussed in terms of process parameters and the gel compositions. The physicochemical nature of gels prepared by three different procedures was found to be significantly different. Infrared absorption spectra indicate finite differences in the molecular structures of the different gels. The melting of the gel powders and the transformation of porous gel monoliths to transparent 'glass' without melting are described.

Spectroscopic features of Ni(2+) ion in PbO-Bi2O3-SiO2 glass system.

Science.gov (United States)

Suresh, B; Srinivasa Reddy, M; Siva Sesha Reddy, A; Gandhi, Y; Ravi Kumar, V; Veeraiah, N

2015-04-15

Glasses of the composition (30-x)PbO-5Bi2O3-65SiO2: xNiO (with x ranging from 0 to 1.0 mol%) were synthesized. A variety of spectroscopic studies, viz., IR, Raman optical absorption and luminescence properties of these glasses have been carried out as a function of NiO concentration. The analysis of results of all these studies has indicated that the nickel ions occupy both octahedral and tetrahedral positions. However, with the increase of NiO concentration the octahedral occupancy of Ni(2+) ions prevailed over the tetrahedral ions. The luminescence spectra of these glasses have exhibited a broad NIR emission band in region 1100-1500 nm. This band is identified as being due to (3)T2(3F)→(3)A2(3F) octahedral transition of Ni(2+) ions. The luminescence efficiency and cross section have been found to be the highest for the glass containing the highest concentration of NiO. The reasons for such high luminescence efficiency have been discussed in the light of structural variations taking place in the host glass network. Copyright © 2015 Elsevier B.V. All rights reserved.

Self induced gratings in ternary SiO2:SnO2:Na2O bulk glasses by UV light seeding.

Science.gov (United States)

Lancry, M; Douay, M; Niay, P; Beclin, F; Menke, Y; Milanese, D; Ferraris, M; Poumellec, B

2005-09-05

The diffraction efficiency of gratings written in ternary SnO2:SiO2:Na2O bulk glasses rises dramatically with time after the occultation of the cw 244nm light used to write the thick hologram. This self-induced behavior lasts for several hours and ultimately leads to refractive index changes as high as 3 10-3.

Theoretical prediction of Grüneisen parameter for SiO_2.TiO_2 bulk metallic glasses

International Nuclear Information System (INIS)

Singh, Chandra K.; Pandey, Brijesh K.; Pandey, Anjani K.

2016-01-01

The Grüneisen parameter (γ) is very important to decide the limitations for the prediction of thermoelastic properties of bulk metallic glasses. It can be defined in terms of microscopic and macroscopic parameters of the material in which former is based on vibrational frequencies of atoms in the material while later is closely related to its thermodynamic properties. Different formulation and equation of states are used by the pioneer researchers of this field to predict the true sense of Gruneisen parameter for BMG but for SiO_2.TiO_2 very few and insufficient information is available till now. In the present work we have tested the validity of two different isothermal EOS viz. Poirrior-Tarantola EOS and Usual-Tait EOS to predict the true value of Gruneisen parameter for SiO_2.TiO_2 as a function of compression. Using different thermodynamic limitations related to the material constraints and analyzing obtained result it is concluded that the Poirrior-Tarantola EOS gives better numeric values of Grüneisen parameter (γ) for SiO_2.TiO_2 BMG.

Attenuation of glass dissolution in the presence of natural additives

Energy Technology Data Exchange (ETDEWEB)

Sang, Jing C.; Barkatt, Aaron [Department of Chemistry, The Catholic University of America, Washington, DC (United States); O`Keefe, John A. [National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, MD (United States)

1996-11-01

The dissolution kinetics of silicate glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase are reported. The results demonstrate the possibility of a dramatic decrease in the rate of dissolution of silicate glass in the presence of certain varieties of olivine-based materials. This decrease in dissolution rate was shown to be due to the fact that these additives consist mostly of Mg-based material but also contain minor amounts of Al and Ca. The combined presence of Mg with these minor species affected the corrosion rate of the glass as a whole, including its most soluble components such as boron. This study has potentially important implications to the durability of glasses exposed to natural environments. The results may be relevant to the use of active backfill materials in burial sites for nuclear waste glasses, as well as to better understanding of the environmental degradation of natural and ancient glasses.

Crystallization behavior and properties of BaO-Al2O3-2SiO2 glass matrices

Science.gov (United States)

Drummond, Charles H., III; Bansal, Narottam P.

1990-01-01

Glass of stoichiometric celsian composition, BaO-Al2O3-SiO2, has a density of 3.39 g/cu cm, a thermal expansion coefficient of 6.6 x 10 to the -6th/C, a glass-transition temperature of 910 C, and a dilatometric softening point of 925 C. On heat treatment, only hexacelsian crystallized out on the surface, but both celsian and hexacelsian were present in the bulk. Effects of cold isostatic pressing (CIP), sintering, and hot-pressing, in the presence and absence of an additive, on the formation of the celsian phase in the glass have been studied. CIP'd samples, after appropriate heat treatments, always crystallized out as celsian, whereas presence of 5-10 wt pct of an additive was necessary for formation of celsian in sintered as well as hot-pressed specimens. Green density increased with CIP'ing pressure but had no effect on sintered density. Hot-pressing resulted in fully dense samples.

The dissolution behavior of borosilicate glasses in far-from equilibrium conditions

Science.gov (United States)

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin P.; Ryan, Joseph V.; Asmussen, R. Matthew

2018-04-01

An area of agreement in the waste glass corrosion community is that, at far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this work is to study the effects of temperature and pH on the dissolution rate of three model nuclear waste glasses (SON68, ISG, AFCI). The dissolution rate data are then used to parameterize a kinetic rate model based on Transition State Theory that has been developed to model glass corrosion behavior in dilute conditions. To do this, experiments were conducted at temperatures of 23, 40, 70, and 90 °C and pH (22 °C) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies though quantifiable differences exist. The glass dissolution rates were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), with which a robust uncertainty analysis is performed. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, a mathematical description of the effect of glass composition on the rate parameter values should be possible. This would allow for the possibility of calculating the forward dissolution rate of glass based solely on composition. In addition, the method of determination of parameter uncertainty and correlation provides a framework for other rate models that describe the dissolution rates of other amorphous and crystalline materials in a wide range of chemical conditions. The higher level of uncertainty analysis would provide

Bioactive SrO-SiO2 glass with well-ordered mesopores: characterization, physiochemistry and biological properties.

Science.gov (United States)

Wu, Chengtie; Fan, Wei; Gelinsky, Michael; Xiao, Yin; Simon, Paul; Schulze, Renate; Doert, Thomas; Luo, Yongxiang; Cuniberti, Gianaurelio

2011-04-01

For a biomaterial to be considered suitable for bone repair it should ideally be both bioactive and have a capacity for controllable drug delivery; as such, mesoporous SiO(2) glass has been proposed as a new class of bone regeneration material by virtue of its high drug-loading ability and generally good biocompatibility. It does, however, have less than optimum bioactivity and controllable drug delivery properties. In this study, we incorporated strontium (Sr) into mesoporous SiO(2) in an effort to develop a bioactive mesoporous SrO-SiO(2) (Sr-Si) glass with the capacity to deliver Sr(2+) ions, as well as a drug, at a controlled rate, thereby producing a material better suited for bone repair. The effects of Sr(2+) on the structure, physiochemistry, drug delivery and biological properties of mesoporous Sr-Si glass were investigated. The prepared mesoporous Sr-Si glass was found to have an excellent release profile of bioactive Sr(2+) ions and dexamethasone, and the incorporation of Sr(2+) improved structural properties, such as mesopore size, pore volume and specific surface area, as well as rate of dissolution and protein adsorption. The mesoporous Sr-Si glass had no cytotoxic effects and its release of Sr(2+) and SiO(4)(4-) ions enhanced alkaline phosphatase activity - a marker of osteogenic cell differentiation - in human bone mesenchymal stem cells. Mesoporous Sr-Si glasses can be prepared to porous scaffolds which show a more sustained drug release. This study suggests that incorporating Sr(2+) into mesoporous SiO(2) glass produces a material with a more optimal drug delivery profile coupled with improved bioactivity, making it an excellent material for bone repair applications. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Impact of iron chelators on short-term dissolution of basaltic glass

Science.gov (United States)

Perez, Anne; Rossano, Stéphanie; Trcera, Nicolas; Verney-Carron, Aurélie; Huguenot, David; van Hullebusch, Eric D.; Catillon, Gilles; Razafitianamaharavo, Angelina; Guyot, François

2015-08-01

Although microorganisms seem to play an important role in the alteration processes of basaltic glasses in solution, the elementary mechanisms involved remain unclear in particular with regard to the role of organic ligands excreted by the cells. Two glasses, one with Fe and one without Fe were synthesized to model basaltic glass compositions. Fe in the glass was mostly Fe(III) for enhancing interaction with siderophores, yet with small but significant amounts of Fe(II) (between 10% and 30% of iron). The prepared samples were submitted to abiotic alteration experiments in buffered (pH 6.4) diluted solutions of metal-specific ligands, namely oxalic acid (OA, 10 mM), desferrioxamine (DFA, 1 mM) or 2,2‧-bipyridyl (BPI, 1 mM). Element release from the glass into the solution after short term alteration (maximum 1 week) was measured by ICP-OES, and normalized mass losses and relative release ratios (with respect to Si) were evaluated for each element in each experimental condition. The presence of organic ligands had a significant effect on the dissolution of both glasses. Trivalent metals chelators (OA, DFA) impacted on the release of Fe3+ and Al3+, and thus on the global dissolution of both glasses, enhancing all release rates and dissolution stoichiometry (release rates were increased up to 7 times for Al or Fe). As expected, the mostly divalent metal chelator BPI interacted preferentially with Ca2+, Mg2+ and Fe2+. This study thus allows to highlight the central roles of iron and aluminium in interaction with some organic ligands in the alteration processes of basaltic glasses. It thus provides a step toward understanding the biological contribution of this fundamental geological process.

Non-isothermal crystallization kinetics and phase transformation of Bi2O3-SiO2 glass-ceramics

Directory of Open Access Journals (Sweden)

Guo H.W.

2011-01-01

Full Text Available The Bi2O3-SiO2 (BS glass-ceramics were prepared by melt-quench technique, and the crystallization kinetics and phase transformation behavior were investigated in accordance with Kissinger and Johson-Mehl-Avrami equation, DSC, XRD and SEM. The results show that in the heat treatment process (or termed as re-crystallizing process Bi2SiO5 and Bi4Si3O12 crystals were found consequently. Respectively, the crystallization activation energies of the two crystals are Ep1=14.8kJ/mol and Ep2=34.1kJ/mol. And the average crystallization index of n1=1.73 and n2=1.38 suggested volume nucleation, one-dimensional growth and surface nucleation, one-dimensional growth from surface to the inside respectively. The meta-stable needle-like Bi2SiO5 crystals are easily to be transformed into stable prismatic Bi4Si3O12 crystals. By quenching the melt and hold in 850°C for 1h, the homogenous single Bi4Si3O12 crystals were found in the polycrystalline phase of the BS glassceramics system.

Phonon spectra in SiO2 glasses

International Nuclear Information System (INIS)

Perez R, J.F.; Jimenez S, S.; Gonzalez H, J.; Vorobiev, Y.V.; Hernandez L, M.A.; Parga T, J.R.

1999-01-01

Phonon spectra in SiO 2 sol-gel made glasses annealed under different conditions are investigated using infrared absorption and Raman scattering. These data are compared with those obtained in commercial optical-quality quartz. All the materials exhibit the same phonon bands, the exact position and the intensity depend on the measuring technique and on the sample preparation method. The phonon spectra in this material are interpreted on the basis of a simple quasi-linear description of elastic waves in an O-Si-O chain. It is shown that the main features observed in the range 400-1400 cm -1 can be predicted using a quasi-linear chain model in which the band at 1070 cm -1 is assigned to the longitudinal optical waves in the O-Si-O chain with the smallest possible wavelength at the Brillouin zone boundary, the band located around 450 cm -1 is assigned to the transversal optical waves and the band at 800 cm -1 to the longitudinal acoustical waves with the same wavelength. The degree of structural disorder can be also deduced within the framework of the proposed model. (Author)

Kinetics of dissolution of sapphire in melts in the CaO-Al2O3-SiO2 system

Science.gov (United States)

Shaw, Cliff S. J.; Klausen, Kim B.; Mao, Huahai

2018-05-01

diffusion is itself controlled by the structural modifications required by the addition of new components to the melt. Comparison of quartz dissolution rates in similar melts shows that dissolution is much faster for quartz than for sapphire and that dissolution rates show the same correlation with silica activity and viscosity. We suggest that diffusive fluxes are related to changes in melt structure and the nature of the reaction that incorporates the added component. For the slow eigendirection, SiO2 addition occurs by a single reaction whereas Al2O3 addition requires a more complex two part reaction in which Al is accommodated by charge balance with Ca until Al is in excess of that which can be charge balanced. The Alxs incorporation reaction, is slower than the Si incorporation reaction which inhibits sapphire dissolution relative to quartz in melts of the same composition.

Glass composition and solution speciation effects on stage III dissolution

International Nuclear Information System (INIS)

Trivelpiece, Cory L.; Rice, Jarret A.; Pantano, Carlo G.

2017-01-01

To understand and mitigate the onset of Stage III corrosion of multicomponent oxides waste glasses. Stage III refers to a resumption of the high initial rate of glass dissolution in some glass samples that have otherwise exhibited dissolution at the much lower residual rate for a long time (Stage II). Although the onset of Stage III is known to occur concurrently with the precipitation of particular alteration products, the root cause of the transition is still unknown. Certain glass compositions (notably AFCI) and high pH environmental conditions are also associated with this observed transition.

Glass composition and solution speciation effects on stage III dissolution

Energy Technology Data Exchange (ETDEWEB)

Trivelpiece, Cory L. [Pennsylvania State Univ., University Park, PA (United States); Rice, Jarret A. [Pennsylvania State Univ., University Park, PA (United States); Pantano, Carlo G. [Pennsylvania State Univ., University Park, PA (United States)

2017-10-03

To understand and mitigate the onset of Stage III corrosion of multicomponent oxides waste glasses. Stage III refers to a resumption of the high initial rate of glass dissolution in some glass samples that have otherwise exhibited dissolution at the much lower residual rate for a long time (Stage II). Although the onset of Stage III is known to occur concurrently with the precipitation of particular alteration products, the root cause of the transition is still unknown. Certain glass compositions (notably AFCI) and high pH environmental conditions are also associated with this observed transition.

CHARACTERIZATION OF COMMERCIALLY AVAILABLE ALKALI RESISTANT GLASS FIBER FOR CONCRETE REINFORCEMENT AND CHEMICAL DURABILITY COMPARISON WITH SrO-Mn2O3-Fe2O3-MgO-ZrO2-SiO2 (SMFMZS SYSTEM GLASSES

Directory of Open Access Journals (Sweden)

Göktuğ GÜNKAYA

2012-12-01

Full Text Available According to the relevant literature, the utilization of different kind of glass fibers in concrete introduces positive effect on the mechanical behavior, especially toughness. There are many glassfibers available to reinforce concretes. Glass fiber composition is so important because it may change the properties such as strength, elastic modulus and alkali resistance. Its most important property to be used in concrete is the alkali resistance. Some glasses of SrO–MgO–ZrO2–SiO2 (SMZS quaternary system, such as 26SrO, 20MgO, 14ZrO2, 40SiO2 (Zrn glass, have been found to be highly alkali resistant thanks to their high ZrO2 and MgO contents. Previous researches on these glasses with MnO and/or Fe2O3 partially replacing SrO have been made with the aim of improving the chemical resistance and decreasing the production cost.The main target of the present study, first of all, was to characterize commercially available alkali resistant glass fiber for concrete reinforcement and then to compare its alkali durability with those of the SrO-Mn2O3-Fe2O3-MgO-ZrO2-SiO2 (SMFMZS system glasses. For such purposes, XRF, Tg-DTA, alkali resistance tests and SEM analysis conducted with EDX were employed. According tothe alkali endurance test results it was revealed that some of the SMFMZS system glass powders are 10 times resistant to alkali environments than the commercial glass fibers used in this study.Therefore, they can be considered as alternative filling materials on the evolution of chemically resistant concrete structures.

DISSOLUTION BEHAVIOR OF BIOACTIVE GLASS CERAMICS WITH DIFFERENT CaO/MgO RATIOS

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MUHAMMAD USMAN HASHMI

2010-03-01

Full Text Available In this work, powders of three different compositions, each having 34 SiO2-14.5 P2O5-1 CaF2-0.5 MgF (% wt and ratio of CaO/MgO varying from 11.5:1 to 1:11.5 were thoroughly mixed and melted under oxy-acetylene flame in a fire clay crucible that made the glass formation cheaper in time and cost. The melt of each composition was quenched in water to form three different glasses. Every glass was sintered at 950°C to form three glass ceramics named G1, G2 and G3 respectively. To study the dissolution behavior, each sample was immersed in a simulated body fluid (SBF for 2, 5, 10, 20 and 25 days at room temperature. Thin film XRD analysis revealed that the samples with larger CaO/MgO ratio exhibited better bioactivity. pH of SBF increased efficiently in case of G1 whereas in case of G2 and G3, this increase was slower due to greater amount of MgO. The concentrations of Ca, P, Mg and Si ions were measured by Atomic Absorption Spectroscopy. EDS analysis showed the increase in P and Ca ions and presence of C in G1 after 5 days immersion and after 10 days, in case of G2 indicating the higher formation rate of hydroxycarbonate Apatite layer in G1 as compared to G2 due to greater CaO/MgO ratio whereas in G3 Mg-hydroxycarbonate apatite (Ca(Mg5(CO3(PO43(OH (heneuite layer was recognized after 20 days showing the least bioactivity due to very large amount of Mg and the least CaO/MgO ratio.

Structural studies of gels and gel-glasses in the SiO2-GeO2 system using vibrational spectroscopy

Science.gov (United States)

Mukherjee, Shyama P.; Sharma, Shiv K.

1986-01-01

GeO2 gel and gels in the SiO2-GeO2 system synthesized by the hydrolytic polycondensation of metal alkoxides have been studied by infrared and Raman spectroscopic techniques. The molecular structures, hydroxyl contents, and crystallinity of gels and gel-glasses in relation to the thermal history and GeO2 concentration were investigated. The binary compositions having up to 70 mol percent GeO2 were examined.

Predicting the dissolution kinetics of silicate glasses using machine learning

Science.gov (United States)

Anoop Krishnan, N. M.; Mangalathu, Sujith; Smedskjaer, Morten M.; Tandia, Adama; Burton, Henry; Bauchy, Mathieu

2018-05-01

Predicting the dissolution rates of silicate glasses in aqueous conditions is a complex task as the underlying mechanism(s) remain poorly understood and the dissolution kinetics can depend on a large number of intrinsic and extrinsic factors. Here, we assess the potential of data-driven models based on machine learning to predict the dissolution rates of various aluminosilicate glasses exposed to a wide range of solution pH values, from acidic to caustic conditions. Four classes of machine learning methods are investigated, namely, linear regression, support vector machine regression, random forest, and artificial neural network. We observe that, although linear methods all fail to describe the dissolution kinetics, the artificial neural network approach offers excellent predictions, thanks to its inherent ability to handle non-linear data. Overall, we suggest that a more extensive use of machine learning approaches could significantly accelerate the design of novel glasses with tailored properties.

The phenomenon of phase separated in Na2O-B2O3-SiO2, Na2O-SiO2-P2O5 glasses

International Nuclear Information System (INIS)

Procyk, B.; Bieniarz, P.; Plichta, E.; Pudelek, B.; Kucinski, G.; Staniewicz-Brudnik, B.

1997-01-01

During the thermal treatment, the phenomenon of phase separation has been observed in the some glasses. The glass has became opaque, due to the opalescence of phase separated. Investigations of the phenomenon of phase separation were conducted using the basic systems: Na 2 O-B 2 O 3 -SiO 2 , Na 2 O-SiO 2 -P 2 O 5 and theirs modifications. The occurrence of binodal and spinodal phase decomposition was observed by TEM. The phase separation inhomogeneities have drop-like character and with higher concentration shows a tendency for coalescence. The influence of the chemical composition, temperature and time on the phenomenon of phase separation in the investigated glasses has been defined. (author)

Processamento e caracterização de espumas vitrocerâmicas do sistema sncp (Sio2-Na2o-Cao-P2 O5 Processing and characterization of sncp (Sio2-Na2o-Cao-P2o5 glass-ceramic foams

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Karoline Bastos Mundstock

2010-01-01

Full Text Available Glass-ceramics foams prepared from glasses of the SiO2-Na2O-CaO-P2O5 by replication process were obtained and characterized in terms of their chemical and physical properties by X-ray fluorescence, X-ray diffraction, laser diffraction, thermal analysis, density, mechanical strength, microstructural and cytotoxic analysis. The results showed that it is possible to produce glass-ceramic foams by the replication method with optimized properties but cytotoxic analysis indicates that the glass-ceramic foams are not bioactive materials. Mechanical strength values varying from 0.5 to 1.0 MPa and from 0.8 to 2.3 MPa were reached for mean particle sizes of 10 and 6 µm, respectively.

TiO2 effect on crystallization mechanism and physical properties of nano glass-ceramics of MgO-Al2O3-SiO2 glass system.

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Jo, Sinae; Kang, Seunggu

2013-05-01

The effect of TiO2 on the degree of crystallization, thermal properties and microstructure for MgO-Al2O3-SiO2 glass-ceramics system containing 0-13 wt% TiO2 and 0-1.5 wt% B2O3 in which the cordierite is the main phase was studied. Using Kissinger and Augis-Bennett equations, the activation energy, 510 kJ/mol and Avrami constant, 1.8 were calculated showing the surface-oriented crystallization would be preferred. The alpha-cordierite phase was generated in the glass-ceramics of containing TiO2 of 0-5.6 wt%. However, for the glass-ceramics of TiO2 content above 7 wt%, an alpha-cordierite disappeared and micro-cordierite phase was formed. The glass-ceramics of no TiO2 added had spherical crystals of few tens nanometer size spread in the matrix. As TiO2 content increased up to 5.6 wt%, a lump of dendrite was formed. In the glass-ceramics containing TiO2 7-13 wt%, in which the main phase is micro-cordierite, the dendrite crystal disappeared and a few hundred nanometer sized crystal particles hold tightly each other were generated. The thermal conductivity of glass-ceramics of both a-cordierite and micro-cordierite base decreased with TiO2 contend added. The thermal conductivity of glass-ceramics of 1.5 wt% TiO2 added was 3.4 W/mK which is 36% higher than that of glass-ceramics of no TiO2 added. The sintering temperature for 1.5 wt% TiO2 glass-ceramics was 965 degrees C which could be concluded as to apply to LTCC process for LED packaging.

Mechanisms and kinetics laws of inactive R7T7 reference glass dissolution in water at 90 deg C: initial dissolution rate measurements

International Nuclear Information System (INIS)

Advocat, T.; Ghaleb, D.; Vernaz, E.

1993-02-01

The initial dissolution rate of inactive R7T7 reference glass was measured at 90 deg C in dilute aqueous solutions first at unspecified pH, then with imposed pH values. In distilled water, R7T7 glass corrosion initially involved preferential extraction of boron and network modifier elements (Li, Na, Ca) as long as the solution pH remained acid. When the solution pH became alkaline, glass dissolution was stoichiometric. These two mechanisms were confirmed by dissolution tests in aqueous solutions at imposed pH values under acid and alkaline conditions. The initial dissolution rate r 0 in mole.cm -3 .s -1 also increased significantly in alkaline media when the pH of the aqueous phase increased: in slightly acid media, selective glass dissolution formed a residual, de-alkalinized, hydrated glass that was characterized by transmission electron microscopy and secondary ion mass spectrometry. Under steady-state dissolution conditions, the initial glass corrosion rate (in mole.cm -3 .s -1 ) was: in acid and alkaline media, amorphous and crystallized alteration products formed after complete dissolution of the silicated glass network. The first products formed consisted mainly of Zr, Rare Earths, Fe and Al. (author). 67 refs., 29 figs., 26 tabs., 21 plates

Optical properties of transparent Li2O-Ga2O3-SiO2 glass-ceramics embedding Ni-doped nanocrystals

International Nuclear Information System (INIS)

Suzuki, Takenobu; Murugan, Ganapathy Senthil; Ohishi, Yasutake

2005-01-01

Transparent Li 2 O-Ga 2 O 3 -SiO 2 (LGS) glass-ceramics embedding Ni:LiGa 5 O 8 nanocrystals were fabricated. An intense emission centered around 1300 nm with the width of more than 300 nm was observed by 976 nm photoexcitation of the glass-ceramics. The lifetime was more than 900 μs at 5 K and 500 μs at 300 K. The emission could be attributed to the 3 T 2g ( 3 F)→ 3 A 2g ( 3 F) transition of Ni 2+ in distorted octahedral sites in LiGa 5 O 8 . The product of stimulated emission cross section and lifetime for the emission was about 3.7x10 -24 cm 2 s and was a sufficiently practical value

Effect of alkali earth oxides on hydroxy-carbonated apatite nano layer formation for SiO2-BaO-CaO-Na2O-P2O5 glass system

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Kiran, P.; Ramakrishna, V.; Shashikala, H. D.; Udayashankar, N. K.

2017-11-01

Barium soda lime phosphosilicate [(58SiO2-(32 - x)BaO- xCao-6Na2O-4P2O5 (where x = 15, 20, 25 and 30 mol%)] samples were synthesised using conventional sol-gel method at 700 °C sintering temperature. Thermal, structural properties were studied using thermo gravimetric analysis and differential thermal analysis, X-ray diffraction, scanning electron microscopy, fourier transform infrared and Raman spectroscopy. Using Raman spectra non-bridging oxygen concentrations were estimated. The hydroxy-carbonated apatite (HCA) layer formation on samples was analysed for 7 days using simulated body fluid (SBF) soaked samples. The growth of HCA layers self-assembled on the sample surface was discussed as a function of NBO/BO ratio. Results indicated that the number of Ca2+ ions released into SBF solution in dissolution process and weight loss of SB-treated samples vary with NBO/BO ratio. The changes in NBO/BO ratios were observed to be proportional to HCA forming ability of barium soda lime phosphosilicate glasses.

The effect on phase separation of the oxidation state of molybdenum in a Na2O-B2O3-SiO2 glass

International Nuclear Information System (INIS)

Kawamoto, Y.; Clemens, K.; Tomozawa, M.; Warden, J.T.

1981-01-01

The effect of oxidation state on phase separation was studied for 13Na 2 O, 49B 2 O 3 , 38SiO 2 (mol%) glasses containing 1 mol% Mo oxide. The glasses were melted under various conditions to vary the oxidation states of Mo ions. The oxidation states of Mo ions were determined by chemical analysis and ESR. The crystallisation tendency, the immiscibility temperature, and the phase separation morphology of the glasses were examined by DTA, x-ray diffraction, opalescence method, and replica electron microscopy. Glasses containing Mo 4+ ions have a great tendency to precipitate MoO 2 crystals. The immiscibility temperature of glass goes through a minimum when the oxidation states of Mo ions are changed. It was suggested that there is an optimum oxidation state to prevent crystallisation and to suppress the phase separation tendency of this system. (author)

Investigating the effect of SiO2-TiO 2-CaO-Na 2O-ZnO bioactive glass doped hydroxyapatite: characterisation and structural evaluation.

Science.gov (United States)

Yatongchai, Chokchai; Wren, Anthony W; Curran, Declan J; Hampshire, Stuart; Towler, Mark R

2014-07-01

The effects of increasing bioactive glass additions, SiO2-TiO2-CaO-Na2O-ZnO up to 25 wt% in increments of 5 wt%, on the physical and mechanical properties of hydroxyapatite (HA) sintered at 900, 1000, 1100 and 1200 °C for 2 h was investigated. Increasing both the glass content and the temperature resulted in increased HA decomposition. This resulted in the formation of a number of bioactive phases. However the presence of the liquidus glass phase did not result in increased densification levels. At 1000 and 1100 °C the additions of 5 wt% glass resulted in a decrease in density which never recovered with increasing glass content. At 1200 °C a cyclic pattern resulted from increasing glass content. There was no direct relationship between strength and density with all samples experiencing no change or a decrease in strength with increasing glass content. Weibull statistics displayed no pattern with increasing glass content.

Effect of phase transformation and partial crystallization on the mechanical properties of glass and glass-ceramics based on 3CaO.P_2O_5-SiO_2-MgO system

International Nuclear Information System (INIS)

Daguano, J.K.M.F.; Simba, B.G.; Santos, C.

2011-01-01

In this work, glass and glass-ceramics of the 3CaO.P_2O_5-SiO_2-MgO system were developed aiming to produce different crystallization degrees. Glasses were melted at 1600 deg C and heat treated at 700 deg C. Part of the glasses was crystallized using heat treatments at 770 deg C and 1150 deg C for 4h. The partial crystallization and phase transformations were responsible for different mechanical properties (bending strength, young modulus, fracture toughness and hardness) in each temperature. The mechanical response of the material is discussed in relation to the microstructure, crystalline phases, and porosity of the materials. (author)

Haw-glass dissolution and radionuclide release: mechanism - modelling - source term

Energy Technology Data Exchange (ETDEWEB)

Grambow, B [Forschungszentrum Karlsruhe, Institut fur Nukleare, Karlsruhe (Germany)

1997-07-01

Important release controlling processes are: 1) kinetics of glass matrix dissolution (leaching), 2) formation of secondary alteration products (controlling thermodynamic solubility), 3) sorption on surfaces in the engineered barrier system and 4) formation of mobile species. Quantification of these processes requires assessment of the energetics and dynamics of the various reversible and irreversible processes within an overall open non-equilibrium system. Corrosion/dissolution of the waste matrices is not necessarily associated with a proportional release of radionuclides. The formation of new secondary phases, such as silicates, molybdates, uranates, carbonates... establishes a new geochemical barrier for re-immobilization of radionuclides dissolved from the waste matrices. The presence of iron (corroding canisters during glass alteration) reduces the solution concentration of redox sensitive radionuclides. Consequently, the container, after being corroded, constitutes an important geochemical barrier for radionuclide re-immobilization. Geochemical modelling of the long-term behaviour of glasses must be performed in an integrated way, considering simultaneous reactions of the glass, of container corrosion, of repository rock and of backfill material. Until now, only few attempts were made for integral systems modelling. (A.C.)

Effect of V2O5 on SrO-ZnO-B2O3-SiO2 glass-ceramics for high temperature sealant application

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Tiwari, Babita; Bhatacharya, S.; Dixit, A.; Gadkari, S. C.; Kothiyal, G. P.

2012-06-01

Glasses in the SrO-ZnO-B2O3-SiO2 (SZBS) system with and without V2O5 were prepared by melt-quench method and transformed into glass-ceramics by controlled crystallization. Investigated glasses and glass-ceramics have thermal expansion coefficients (TEC) in the range of 95-120 × 10-7/°C (30-600 °C), which match closely with TEC of other components of solid oxide fuel cell (SOFC). Study of thermo-physical properties of SZBS glasses revealed the network modifying effect of V2O5. Addition of V2O5 increases the TEC and decreases the viscosity of the glass which is beneficial for making seal with Crofer-22-APU. Microstructural investigations have shown good bonding of SZBS glasses with Crofer-22-APU. Elemental line scans indicate that inter-diffusion of Fe, Cr and Si across interface, which is thought to be responsible for good bonding with Crofer-22-APU.

Enhancement of the glass corrosion in the presence of clay minerals: testing experimental results with an integrated glass dissolution model

International Nuclear Information System (INIS)

Godon, N.; Vernaz, E.Y.

1992-01-01

Recent glass dissolution experiments, conducted at 90 deg C in the presence of potential backfill materials, indicate remarkably faster glass corrosion in the presence of clay, compared to tests where the glass is leached either alone or with alternative backfill materials. This effect correlates with the clay content in the backfill, and may be attributed to the removal of silica from solution. Scorpion, or dissolution with reprecipitation of a silica-rich clay, have been proposed as possible mechanisms for the silica consumption. The results of some experiments have been tested against a glass dissolution model, in which a widely used kinetic equation for glass corrosion is coupled with diffusive silica transport through a single porosity, linearly sorbing medium, which represents the backfilling. Because the glass corrosion rates imposed by the kinetic equation are inversely proportional to the silicic acid concentration of the leachant contacting the glass, the model predicts enhanced glass dissolution if silica is sorbed by the porous medium. The experimental data proved to be consistent with the predicted enhancement of the glass dissolution. Moreover, the model-estimated distribution coefficients for silica sorption (K d ) fall within the range of values extracted from available literature data, thus supporting the hypothesis that the observed high corrosion rates are due to sorption of silica on the clay mineral surfaces. (author)

Suppressing Structural Colors of Photocatalytic Optical Coatings on Glass: The Critical Role of SiO2.

Science.gov (United States)

Li, Ronghua; Boudot, Mickael; Boissière, Cédric; Grosso, David; Faustini, Marco

2017-04-26

The appearance of structural colors on coated-glass is a critical esthetical drawback toward industrialization of photocatalytic coatings on windows for architecture or automobile. Herein we describe a rational approach to suppress the structural color of mesoporous TiO 2 -based coatings preserving photoactivity and mechanical stiffness. Addition of SiO 2 as third component is discussed. Ti x Si (1-x) O 2 mesoporous coatings were fabricated by one-step liquid deposition process through the evaporation induced self-assembling and characterized by GI-SAXS, GI-WAXS, electron microscopies, and in situ Environmental Ellipsometry Porosimetry. Guided by optical simulation, we investigated the critical role of SiO 2 on the optical responses of the films but also on the structural, mechanical, and photocatalytic properties, important requirements to go toward real applications. We demonstrate that adding SiO 2 to porous TiO 2 allows tuning and suppression of structural colors through refractive index matching and up to 160% increase in mechanical stiffening of the films. This study leads us to demonstrate an example of "invisible" coating, in which the light reflection is angle- and thickness-independent, and exhibiting high porosity, mechanical stiffness, and photoactivity.

Effect of calcium fluoride on sintering behaviour of SiO2-CaO-Na2O-MgO glass-ceramic system

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Bahman Mirhadi

2012-09-01

Full Text Available The crystallization characteristics of glasses based on the SiO2-CaO-Na2O-MgO (SCNM system containing calcium fluoride (CaF2 have been investigated by differential thermal analysis (DTA, X-ray diffraction (XRD and scanning electron microscopy (SEM. The partial replacement of CaO by CaF2 in the studied glass-ceramics led to the development of different crystalline phase assemblages, including wollastonite and diopside using various heat-treatment processes. With the increase of CaF2 content, the crystallization temperature of the glass and the strength of the crystallization peak temperature decreases. Addition of CaF2 up to 6.0 mol%, as expected, improved the sinterability. This sample reached to maximum density by sintering at 950 °C.

Investigation of 70SiO2-15CaO-10P2O5-5Na2O Glass Composition for Bone Regeneration Applications

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Vikas Anand

2014-11-01

Full Text Available Glass with the composition 70SiO2-15CaO -10P2O5-5Na2O has been prepared by using sol gel technique. Bioactive behavior of the glass sample has been checked by in vitro study using TRIS simulated body fluid. Bioactive properties of the sample has been analyzed by using XRD, Raman, FE-SEM, EDX and Brunauer Emmett Teller studies. pH study has been conducted to check the non- acidic nature of the glass sample. Drug delivery behavior of the sample has been estimated by using gentamicin as an antibiotic. Reported sample has been found to be potential candidate for bone regeneration applications.

Structural study of Na2O-B2O3-SiO2 glasses from molecular simulations using a polarizable force field.

Science.gov (United States)

Pacaud, Fabien; Delaye, Jean-Marc; Charpentier, Thibault; Cormier, Laurent; Salanne, Mathieu

2017-10-28

Sodium borosilicate glasses Na 2 O-B 2 O 3 -SiO 2 (NBS) are complex systems from a structural point of view. Three main building units are present: tetrahedral SiO 4 and BO 4 (B IV ) and triangular BO 3 (B III ). One of the salient features of these compounds is the change of the B III /B IV ratio with the alkali concentration, which is very difficult to capture in force fields-based molecular dynamics simulations. In this work, we develop a polarizable force field that is able to reproduce the boron coordination and more generally the structure of several NBS systems in the glass and in the melt. The parameters of the potential are fitted from density functional theory calculations only, in contrast with the existing empirical potentials for NBS systems. This ensures a strong improvement on the transferability of the parameters from one composition to another. Using this new force field, the structure of NBS systems is validated against neutron diffraction and nuclear magnetic resonance experiments. A special focus is given to the distribution of B III /B IV with respect to the composition and the temperature.

Bioactivity and cell proliferation in radiopaque gel-derived CaO-P2O5-SiO2-ZrO2 glass and glass-ceramic powders.

Science.gov (United States)

Montazerian, Maziar; Yekta, Bijan Eftekhari; Marghussian, Vahak Kaspari; Bellani, Caroline Faria; Siqueira, Renato Luiz; Zanotto, Edgar Dutra

2015-10-01

In this study, 10 mol% ZrO2 was added to a 27CaO-5P2O5-68SiO2 (mol%) base composition synthesized via a simple sol-gel method. This composition is similar to that of a frequently investigated bioactive gel-glass. The effects of ZrO2 on the in vitro bioactivity and MG-63 cell proliferation of the glass and its derivative polycrystalline (glass-ceramic) powder were investigated. The samples were characterized using thermo-gravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) coupled to energy dispersive X-ray spectroscopy (EDS). Release of Si, Ca, P and Zr into simulated body fluid (SBF) was determined by inductively coupled plasma (ICP). Upon heat treatment at 1000 °C, the glass powder crystallized into an apatite-wollastonite-zirconia glass-ceramic powder. Hydroxycarbonate apatite (HCA) formation on the surface of the glass and glass-ceramic particles containing ZrO2 was confirmed by FTIR and SEM. Addition of ZrO2 to the base glass composition decreased the rate of HCA formation in vitro from one day to three days, and hence, ZrO2 could be employed to control the rate of apatite formation. However, the rate of HCA formation on the glass-ceramic powder containing ZrO2 crystal was equal to that in the base glassy powder. Tests with a cultured human osteoblast-like MG-63 cells revealed that the glass and glass-ceramic materials stimulated cell proliferation, indicating that they are biocompatible and are not cytotoxic in vitro. Moreover, zirconia clearly increased osteoblast proliferation over that of the Zr-free samples. This increase is likely associated with the lower solubility of these samples and, consequently, a smaller variation in the media pH. Despite the low solubility of these materials, bioactivity was maintained, indicating that these glassy and polycrystalline powders are potential candidates for bone graft substitutes and bone cements with

Constraints on the affinity term for modeling long-term glass dissolution rates

International Nuclear Information System (INIS)

Bourcier, W.L.; Carroll, S.A.; Phillips, B.L.

1993-11-01

Predictions of long-term glass dissolution rates are highly dependent on the form of the affinity term in the rate expression. Analysis of the quantitative effect of saturation state on glass dissolution rate for CSG glass (a simple analog of SRL-165 glass), shows that a simple (1-Q/K) affinity term does not match experimental results. Our data at 100 degree C show that the data is better fit by an affinity term having the form (1 - (Q/K) 1 /σ) where σ = 10

Gels and gel-derived glasses in the Na2O-B2O3-SiO2 system. [containerless melting in space

Science.gov (United States)

Mukherjee, S. P.

1982-01-01

The containerless melting of high-purity multicomponent homogeneous gels and gel-monoliths offers a unique approach to making ultrapure multicomponent optical glasses in the reduced gravity environment of space. Procedures for preparing and characterizing gels and gel-derived glasses in the Na2O-B2O3-SiO2 system are described. Preparation is based on the polymerization reactions of alkoxysilane with trimethyl borate or boric acid and a suitable sodium compound. The chemistry of the gelling process is discussed in terms of process parameters and the gel compositions. The physicochemical nature of gels prepared by three different procedures were found to be significantly different. IR absorption spectra indicate finite differences in the molecular structures of the different gels. The melting of the gel powders and the transformation of porous gel-monoliths to transparent 'glass' without melting are described.

The Dissolution Behavior of Borosilicate Glasses in Far-From Equilibrium Conditions

Energy Technology Data Exchange (ETDEWEB)

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin PG; Ryan, Joseph V.; Asmussen, Robert M.

2018-02-10

In far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this paper is to study effects of these variables on three model waste glasses (SON68, ISG, AFCI). To do this, experiments were conducted at temperatures of 23, 40, 70, and 90 °C and pH(RT) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. The results from these tests were then used to parameterize a kinetic rate model based on transition state theory. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Discrepancies in the absolute dissolution rates as compared to those obtained using other test methods are discussed. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies. The results were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), which is capable of providing a robust uncertainty analysis. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, the effect of glass composition on the rate parameter values could possibly be obtained. This would allow for the possibility of predicting the forward dissolution rate of glass based solely on composition

Use of fission track for deciphering the dissolution mechanism of silicates glasses

International Nuclear Information System (INIS)

Petit, J.C.; Brousse, C.

1985-09-01

Polished sections of silicate glasses containing latent or pre-etched fission tracks have been subjected to corrosion in deionized water or NaCl brines at 20, 50 and 100 0 C. The evolution of glass surface helps deciphering among reported dissolution models. We show that ion-exchange is dominant in simple glasses while in complex ones, dissolution involves several steps including an in-situ transformation of the pristine material and a reprecipitation of dissolved species

Glass-ceramic enamels derived from the Li2O-Na2O-Al2O3-TiO2-SiO2 system

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SNEZANA R. GRUJIC

2002-02-01

Full Text Available The results of research on the conditions for obtaining model glass-ceramic enamels, derived from the basic Li2O-Na2O-Al2O3-TiO2-SiO2 system, by varying the initial composition and thermal treatment conditions, are presented in this paper. Segregation of the crystal phases in the glassy-matrix was carried out during subsequent thermal treatment. The formation of different crystal phases was evidenced through the results of differential-thermal analysis and X-ray powder diffraction analysis.

The phase transformation and crystallization kinetics of (1 - x)Li2O-xNa2O-Al2O3-4SiO2 glasses

International Nuclear Information System (INIS)

Wang, Moo-Chin; Li, Wang-Long; Cheng, Chih-Wei; Chang, Kuo-Ming; Chen, Yong-Feng; Hsi, Chi-Shiung

2010-01-01

The phase transformation and crystallization kinetics of (1 - x)Li 2 O-xNa 2 O-Al 2 O 3 -4SiO 2 glasses have been studied by using differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron diffraction (ED) analysis. The crystallization temperature at the exothermic peak increases from 1171 to 1212 K when the Na 2 O content increases from 0 to 0.6 mol. The crystalline phase is composed of spodumene crystallization when the Na 2 O content increases from 0 to 0.6 mol. The activation energy of spodumene crystallization decreases from 444.0 ± 22.2 to 284.0 ± 10.8 kJ mol -1 when the Na 2 O content increases from 0 to 0.4 mol. Moreover, the activation energy increases from 284.0 ± 10.8 to 446.0 ± 23.2 kJ mol -1 when the Na 2 O content increases from 0.4 to 0.6 mol. The crystallization parameters m and n approach 2, indicating that the surface nucleation and two-dimensional growth are dominant in (1 - x)Li 2 O-xNa 2 O-Al 2 O 3 -4SiO 2 glasses.

Q(n) species distribution in K2O.2SiO2 glass by 29Si magic angle flipping NMR.

Science.gov (United States)

Davis, Michael C; Kaseman, Derrick C; Parvani, Sahar M; Sanders, Kevin J; Grandinetti, Philip J; Massiot, Dominique; Florian, Pierre

2010-05-06

Two-dimensional magic angle flipping (MAF) was employed to measure the Q((n)) distribution in a (29)Si-enriched potassium disilicate glass (K(2)O.2SiO(2)). Relative concentrations of [Q((4))] = 7.2 +/- 0.3%, [Q((3))] = 82.9 +/- 0.1%, and [Q((2))] = 9.8 +/- 0.6% were obtained. Using the thermodynamic model for Q((n)) species disproportionation, these relative concentrations yield an equilibrium constant k(3) = 0.0103 +/- 0.0008, indicating, as expected, that the Q((n)) species distribution is close to binary in the potassium disilicate glass. A Gaussian distribution of isotropic chemical shifts was observed for each Q((n)) species with mean values of -82.74 +/- 0.03, -91.32 +/- 0.01, and -101.67 +/- 0.02 ppm and standard deviations of 3.27 +/- 0.03, 4.19 +/- 0.01, and 5.09 +/- 0.03 ppm for Q((2)), Q((3)), and Q((4)), respectively. Additionally, nuclear shielding anisotropy values of zeta =-85.0 +/- 1.3 ppm, eta = 0.48 +/- 0.02 for Q((2)) and zeta = -74.9 +/- 0.2 ppm, eta = 0.03 +/- 0.01 for Q((3)) were observed in the potassium disilicate glass.

Optical properties of the Al2O3/SiO2 and Al2O3/HfO2/SiO2 antireflective coatings

Science.gov (United States)

Marszałek, Konstanty; Winkowski, Paweł; Jaglarz, Janusz

2014-01-01

Investigations of bilayer and trilayer Al2O3/SiO2 and Al2O3/HfO2/SiO2 antireflective coatings are presented in this paper. The oxide films were deposited on a heated quartz glass by e-gun evaporation in a vacuum of 5 × 10-3 [Pa] in the presence of oxygen. Depositions were performed at three different temperatures of the substrates: 100 °C, 200 °C and 300 °C. The coatings were deposited onto optical quartz glass (Corning HPFS). The thickness and deposition rate were controlled with Inficon XTC/2 thickness measuring system. Deposition rate was equal to 0.6 nm/s for Al2O3, 0.6 nm - 0.8 nm/s for HfO2 and 0.6 nm/s for SiO2. Simulations leading to optimization of the thin film thickness and the experimental results of optical measurements, which were carried out during and after the deposition process, have been presented. The optical thickness values, obtained from the measurements performed during the deposition process were as follows: 78 nm/78 nm for Al2O3/SiO2 and 78 nm/156 nm/78 nm for Al2O3/HfO2/SiO2. The results were then checked by ellipsometric technique. Reflectance of the films depended on the substrate temperature during the deposition process. Starting from 240 nm to the beginning of visible region, the average reflectance of the trilayer system was below 1 % and for the bilayer, minima of the reflectance were equal to 1.6 %, 1.15 % and 0.8 % for deposition temperatures of 100 °C, 200 °C and 300 °C, respectively.

A Novel SOFC/SOEC Sealing Glass with a Low SiO2 Content and a High Thermal Expansion Coefficient

DEFF Research Database (Denmark)

Kiebach, Wolff-Ragnar; Agersted, Karsten; Zielke, Philipp

2017-01-01

the amount of Si emission, a low Si containing sealing glass (chemical composition: 50 mol% CaO, 20 mol% ZnO, 20 mol% B2O3 and 10 mol% SiO2) was developed at DTU. In this work, the results from thermal characterization, the crystallization behavior of the glass and the long-term stability and adhesion......Solid oxide cells require seals that can function in harsh, elevated temperature environments. In addition, a low Si content can be advantageous, since Si impurities from the glass sealant can be transported to the active fuel electrode and poison the Ni-YSZ triple phase boundaries. To reduce...... behavior of the glass were studied under SOFC and SOEC relevant conditions. The glass-ceramic sealant performed well over 400 h, and no cell degradation or leakage related to the seal was found, indicating that the developed glass system is applicable for the use in SOFC/SOEC stacks....

Investigating the Effect of Glass Ion Release on the Cytocompatibility, Antibacterial Eflcacy and Antioxidant Activity of Y2O3 / CeO2 doped SiO2-SrO-Na2O glasses

Directory of Open Access Journals (Sweden)

Placek L. M.

2018-02-01

Full Text Available The effect on ion release and cytocompatibility of Yttrium (Y and Cerium (Ce are investigated when substituted for Sodium (Na in a 0.52SiO2-0.24SrO-0.24-Na2OMOglass series (where MO= Y2O3 or CeO2. Glass leaching was evaluated through pH measurements and Inductive Coupled Plasma-Optical Emission Spectrometry (ICP-OES analysiswhere the extract pH increased during incubation (11.2 - 12.5. Ion release of Silicon (Si, Na and Strontium (Sr from the Con glass was at higher than that of glasses containing Y or Ce, and reached a limit after 1 day. Ion release from Y and Ce containing glasses reached a maximum of 1800 μg/mL, 1800 μg/mL, and 10 μg/mL for Si, Na, and Sr, respectively. Release of Y and Cewas below the ICP- OES detection limit 75% of bacteria at a 9% extract concentration. Antioxidant capacity (mechanism for neuroprotection was evaluated using the ABTS assay. All glasses had inherent radical oxygen species (ROS scavenging capability with Con reaching 9.5 mMTE.

Glass material oxidation and dissolution system: Converting miscellaneous fissile materials to glass

International Nuclear Information System (INIS)

Forsberg, C.W.; Ferrada, J.J.

1996-01-01

The cold war and the development of nuclear energy have resulted in significant inventories of miscellaneous fissile materials (MFMs). MFMs include (1) plutonium scrap and residue, (2) miscellaneous spent nuclear fuel (SNF), (3) certain hot cell wastes, and (4) many one-of-a-kind materials. Major concerns associated with the long-term management of these materials include: safeguards and nonproliferation issues; health, environment, and safety concerns. waste management requirements; and high storage costs. These issues can be addressed by converting the MFMs to glass for secure, long-term storage or repository disposal; however, conventional glass-making processes require oxide-like feed materials. Converting MFMs to oxide-like materials with subsequent vitrification is a complex and expensive process. A new vitrification process has been invented, the Glass Material Oxidation and Dissolution System (GMODS), which directly converts metals, ceramics, and amorphous solids to glass; oxidizes organics with the residue converted to glass; and converts chlorides to borosilicate glass and a secondary sodium chloride (NaCl) stream. Laboratory work has demonstrated the conversion of cerium (a plutonium surrogate), uranium, Zircaloy, stainless steel, multiple oxides, and other materials to glass. However, significant work is required to develop GMODS further for applications at an industrial scale. If implemented, GMODS will provide a new approach to manage these materials

Evaluation method of TiO2-SiO2 ultra-low-expansion glasses with periodic striae using the LFB ultrasonic material characterization system.

Science.gov (United States)

Kushibiki, Jun-ichi; Arakawa, Mototaka; Ohashi, Yuji; Suzuki, Kouji

2006-09-01

Experimental procedures and standard specimens for characterizing and evaluating TiO2-SiO2 ultra-low expansion glasses with periodic striae using the line-focus-beam (LFB) ultrasonic material characterization system are discussed. Two types of specimens were prepared, with specimen surfaces parallel and perpendicular to the striae plane using two different grades of glass ingots. The inhomogeneities of each of the specimens were evaluated at 225 MHz. It was clarified that parallel specimens are useful for accurately measuring velocity variations of leaky surface acoustic waves (LSAWs) excited on a water-loaded specimen surface associated with the striae. Perpendicular specimens are useful for obtaining periodicities in the striae for LSAW propagation perpendicular to the striae plane on a surface and for precisely measuring averaged velocities for LSAW propagation parallel to the striae plane. The standard velocity of Rayleigh-type LSAWs traveling parallel to the striae plane for the perpendicular specimens was numerically calculated using the measured velocities of longitudinal and shear waves and density. Consequently, a reliable standard specimen with an LSAW velocity of 3308.18 +/- 0.35 m/s at 23 degrees C and its temperature coefficient of 0.39 (m/s)/degrees C was obtained for a TiO2-SiO2 glass with a TiO2 concentration of 7.09 wt%. A basis for the striae analysis using this ultrasonic method was established.

Reduction Mechanisms of Cu2+-Doped Na2O-Al2O3-SiO2 Glasses during Heating in H2 Gas.

Science.gov (United States)

Nogami, Masayuki; Quang, Vu Xuan; Ohki, Shinobu; Deguchi, Kenzo; Shimizu, Tadashi

2018-01-25

Controlling valence state of metal ions that are doped in materials has been widely applied for turning optical properties. Even though hydrogen has been proven effective to reduce metal ions because of its strong reducing capability, few comprehensive studies focus on practical applications because of the low diffusion rate of hydrogen in solids and the limited reaction near sample surfaces. Here, we investigated the reactions of hydrogen with Cu 2+ -doped Na 2 O-Al 2 O 3 -SiO 2 glass and found that a completely different reduction from results reported so far occurs, which is dominated by the Al/Na concentration ratio. For Al/Na glass body. For Al/Na > 1, on the other hand, the reduction of Cu 2+ ions occurred simultaneously with the formation of OH bonds, whereas the reduced Cu metal moved outward and formed a metallic film on glass surface. The NMR and Fourier transform infrared results indicated that the Cu 2+ ions were surrounded by Al 3+ ions that formed AlO 4 , distorted AlO 4 , and AlO 5 units. The diffused H 2 gas reacted with the Al-O - ···Cu + units, forming Al-OH and metallic Cu, the latter of which moved freely toward glass surface and in return enhanced H 2 diffusion.

Investigating the influence of Na+ and Sr2+ on the structure and solubility of SiO2-TiO2-CaO-Na2O/SrO bioactive glass.

Science.gov (United States)

Li, Y; Placek, L M; Coughlan, A; Laffir, F R; Pradhan, D; Mellott, N P; Wren, A W

2015-02-01

This study was conducted to determine the influence that network modifiers, sodium (Na+) and strontium (Sr2+), have on the solubility of a SiO2-TiO2-CaO-Na2O/SrO bioactive glass. Glass characterization determined each composition had a similar structure, i.e. bridging to non-bridging oxygen ratio determined by X-ray photoelectron spectroscopy. Magic angle spinning nuclear magnetic resonance (MAS-NMR) confirmed structural similarities as each glass presented spectral shifts between -84 and -85 ppm. Differential thermal analysis and hardness testing revealed higher glass transition temperatures (Tg 591-760 °C) and hardness values (2.4-6.1 GPa) for the Sr2+ containing glasses. Additionally the Sr2+ (~250 mg/L) containing glasses displayed much lower ion release rates than the Na+ (~1,200 mg/L) containing glass analogues. With the reduction in ion release there was an associated reduction in solution pH. Cytotoxicity and cell adhesion studies were conducted using MC3T3 Osteoblasts. Each glass did not significantly reduce cell numbers and osteoblasts were found to adhere to each glass surface.

Estimate of long-term dissolution rate of basaltic glass. A case study on Mt. Fuji area

Energy Technology Data Exchange (ETDEWEB)

Shikazono, Naotatsu; Takino, Akitsugu [Keio Univ., Environmental Geochemistry, Tokyo (Japan)

2002-03-01

Bulk compositional, mineralogical and physical properties of weathered basaltic ash soil ('Andisol') derived mainly from Mt. Fuji were studied. Mineralogical studies revealed that the dominant primary material and weathering products are volcanic glass, allophane and halloysite and the sequence of weathering is volcanic glass {yields} allophane {yields} 10A halloysite {yields} 7A halloysite. X-ray fluorescence analysis indicates that the relative elemental mobilities during the weathering is Na, Ca>K>Mg>P>Si>Ti, Fe>Al>Mn. The trends of soilwater chemistry (H{sub 4}SiO{sub 4} concentration) with depth were calculated based on dissolution - precipitation kinetics - fluid flow coupling model. In order to calculate the trends, the data on present-day annual rainfall, solubility of basalt glass, porosity and specific weight of soil, deposition rate of volcanic ash and grain size of volcanic glass were used. The calculated results were compared with analytical trends of soilwater chemistry. From this comparison the dissolution rate constant of basalt glass was estimated to be 10{sup -9.4} - 10{sup -9.2} (mole Si m{sup -2} s{sup -1}). This value is consistent with previous experimental dissolution rate constant of basalt glass reported in the literature. (author)

Biologically mediated dissolution of volcanic glass in seawater

NARCIS (Netherlands)

Staudigel, H; Yayanos, A; Chastain, R; Davies, G.T.; Verdurmen, E.A Th; Schiffmann, P; Bourcier, R; de Baar, H.J.W.

1998-01-01

We studied the effects of biological mediation on the dissolution of basaltic glass in seawater. Experiments with typical seawater microbial populations were contrasted with a sterile control, and reactions were monitored chemically and isotopically. Biologically mediated experiments produce twice

Formation enthalpy of alkali-borosilicate glass

International Nuclear Information System (INIS)

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

1991-01-01

Temperature dependence of formation enthalpy of glass of the composition 0.0438Na 2 O-0.0385K 2 O-0.3394B 2 O 3 -0.5783SiO 2 was determined using the method of high-temperature colorimetry-dissolution, mixing and differential scanning calorimetry. The glass considered has liquation nature-two-vitrification ranges at 713 K and 817 K are detected. The brightening point is 922 K. The calculation of formation enthalpy using the method of partial heat capacities is made in the temperature range of 973-1473 K. Formation enthalpy does not depend on temperature in the temperature range of 298-1273 K

LOW-TEMPERATURE SINTERED (ZnMg2SiO4 MICROWAVE CERAMICS WITH TiO2 ADDITION AND CALCIUM BOROSILICATE GLASS

Directory of Open Access Journals (Sweden)

BO LI

2011-03-01

Full Text Available The low-temperature sintered (ZnMg2SiO–TiO2 microwave ceramic using CaO–B2O3–SiO2 (CBS as a sintering aid has been developed. Microwave properties of (Zn1-xMgx2SiO4 base materials via sol-gel method were highly dependent on the Mg-substituted content. Further, effects of CBS and TiO2 additives on the crystal phases, microstructures and microwave characteristics of (ZnMg2SiO4 (ZMS ceramics were investigated. The results indicated that CBS glass could lower the firing temperature of ZMS dielectrics effectively from 1170 to 950°C due to the liquid-phase effect, and significantly improve the sintering behavior and microwave properties of ZMS ceramics. Moreover, ZMS–TiO2 ceramics showed the biphasic structure and the abnormal grain growth was suppressed by the pinning effect of second phase TiO2. Proper amount of TiO2 could tune the large negative temperature coefficient of resonant frequency (tf of ZMS system to a near zero value. (Zn0.8Mg0.22SiO4 codoped with 10 wt.% TiO2 and 3 wt.% CBS sintered at 950°C exhibits the dense microstructure and excellent microwave properties: εr = 9.5, Q·f = 16 600 GHz and tf = −9.6 ppm/°C.

High Energy Ion Beam Studies of Ion Exchange in a Na2O-Al2O3-SiO2 Glass

International Nuclear Information System (INIS)

Shutthanadan, Vaithiyalingam; Baer, Donald R.; Thevuthasan, Suntharampillai; Adams, Evan M.; Maheswaran, Saravanamuthu; Engelhard, Mark H.; Icenhower, Jonathan P.; McGrail, Bernard P.

2002-01-01

As part of understanding the processes leading to sodium release and ion exchange, the surface and near surface reaction regions on several specimens of a Na2O-Al2O3-SiO2 glass have been examined after exposures to isotopically labeled aqueous solutions. The majority of the analyses describe here have been carried out using energetic ion beam analysis. Rutherford backscattering spectrometry (RBS) has been used to measure the overall glass composition and to determine the profiles and amounts of Na released from the surface. An important part of the ion exchange process is the uptake and incorporation of hydrogen and oxygen in the glass from the solution. To facilitate this analysis, the glasses were exposed to a solution containing 18O and deuterium and analyzed by accelerator based nuclear reaction analysis (NRA). To confirm some of the RBS depth profile data very near the surface, XPS depth profiles were collected on some samples. Although the Na concentration is decreased in the near surface region, it is not totally removed from the outer surface. In this same region, there is also a significant amount of 18O incorporated demonstrating considerable interaction between the water and the glass. Deeper into the material the amounts of deuterium and 18O are more consistent with water or H3O+ diffusion. These results suggest that there exist an outer reaction layer and an inner diffusion controlled layer in the surface region of the reacted glass

Determining the dissolution rates of actinide glasses: A time and temperature Product Consistency Test study

International Nuclear Information System (INIS)

Daniel, W.E.; Best, D.R.

1995-01-01

Vitrification has been identified as one potential option for the e materials such as Americium (Am), Curium (Cm), Neptunium (Np), and Plutonium (Pu). A process is being developed at the Savannah River Site to safely vitrify all of the highly radioactive Am/Cm material and a portion of the fissile (Pu) actinide materials stored on site. Vitrification of the Am/Cm will allow the material to be transported and easily stored at the Oak Ridge National Laboratory. The Am/Cm glass has been specifically designed to be (1) highly durable in aqueous environments and (2) selectively attacked by nitric acid to allow recovery of the valuable Am and Cm isotopes. A similar glass composition will allow for safe storage of surplus plutonium. This paper will address the composition, relative durability, and dissolution rate characteristics of the actinide glass, Loeffler Target, that will be used in the Americium/Curium Vitrification Project at Westinghouse Savannah River Company near Aiken, South Carolina. The first part discusses the tests performed on the Loeffler Target Glass concerning instantaneous dissolution rates. The second part presents information concerning pseudo-activation energy for the one week glass dissolution process

Study of the surface crystallization and resistance to dissolution of niobium phosphate glasses for nuclear waste immobilization

International Nuclear Information System (INIS)

Vieira, Heveline

2008-01-01

The surface crystallization and the dissolution rate of three phosphate glass compositions containing different amounts of niobium oxide were studied. The glasses were named Nb30, Nb37, and Nb44 according to the nominal content of niobium oxide in the glass composition. The three compositions were evaluated keeping the P 2 O 5 /K 2 O ratio constant and varying the amount of Nb 2 O 5 . These glasses were produced by melting appropriate chemical compounds at 1500 deg C for 0.5 hour. The crystalline phases which were nucleated on the glass surface after heat treatment were determined by X-ray diffraction. The crystalline structures depend on the amount of niobium oxide in the glass composition. The crystal morphologies were observed by using an optical microscope, and their characteristics are specific for each kind of crystalline phase. The crystal growth rate and the surface nuclei density were determined for each glass composition, and they depend on each crystalline phase nucleated on the surface. From the differential thermal analysis curves it was determined that the Nb44 glass containing 46.5 mol por cent of niobium oxide is the most thermally stable against crystallization when compared to the Nb30 and Nb37 glasses. According to the activation energies determined for crystal growth on the surface of each glass type, the Nb44 glass can also be considered the most resistant one against crystallization. The dissolution rate for the Nb44 glass after 14 days immersed in an aqueous solution with pH equals to 7 at 90 deg C is the lowest (9.0 x 10 -7 g. cm -2 . day -1 ) when compared to the other two glass compositions. The dissolution rates in acidic and neutral solutions of all studied glasses meet the international standards for materials which can be used in the immobilization of nuclear wastes. (author)

Optical properties of ZrO2, SiO2 and TiO2-SiO2 xerogels and coatings doped with Eu3+ and Eu2+

Directory of Open Access Journals (Sweden)

Gonçalves Rogéria R.

1999-01-01

Full Text Available Eu3+ doped bulk monoliths and thin films were obtained by sol-gel methods in the ZrO2, SiO2 and SiO2-TiO2 systems. Eu3+ 5D0 ® 7FJ emission and decay time characteristics were measured during the entire experimental preparation route from the initial sol to the final xerogels. The crystalline phases identified were tetragonal ZrO2 and mixtures of rutile and anatase TiO2 at high temperature treatments in bulk samples. Good quality thin films were obtained for all systems by dip-coating optical glasses (Schott BK270. The same spectroscopic features were observed either for the bulk monoliths or the films. By appropriate heat treatments under H2 atmosphere Eu2+ containing samples could be obtained in the SiO2-TiO2 system.

Effect of magnesia on the degradability and bioactivity of sol-gel derived SiO2-CaO-MgO-P2O5 system glasses.

Science.gov (United States)

Ma, J; Chen, C Z; Wang, D G; Jiao, Y; Shi, J Z

2010-11-01

Mesoporous 58SiO(2)-(38-x)CaO-xMgO-4P(2)O(5) glasses (where x=0, 5, 10 and 20 mol%) have been prepared by the sol-gel synthesis route. The effects of the substitution of MgO for CaO on glass degradation and bioactivity were studied in tris-(hydroxymethyl)-aminomethane and hydrochloric acid buffer solution (Tris-HCl) and simulated body fluid (SBF), respectively. It is observed that the synthesized glasses with various MgO contents possess the similar textural properties. The studies of in vitro degradability and bioactivity show that the rate of glass degradation gradually decreases with the increase of MgO and the formation of apatite layer on glass surface is retarded. The influences of the composition upon glass properties are explained in terms of their internal structures. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Standard practice for measurement of the glass dissolution rate using the single-pass flow-through test method

CERN Document Server

American Society for Testing and Materials. Philadelphia

2010-01-01

1.1 This practice describes a single-pass flow-through (SPFT) test method that can be used to measure the dissolution rate of a homogeneous silicate glass, including nuclear waste glasses, in various test solutions at temperatures less than 100°C. Tests may be conducted under conditions in which the effects from dissolved species on the dissolution rate are minimized to measure the forward dissolution rate at specific values of temperature and pH, or to measure the dependence of the dissolution rate on the concentrations of various solute species. 1.2 Tests are conducted by pumping solutions in either a continuous or pulsed flow mode through a reaction cell that contains the test specimen. Tests must be conducted at several solution flow rates to evaluate the effect of the flow rate on the glass dissolution rate. 1.3 This practice excludes static test methods in which flow is simulated by manually removing solution from the reaction cell and replacing it with fresh solution. 1.4 Tests may be conducted wit...

Material interactions between system components and glass product melts in a ceramic melter

International Nuclear Information System (INIS)

Knitter, R.

1989-07-01

The interactions of the ceramic and metallic components of a ceramic melter for the vitrification of High Active Waste were investigated with simulated glass product melts in static crucible tests at 1000 0 C and 1150 0 C. Corrosion of the fusion-cast Al 2 O 3 -ZrO 2 -SiO 2 - and Al 2 O 3 -ZrO 2 -SiO 2 -Cr 2 O 3 -refractories (ER 1711 and ER 2161) is characterized by homogeneous chemical dissolution and diffusion through the glass matrix of the refractory. The resulting boundary compositions lead to characteristic modification and formation of phases, not only inside the refractory but also in the glass melt. The attack of the electrode material, a Ni-Cr-Fe-alloy Inconel 690, by the glass melt takes place via grain boundaries and leads to the oxidation of Cr and growth of Cr 2 O 3 -crystals at the boundary layer. Noble metals, added to the glass melt can form solid solutions with the alloy with varying compositions. (orig.) [de

Modeling surface area to volume effects on borosilicate glass dissolution

International Nuclear Information System (INIS)

Bourcier, W.L.; Ebert, W.L.; Feng, X.

1992-11-01

We simulated the reaction of SRL-131 glass with equilibrated J-13 water in order to investigate the effects of surface area to volume ratio (SA/V) on glass dissolution. We show that glass-fluid ion exchange causes solution pH to rise to progressively higher values as SA/V increases. Because the ion exchange is rapid relative to the duration of the glass dissolution experiment, the pH effect does not scale with (SA/V)*time. Experiments compared at the same (SA/V)*time value therefore have different pHs, with higher pHs at higher SA/V ratios. Both experimental data and our simulation results show similar trends of increasing reaction rate as a function of SA/V ratio when scaled to (SA/V)*time. Glasses which react in systems of differing SA/V ratio therefore follow different reaction paths and high SA/V ratios cannot be used to generate data which accurately scales to long time periods unless the ion exchange effect is taken into account. We suggest some simple test designs which enable more reliable high. SA/V accelerated tests

Thermodynamic and structural models compared with the initial dissolution rates of SON glass samples

International Nuclear Information System (INIS)

Tovena, I.; Advocat, T.; Ghaleb, D.; Vernaz, E.

1993-01-01

The experimentally determined initial dissolution rate R 0 of nuclear glass was correlated with thermodynamic parameters and structural parameters. The initial corrosion rates of six ''R7T7'' glass samples measured at 100 deg C in a Soxhlet device were correlated with the glass free hydration energy and the glass formation enthalpy. These correlations were then tested with a group of 26 SON glasses selected for their wide diversity of compositions. The thermodynamic models provided a satisfactory approximation of the initial dissolution rate determined under Soxhlet conditions for SON glass samples that include up to 15 wt% of boron and some alumina. Conversely, these models are inaccurate if the boron concentration exceeds 15 wt% and the glass contains no alumina. Possible correlations between R 0 and structural parameters, such as the boron coordination number and the number of nonbridging oxygen atoms, were also investigated. The authors show that R 0 varies inversely with the number of 4-coordinate boron atoms; conversely, the results do not substantiate published reports of a correlation between R 0 and the number of nonbridging oxygen atoms. (authors). 13 refs., 2 figs., 4 tabs

In vitro evaluation of bioactivity of SiO2-CaO-P2O5-Na2O-CaF2-ZnO glass-ceramics

Science.gov (United States)

Riaz, Madeeha; Zia, Rehana; Saleemi, Farhat; Bashir, Farooq; Hossain, Tousif; Kayani, Zohra

2014-09-01

Zinc is an essential trace element that stimulates bone formation but it is also known as an inhibitor of apatite crystal growth. In this work addition of ZnO to SiO2-CaO-P2O5-Na2O-CaF2 glass-ceramic system was made by conventional melt-quenching technique. DSC curves showed that the addition of ZnO moved the endothermic and exothermic peaks to lower temperatures. X-ray diffraction analysis did not reveal any additional phase caused by ZnO addition and showed the presence of wollastonite and hydroxyapatite crystalline phases only in all the glass-ceramic samples. As bio-implant apatite forming ability is an essential condition, the surface reactivity of the prepared glass-ceramic specimens was studied in vitro in Kokubo's simulated body fluid (SBF) [1] with ion concentration nearly equal to human blood plasma for 30 days at 37 °C under static condition. Atomic absorption spectroscopy (AAS) was used to study the changes in element concentrations in soaking solutions and XRD, FT-IR and SEM were used to elucidate surface properties of prepared glass-ceramics, which confirmed the formation of HCAp on the surface of all glass-ceramics. It was found that the addition of ZnO had a positive effect on bioactivity of glass-ceramics and made it a potential candidate for restoration of damaged bones.

Heat treatment of Na2O-CaO-P2O5-SiO2 bioactive glasses: densification processes and postsintering bioactivity.

Science.gov (United States)

Sola, A; Bellucci, D; Raucci, M G; Zeppetelli, S; Ambrosio, L; Cannillo, V

2012-02-01

Because of their excellent bioactivity, bioactive glasses are increasingly diffused to produce biomedical devices for bone prostheses, to face the dysfunctions that may be caused by traumatic events, diseases, or even natural aging. However, several processing routes, such as the production of scaffolds or the deposition of coatings, include a thermal treatment to apply or sinter the glass. The exposure to high temperature may induce a devetrification phenomenon, altering the properties and, in particular, the bioactivity of the glass. The present contribution offers an overview of the thermal behavior and properties of two glasses belonging to the Na2O-CaO-P2O5-SiO2 system, to be compared to the standard 45S5 Bioglass(®). The basic goal is to understand the effect of both the original composition and the thermal treatment on the performance of the sintered glasses. The new glasses, the one (BG_Na) with a high content of Na2O, the other (BG_Ca) with a high content of CaO, were fully characterized and sintering tests were performed to define the most interesting firing cycles. The sintered samples, treated at 880°C and 800°C respectively, were investigated from a microstructural point of view and their mechanical properties were compared to those of the bulk (not sintered) glass counterparts. The effect of sintering was especially striking on the BG_Ca material, whose Vickers hardness increased from 598.9 ± 46.7 HV to 1053.4 ± 35.0 HV. The in vitro tests confirmed the ability of the glasses, both in bulk and sintered form, of generating a hydroxyapatite surface layer when immersed in a simulated body fluid. More accurate biological tests performed on the sintered glasses proved the high bioactivity of the CaO-rich composition even after a heat treatment. Copyright © 2011 Wiley Periodicals, Inc.

Physical and thermal behaviour of Sr-La-Al-B-Si based SOFC glass sealants as function of SrO content and B2O3/SiO2 ratio in the matrix

Science.gov (United States)

Ojha, Prasanta Kumar; Rath, S. K.; Chongdar, T. K.; Gokhale, N. M.; Kulkarni, A. R.

2011-05-01

A series of SOFC glass sealants with composition SrO (x), La2O3 (15), Al2O3 (15), B2O3 (40 - x), and SiO2 (30) [x = 10, 15, 20, 25 and 30] (wt.%) [SLABS] are investigated for their structure property correlations at different compositions. Quantitative Fourier transform infrared spectroscopy shows structural rigidity with increasing SrO content, as demonstrate by an increase in the Si-O-Si/O-Si-O bending and B-O-B stretching frequencies. The role of SrO as a modifier dominates the control of the structure and behaviour of glasses compared with the effect of network formers, i.e., the B2O3/SiO2 ratio. Consequent to the structural changes, increasing substitution of B2O3 by SrO the glasses causes increases in the density, glass transition temperature and dilatometric softening point. On the other hand, the crystallization temperatures show a decreasing trend and the coefficient of thermal expansion increases with increase in substitution.

Quantifying Silica Reactivity in Subsurface Environments: Reaction Affinity and Solute Matrix Controls on Quartz and SiO2 Glass Dissolution Kinetics

International Nuclear Information System (INIS)

Dove, Patricia M.

2000-01-01

During the three years of this project, Professor Dove's laboratory made tremendous progress in understanding controls on amorphous silica dissolution kinetics in aqueous solutions. Our findings have already received considerable attention. In hydrothermal and low temperature studies, the work focused on determining quantitative and mechanistic controls on the most abundant silica polymorphs in Earth environments--quartz and amorphous silica. Our studies achieved goals set forth in the original proposal to establish a new quantitative understanding of amorphous silica dissolution. This support has resulted in 10 journal, 12 abstracts and 2 thesis publications. The PI and students were also recognized with 6 awards during this period. The 1998 EMSP conference in Chicago was an important meeting for our project. The symposium, enabled P.I. Dove to establish valuable contacts with ''users'' having specific needs for the findings of our EMSP project related to the urgency of problems in the Tanks Focus Area (TFA). Since that time, our working relations developed as Dove interacted with TFA scientists and engineers on the problems of waste glass properties. These interactions refined our experimental objectives to better meet their needs. Dove presented the results of EMSP research findings to a TFA subgroup at a Product Acceptance Workshop held in Salt Lake City during December 1998. The travel costs to attend this unanticipated opportunity were paid from EMSP project funds. In January 2000, Dove also attended a similar meeting in Atlanta with PNNL, SRL and BNF scientists/engineers to discuss new issues and make another level of decisions on the Product Acceptance goals. Our EMSP-funded research interfaced very well with the ongoing studies of Dr. Pete McGrail and colleagues in the Applied Geochemistry Group at PNNL. The value of our work to ''users'' was further demonstrated when Dove's EMSP-funded Postdoc, Dr. Jonathan Icenhower was hired by the same PNNL group. With

Progress toward bridging from atomistic to continuum modeling to predict nuclear waste glass dissolution.

Energy Technology Data Exchange (ETDEWEB)

Zapol, Peter (Argonne National Laboratory, Argonne, IL); Bourg, Ian (Lawrence Berkeley National Laboratories, Berkeley, CA); Criscenti, Louise Jacqueline; Steefel, Carl I. (Lawrence Berkeley National Laboratories, Berkeley, CA); Schultz, Peter Andrew

2011-10-01

This report summarizes research performed for the Nuclear Energy Advanced Modeling and Simulation (NEAMS) Subcontinuum and Upscaling Task. The work conducted focused on developing a roadmap to include molecular scale, mechanistic information in continuum-scale models of nuclear waste glass dissolution. This information is derived from molecular-scale modeling efforts that are validated through comparison with experimental data. In addition to developing a master plan to incorporate a subcontinuum mechanistic understanding of glass dissolution into continuum models, methods were developed to generate constitutive dissolution rate expressions from quantum calculations, force field models were selected to generate multicomponent glass structures and gel layers, classical molecular modeling was used to study diffusion through nanopores analogous to those in the interfacial gel layer, and a micro-continuum model (K{mu}C) was developed to study coupled diffusion and reaction at the glass-gel-solution interface.

Homogeneity of peraluminous SiO2-B2O3-Al2O3-Na2O-CaO-Nd2O3 glasses: Effect of neodymium content

International Nuclear Information System (INIS)

Gasnier, E.; Bardez-Giboire, I.; Massoni, N.; Montouillout, V.; Pellerin, N.; Allix, M.; Ory, S.; Cabie, M.; Poissonnet, S.; Massiot, D.

2014-01-01

Considering the interest of developing new glass matrices able to immobilize higher concentration of high level nuclear wastes than currently used nuclear borosilicate compositions, glasses containing high rare earth contents are of particular interest. This study focuses on a peraluminous alumino borosilicate system SiO 2 -B 2 O 3 -Al 2 O 3 -Na 2 O-CaO-Nd 2 O 3 defined by a per-alkaline/peraluminous ratio RP = ([Na 2 O] + [CaO])/ ([Na 2 O] + [CaO] + [Al 2 O 3 ]) ≤ 0.5. Samples with various contents of Nd 2 O 3 from 0 to 10 mol% were studied using DSC, XRD, SEM, TEM, STEM and EMPA methods. The glasses present a high thermal stability even after a slow cooling treatment from the melt. Only a slight mullite crystallization is detected for low Nd 2 O 3 content (≤2.3 mol%) and crystallization of a neodymium borosilicate crystalline phase combined to a phase separation occurred at high Nd 2 O 3 content (≥8 mol%). The solubility of neodymium in the presence of aluminum is demonstrated, with higher neodymium incorporation amounts than in per-alkaline glasses. (authors)

A Novel SOFC/SOEC Sealing Glass with a Low SiO2 Content and a High Thermal Expansion Coefficient  

DEFF Research Database (Denmark)

Kiebach, Wolff-Ragnar; Agersted, Karsten; Zielke, Philipp

2017-01-01

phase boundaries. To reduce the amount of Si emission, a low Si containing sealing glass (chemical composition: 48 mol% CaO, 19 mol% ZnO, 21 mol% B2O3 and 12 mol% SiO2) was developed at DTU. In this presentation, the results from thermal characterization, like thermal expansion coefficient, glass......Solid oxide cells require seals that can function in harsh, elevated temperature environments. In the case of solid oxide electrolysis (SOEC), also a low Si content is desired, since Si impurities from the glass sealing can be transported to the active fuel electrode and poison the Ni-YSZ triple...... transition temperature, crystallization temperature, etc., of the glass will be presented. Additionally, the crystallization behavior of the glass was analyzed by in-situ X-ray diffraction, recording temperature resolved XRD spectra from 30 °C up to 900 °C. Furthermore, the long-term stability...

Anomalous dissolution behaviour of tablets prepared from sugar glass-based solid dispersions

NARCIS (Netherlands)

Van Drooge, D.J.; Hinrichs, W.L.J.; Frijlink, H.W.

2004-01-01

In this study, anomalous dissolution behaviour of tablets consisting of sugar glass dispersions was investigated. The poorly aqueous soluble diazepam was used as a lipophilic model drug. The release of diazepam and sugar carrier was determined to study the mechanisms governing dissolution behaviour.

The influence of phosphorus precursors on the synthesis and bioactivity of SiO2-CaO-P 2O 5 sol-gel glasses and glass-ceramics.

Science.gov (United States)

Siqueira, Renato Luiz; Zanotto, Edgar Dutra

2013-02-01

Bioactive glasses and glass-ceramics of the SiO(2)-CaO-P(2)O(5) system were synthesised by means of a sol-gel method using different phosphorus precursors according to their respective rates of hydrolysis-triethylphosphate (OP(OC(2)H(5))(3)), phosphoric acid (H(3)PO(4)) and a solution prepared by dissolving phosphorus oxide (P(2)O(5)) in ethanol. The resulting materials were characterised by differential scanning calorimetry and thermogravimetry, X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and by in vitro bioactivity tests in acellular simulated body fluid. The different precursors significantly affected the main steps of the synthesis, beginning with the time required for gel formation. The most striking influence of these precursors was observed during the thermal treatments at 700-1,200 °C that were used to convert the gels into glasses and glass-ceramics. The samples exhibited very different mineralisation behaviours; especially those prepared using the phosphoric acid, which had a reduced onset temperature of crystallisation and an increased resistance to devitrification. However, all resulting materials were bioactive. The in vitro bioactivity of these materials was strongly affected by the heat treatment temperature. In general, their bioactivity decreased with increasing treatment temperature. For crystallised samples obtained above 900 °C, the bioactivity was favoured by the presence of two crystalline phases: wollastonite (CaSiO(3)) and tricalcium phosphate (α-Ca(3)(PO(4))(2)).

Progress in development of a source term for sphene glass-ceramic dissolution under vault conditions

International Nuclear Information System (INIS)

Hayward, P.J.; Tait, J.C.; George, I.M.; Carmichael, A.A.; Ross, J.M.P.

1986-01-01

This report describes the results of ongoing leaching experiments, involving aluminosilicate glass and sphene (CaTiSiO/sub 5/) ceramics, doped with /sup 22/Na or /sup 45/Ca, and leached in a simulated Ca-NA-Cl brine at 25 0 or 100 0 C. The experiments are designed to aid development of separate models for the dissolution of the glass and the ceramic phase in a sphene glass-ceramic, and to help evaluate a composite model for the dissolution of the glass-ceramic

Dependence of glass-forming ability on starting compositions in Y2O3–Al2O3–SiO2 system

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Yixiang Chen

2011-09-01

Full Text Available The dependence of glass-forming ability on starting compositions in Y2O3–Al2O3–SiO2 (YAS system has been investigated by melting experiment. Transparent YAS glasses have been prepared under the condition of furnace cooling instead of quenching. It is found that, in the YAS ternary phase diagram, the compositions on the Y3Al5O12–SiO2 line and with 52-68 mol% SiO2 have a higher glass-forming ability to produce pure glass. For the compositions with too much or less SiO2 or with Y/Al = 5/3, 1/1, or 1/3, crystallization occurs with the formation of Y3Al5O12, Y2Si2O7, Al6Si2O13, or SiO2. The densities of the YAS glasses increase with decreasing SiO2 contents and increasing Y/Al ratios, and for the samples with Y/Al = 3/5 there is a good linear relationship between the density and SiO2 content.

Crystallization Mechanism and Kinetics of BaO-Li2O-ZrO2-SiO2 Glasses

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Cristian Berto da Silveira

2002-03-01

Full Text Available Differential thermal analysis and scanning electron microscopy were used to determine the influence of the addition of BaO on the crystallization mechanism of Li2O-ZrO2-SiO2 systems. As the concentration of BaO in the samples increased, a transition occurred in the predominant crystallization mechanism, which passed from superficial to volumetric. To determine the maximum nucleation rate, the crystallization kinetics of the sample containing 20 mole % BaO, which showed the most uniform crystallization, was studied by counting the nuclei with an image analyzer. The first nuclei appeared at the first endothermic inflection point (at the start of Tg, at 440 °C, while the maximum number of nuclei was counted at the midpoint of the glass transition region (446 °C. These results are similar to those observed for other materials that crystallize in volume, and confirm scanning electron microscopy data.

Ion-Exchange Processes and Mechanisms in Glasses

International Nuclear Information System (INIS)

McGrail, B.P.; Icenhower, J.P.; Darab, J.G.; Shuh, D.K.; Baer, D.R.; Shutthanandan, V.; Thevuthasan, S.; Engelhard, M.H.; Steele, J.L.; Rodriguez, E.A.; Liu, P.; Ivanov, K.E.; Booth, C.H.; Nachimuthu, P.

2001-01-01

Leaching of alkalis from glass is widely recognized as an important mechanism in the initial stages of glass-water interactions. Pioneering experimental studies [1-3] nearly thirty-five years ago established that alkali (designated as M + ) are lost to solution more rapidly than network-forming cations. The overall chemical reaction describing the process can be written as: (triple b ond)Si-O-M + H + → (triple b ond)Si-OH + M + (1) or (triple b ond)Si-O-M + H 3 O + → (triple b ond)Si-OH + M + + H 2 O. (2) Doremus and coworkers [4-7] fashioned a quantitative model where M + ions in the glass are exchanged for counter-diffusing H 3 O + or H + . Subsequent investigations [8], which have relied heavily on reaction layer analysis, recognized the role of H 2 O molecules in the alkali-exchange process, without minimizing the importance of charged hydrogen species. Beginning in the 1980s, however, interest in M + -H + exchange reactions in silicate glasses diminished considerably because important experimental observations showed that network hydrolysis and dissolution rates were principally controlled by the chemical potential difference between the glass and solution (chemical affinity) [9]. For nuclear waste glasses, formation of alteration products or secondary phases that remove important elements from solution, particularly Si, was found to have very large impacts on glass dissolution rates [10,11]. Consequently, recent work on glass/water interactions has focused on understanding this process and incorporating it into models [12]. The ion-exchange process has been largely ignored because it has been thought to be a short duration, secondary or tertiary process that had little or no bearing on long-term corrosion or radionuclide release rates from glasses [13]. The only significant effect identified in the literature that is attributed to alkali ion exchange is an increase in solution pH in static laboratory tests conducted at high surface area-to-volume ratios

Fabrication and characterization of Er+3 doped SiO2/SnO2 glass-ceramic thin films for planar waveguide applications

Science.gov (United States)

Guddala, S.; Chiappini, A.; Armellini, C.; Turell, S.; Righini, G. C.; Ferrari, M.; Narayana Rao, D.

2015-02-01

Glass-ceramics are a kind of two-phase materials constituted by nanocrystals embedded in a glass matrix and the respective volume fractions of crystalline and amorphous phase determine the properties of the glass-ceramics. Among these properties transparency is crucial in particular when confined structures, such as, dielectric optical waveguides, are considered. Moreover, the segregation of dopant rare-earth ions, like erbium, in low phonon energy crystalline medium makes these structures more promising in the development of waveguide amplifiers. Here we are proposing a new class of low phonon energy tin oxide semiconductor medium doped silicate based planar waveguides. Er3+ doped (100-x) SiO2-xSnO2 (x= 10, 20, 25 and 30mol%), glass-ceramic planar waveguide thin films were fabricated by a simple sol-gel processing and dip coating technique. XRD and HRTEM studies indicates the glass-ceramic phase of the film and the dispersion of ~4nm diameter of tin oxide nanocrystals in the amorphous phase of silica. The spectroscopic assessment indicates the distribution of the dopant erbium ions in the crystalline medium of tin oxide. The observed low losses, 0.5±0.2 dB/cm, at 1.54 μm communication wavelength makes them a quite promising material for the development of high gain integrated optical amplifiers.

Molten (Mg0.88Fe0.12)2SiO4 at lower mantle conditions - Melting products and structure of quenched glasses

Science.gov (United States)

Williams, Quentin

1990-01-01

Infrared spectra of quenched magnesium silicate glasses synthesized by fusing olivine at pressures in excess of 50 GPa and temperatures greater than 2500 K demonstrate that silicon is dominantly present in four-fold coordination with respect to oxygen within these quenched glasses. This low coordination is attributed, by analogy with the structural behavior of glasses compressed at 300 K, to the instability of higher coordinations in glasses of these compositions on decompression. Spectra of glasses formed in a hydrous environment document that water is extensively soluble in melts at these high pressures and temperatures. Also, these results are consistent with the melting of (Mg0.88Fe0.12)2SiO4 compositions to liquids near pyroxene in stoichiometry under these conditions, with iron-rich magnesiowuestite being the liquidus phase.

Effects of Y2O3 on crystallization kinetics of SiO2-Al2O3-CaO-CaF2 oxy-fluoride glass-ceramic system

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M. Soleymani Zarabad

Full Text Available Differential thermal analysis (DTA patterns of SiO2-Al2O3-CaO-CaF2 oxy-fluoride glass system with adding different amounts of Y2O3 from 0.5 (wt% to 1.5 (wt% have been studied under isochronal circumstances. It is concluded that, the crystallization of the glasses is a process controlled by Avrami nucleation, three dimensional diffusion controlled growth and anisotropic growth impingement mode. Afterwards, the effective activation energy Qp, growth exponent, nucleation activation energy QN, and growth activation energy QG, have been determined and were in the range of 283–321 kJ mol−1, 2.05–2.25, 190–249 kJ mol−1 and 325–349 kJ mol−1, respectively. Qp, QN, QG and np are increased with increase of Y2O3 amount, which is related to the network forming role of Y2O3 in these systems. Keywords: Oxy-fluoride glass-ceramics, Activation energy, Crystallization mechanism, Growth exponent

Preparation, structural characterization, and in vitro cell studies of three-dimensional SiO2-CaO binary glass scaffolds built ofultra-small nanofibers.

Science.gov (United States)

Luo, Honglin; Li, Wei; Ao, Haiyong; Li, Gen; Tu, Junpin; Xiong, Guangyao; Zhu, Yong; Wan, Yizao

2017-07-01

Three-dimensional (3D) nanofibrous scaffolds hold great promises in tissue engineering and regenerative medicine. In this work, for the first time, 3D SiO 2 -CaO binary glass nanofibrous scaffolds have been fabricated via a combined method of template-assisted sol-gel and calcination by using bacterial cellulose as the template. SEM with EDS, TEM, and AFM confirm that the molar ratio of Ca to Si and fiber diameter of the resultant SiO 2 -CaO nanofibers can be controlled by immersion time in the solution of tetraethyl orthosilicate and ethanol. The optimal immersion time was 6h which produced the SiO 2 -CaO binary glass containing 60at.% Si and 40at.% Ca (named 60S40C). The fiber diameter of 60S40C scaffold is as small as 29nm. In addition, the scaffold has highly porous 3D nanostructure with dominant mesopores at 10.6nm and macropores at 20μm as well as a large BET surface area (240.9m 2 g -1 ), which endow the 60S40C scaffold excellent biocompatibility and high ALP activity as revealed by cell studies using osteoblast cells. These results suggest that the 60S40C scaffold has great potential in bone tissue regeneration. Copyright © 2017 Elsevier B.V. All rights reserved.

The electrorheological properties of nano-sized SiO2 particle materials doped with rare earths

International Nuclear Information System (INIS)

Liu Yang; Liao Fuhui; Li Junran; Zhang Shaohua; Chen Shumei; Wei Chenguan; Gao Song

2006-01-01

Electrorheological (ER) materials of pure SiO 2 and SiO 2 doped with rare earths (RE = Ce, Gd, Y) (non-metallic glasses (silicates)) were prepared using Na 2 SiO 3 and RECl 3 as starting materials. The electrorheological properties are not enhanced by all rare earth additions. The material doped with Ce exhibits the best ER performance

Espumas vítreas do sistema Li2O-ZrO2-SiO2-Al2O 3 produzidas pelo processo gelcasting Li2O-ZrO2-SiO2 -Al2O3 glass-ceramic foams produced by the gelcasting process

Directory of Open Access Journals (Sweden)

E. de Sousa

2009-06-01

Full Text Available Espumas vítreas do sistema Li2O-ZrO2-SiO2-Al2O 3 (LZSA foram produzidas pelo processo gelcasting, associado à aeração de suspensões cerâmicas, sem controle atmosférico. Por meio da adição de diferentes concentrações de agente espumante (Fongraminox foi possível obter espumas vítreas com densidade relativa variando entre uma estreita faixa (0,10-0,15. As espumas vítreas apresentaram resistência à compressão de 2,5-3,7 MPa, que correspondem a porosidade entre 85 e 89% e macroestrutra com poros aproximadamente esféricos e interconectados. Tais características tornam esses materiais atraentes para as seguintes aplicações tecnológicas: filtros para metais fundidos e gases quentes e, suportes catalíticos.Vitreous foams in the Li2O-ZrO2-SiO2-Al2O 3 (LZSA system were produced by the gelcasting process with aeration of ceramic suspensions and without atmospheric control. By the addition of different concentrations of foaming agent (Fongraminox it was possible to attain glass-ceramic foams in a narrow range of relative density (0.10-0.15. The glass-ceramic foams showed compressive strength of 2.5-3.7 MPa, which corresponds to porosity between 85-89%, and macrostructure with pores nearly spherical and interconnected, these characteristics make these materials attractive for the following applications technology: filters of molten metals and hot gas, and catalytic support.

Experimental Determination of the Effect of the Ratio of B/Al on Glass Dissolution along the Nepheline (NaAlSiO₄) – Malinkoite (NaBSiO₄) Join

Energy Technology Data Exchange (ETDEWEB)

Pierce, Eric M; Reed, Lunde R; Shaw, Wendy J; McGrail, B Peter; Icenhower, Jonathan P; Windisch, Charles F; Cordova, Elsa A; Broady, Johnathan W

2010-03-27

The dissolution kinetics of five glasses along the NaAlSiO₄-NaBSiO₄ join were used to evaluate how the structural variations associated with boron-aluminum substitution affect the rate of dissolution. The composition of each glass varied inversely in mol% of Al₂O₃ (5 to 25 mol%) and B₂O₃ (20 to 0 mol%) with Na₂O (25 mol%) and SiO₂ (50 mol%) making up the remaining amount, in every case Na/(Al+B) = 1.0. Single-pass flow-through experiments (SPFT) were conducted under dilute conditions as a function of solution pH (from 7.0 to 12.0) and temperature (from 23° to 90°C). Analysis by ²⁷Al and ²⁹Si MAS-NMR suggests Al (~98% ^[4]Al) and Si atoms (~100% ^[4]Si) occupy a tetrahedral coordination whereas, B atoms occupy both tetrahedral ([4]B) and trigonal (^[3]B) coordination. The distribution of [3]B fractionated between ^[3]B(ring) and ^[3]B(non-ring) moieties, with the ^[3]B(ring)/^[3]B(non-ring) ratio increases with the B/Al ratio. The MAS-NMR results also indicated an increase in the fraction of ^[4]B with an increase in the B/Al ratio. But despite the changes in the B/Al ratio and B coordination, the ²⁹Si spectra maintain a chemical shift between -88 to -84 ppm for each glass. Unlike the ²⁹Si spectra, the ²⁷Al resonances shift to more positive values with an increase in the B/Al ratio which suggests mixing between the ^[4]Al and ^[3]B sites, assuming avoidance between tetrahedral trivalent cations (^[4]Al-O-^[4]B avoidance). Raman spectroscopy was use to augment the results collected from MAS-NMR and demonstrated that NeB4 (glass sample with the highest B content) was glass-glass phase separated (e.g., heterogeneous glass). Results from SPFT experiments suggest a forward rate of reaction and pH power law

SiO2 decoration dramatically enhanced the stability of PtRu electrocatalysts with undetectable deterioration in fuel cell performance

Science.gov (United States)

Yu, Xinxin; Xu, Zejun; Yang, Zehui; Xu, Sen; Zhang, Quan; Ling, Ying; Zhang, Yunfeng; Cai, Weiwei

2018-06-01

Prevention of Ru dissolution is essential for steady CO tolerance of anodic electrocatalysts in direct methanol fuel cells. Here, we demonstrate a facile way to stabilize Ru atoms by decorating commercial CB/PtRu with SiO2, which shows a six-fold higher stability and similar activity toward a methanol oxidation reaction leading to no discernible degradation in fuel cell performance compared to commercial CB/PtRu electrocatalysts. The higher stability and stable CO tolerance of SiO2-decorated electrocatalysts originate from the SiO2 coating, since Ru atoms are partially ionized during SiO2 decorating, resulting in difficulties in dissolution; while, in the case of commercial CB/PtRu, the dissolved Ru offers active sites for Pt coalescences and CO species resulting in the rapid decay of the electrochemical surface area and fuel cell performance. To the best of our knowledge, this is the first study about the stabilization of Ru atoms by SiO2. The highest stability is obtained for a PtRu electrocatalyst with negligible effect on the electrochemical properties.

Highly efficient transparent Zn2SiO4:Mn2+ phosphor film on quartz glass

International Nuclear Information System (INIS)

Seo, K.I.; Park, J.H.; Kim, J.S.; Kim, G.C.; Yoo, J.H.

2009-01-01

Highly efficient transparent Zn 2 SiO 4 :Mn 2+ film phosphors on quartz substrates were deposited by the thermal diffusion of sputtered ZnO:Mn film. They show a textured structure with some preferred orientations. Our film phosphor shows, for the best photoluminescence (PL) brightness, a green PL brightness of about 20% of a commercial Zn 2 SiO 4 :Mn 2+ powder phosphor screen. The film shows a high transmittance of more than 10% at the red-color region. The excellence in PL brightness and transmittance can be explained in terms of the textured crystal growth with a continuous gradient of Zn 2 SiO 4 : Mn 2+ crystals.

Synthesis, cytotoxicity, and hydroxyapatite formation in 27-Tris-SBF for sol-gel based CaO-P2O5-SiO2-B2O3-ZnO bioactive glasses.

Science.gov (United States)

Kaur, Gurbinder; Pickrell, G; Kimsawatde, G; Homa, D; Allbee, H A; Sriranganathan, N

2014-03-18

CaO-P2O5-SiO2-B2O3-ZnO bioactive glasses were prepared via an optimized sol-gel method. The current investigation was focused on producing novel zinc based calcium phosphoborosilicate glasses and to evaluate their mechanical, rheological, and biocompatible properties. The morphology and composition of these glasses were studied using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The particle size, mechanical and flexural strength was also determined. Furthermore, the zeta potential of all the glasses were determined to estimate their flocculation tendency. The thermal analysis and weight loss measurements were carried out using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) respectively. For assessing the in-vitro bioactive character of synthesized glasses, the ability for apatite formation on their surface upon their immersion in simulated body fluid (SBF) was checked using SEM and pH measurements. MTS assay cytotoxicity assay and live-dead cell viability test were conducted on J774A.1 cells murine macrophage cells for different glass concentrations.

Physical and Electrical Properties of SiO2 Layer Synthesized by Eco-Friendly Method

Science.gov (United States)

Kim, Jong-Woong; Kim, Young-Seok; Hong, Sung-Jei; Hong, Tae-Hwan; Han, Jeong-In

2010-05-01

SiO2 thin film has a wide range of applications, including insulation layers in microelectronic devices, such as semiconductors and flat panel displays, due to its advantageous characteristics. Herein, we developed a new eco-friendly method for manufacturing SiO2 nanoparticles and, thereby, SiO2 paste to be used in the digital printing process for the fabrication of SiO2 film. By excluding harmful Cl- and NO3- elements from the SiO2 nanoparticle synthetic process, we were able to lower the heat treatment temperature for the SiO2 precursor from 600 to 300 °C and the diameter of the final SiO2 nanoparticles to about 14 nm. The synthesized SiO2 nanoparticles were dispersed in an organic solvent with additives to make a SiO2 paste for feasibility testing. The SiO2 paste was printed onto a glass substrate to test the feasibility of using it for digital printing. The insulation resistance of the printed film was high enough for it to be used as an insulation layer for passivation.

Studies on the Potential of Waste Soda Lime Silica Glass in Glass Ionomer Cement Production

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V. W. Francis Thoo

2013-01-01

Full Text Available Glass ionomer cements (GIC are produced through acid base reaction between calcium-fluoroaluminosilicate glass powder and polyacrylic acid (PAA. Soda lime silica glasses (SLS, mainly composed of silica (SiO2, have been utilized in this study as the source of SiO2 for synthesis of Ca-fluoroaluminosilicate glass. Therefore, the main objective of this study was to investigate the potential of SLS waste glass in producing GIC. Two glasses, GWX 1 (analytical grade SiO2 and GWX 2 (replacing SiO2 with waste SLS, were synthesized and then characterized using X-ray diffraction (XRD and energy dispersive X-ray (EDX. Synthesized glasses were then used to produce GIC, in which the properties were characterized using Fourier transform infrared spectroscopy (FT-IR and compressive test (from 1 to 28 days. XRD results showed that amorphous glass was produced by using SLS waste glass (GWX 2, which is similar to glass produced using analytical grade SiO2 (GWX 1. Results from FT-IR showed that the setting reaction of GWX 2 cements is slower compared to cement GWX 1. Compressive strengths for GWX 1 cements reached up to 76 MPa at 28 days, whereas GWX 2 cements showed a slightly higher value, which is 80 MPa.

Crystallization and sintering characteristics of CaO-Al2O3-SiO2 glasses in the presence of TiO2, CaF2 and ZrO2

International Nuclear Information System (INIS)

Banijamali, S.; Eftekhari Yekta, B.; Rezaie, H.R.; Marghussian, V.K.

2009-01-01

In this study, the effects of different amounts of TiO 2 , ZrO 2 and CaF 2 nucleating agents on sinterability, crystallization, mechanical properties and chemical resistance of glass-ceramics belonging to the CaO-Al 2 O 3 -SiO 2 system were investigated, using differential thermal analysis (DTA), X-ray diffractometry (XRD), scanning electron microscopy (SEM), mechanical and chemical resistance measurements. It was found that in CaF 2 containing samples, the sinterability, crystallization and mechanical properties were improved by increasing of CaF 2 amount. However, addition of ZrO 2 and TiO 2 increases the firing temperature required for complete densification of specimens. Our experiments showed that fluctuations of chemical composition of the residual glass phases during sintering were responsible for these dissimilar trends and greatly influenced mechanical and chemical properties. According to the obtained results, appropriate sinterability, acceptable mechanical and chemical properties, as well as desirable whiteness of the most promising specimens make them suitable choices for floor tile applications. The main crystallization phases in all fully sintered glass-ceramics were wollastonite, anorthite and calcium aluminum silicate.

Study of a Mixed Alkaline–Earth Effect on Some Properties of Glasses of the CaO-MgO-Al2O3-SiO2 System

Directory of Open Access Journals (Sweden)

Valle-Fuentes, J. F.

2007-06-01

Full Text Available In the present work, we studied a “Mixed Alkaline–Earth Effect”, i.e. the non-linear behaviour showed by the glass transition temperature as well as by the compressive strength of glasses of the CaO-MgO-Al2O3-SiO2 system, when a part of the CaO contained in them was substituted by a BaO/SrO mixture, in variable molar proportions. An important factor for the occurrence of this phenomenon was the difference in atomic weight, ionic radii and field strength of the Ba2+ and Sr2+ ions in comparison with those corresponding to the Ca2+ ion. Another factor considered was the likely occurrence of a microphase separation caused by the addition of BaO and/or SrO, together with the presence of F- and Mg2+ in the glasses. Other glass properties studied as a function of the CaO substitution level were density, glass molar volume, oxygen molar volume, packing fraction, and chemical resistance in neutral, basic and acidic aqueous media. In general, the structural reinforcement of the glass network caused by the partial substitution of CaO by a BaO/SrO mixture was accompanied by an improvement in the alkaline resistance of the materials, which were found to be suitable for applications in corrosive environments, especially in basic media. Keywords: Mixed alkaline–earth effect; CaO-MgO-Al2O3-SiO2 system; glass properties.En el presente trabajo, se estudia el comportamiento no lineal mostrado por la temperatura de transición vítrea y por la resistencia a la compresión de vidrios del sistema CaO-MgO-Al2O3-SiO2, cuando una parte del CaO contenido en los mismos es sustituido por una mezcla de BaO/SrO, en relación molar variable. Factores importantes para que se de este comportamiento son la diferencia entre pesos atómicos, radios iónicos e intensidad de campo de los iones Ba2+ y Sr2+ y los del propio ión Ca2+. Otro factor considerado ha sido la probable existencia de una separación de microfases originada por la adición de BaO y/o SrO, junto con la

Aqueous corrosion of french R7T7 nuclear waste glass: selective then congruent dissolution by pH increase

International Nuclear Information System (INIS)

Advocat, T.; Vernaz, E.; Crovisier, J.L.

1991-01-01

A study of the corrosion of a borosilicate nuclear glass shows the strong effect of the pH on the dissolution mechanism. Acidic media lead to selective extraction of the glass modifier elements (Li, Na, Ca) as well as B, while dissolution is congruent under alkaline conditions. The silica dissolution rate significantly increases with increasing pH [fr

JSS project phase 4: Experimental and modelling studies of HLW glass dissolution in repository environments

International Nuclear Information System (INIS)

1987-10-01

A goal of the JSS project was to develop a scientific basis for understanding the effects of waste package components, groundwater chemistry, and other repository conditions on glass dissolution behaviour, and to develop and refine a model for the processes governing glass dissolution. The fourth phase of the project, which was performed by the Hahn-Meitner-Institut, Berlin, FRG, dealt specifically with model development and application. Phase 4 also adressed whether basaltic glasses could serve as natural analogues for nuclear waste glasses, thus providing a means to test the capability of the model for long-term predictions. Additional experiments were performed in order to complete the data base necessary to model interactions between the glass and bentonite and between glass and steel corrosion products. More data on temperature, S/V, and pH dependence of the glass/water reaction were also collected. In this report, the data acquired during phase 4 are presented and discussed. (orig./DG)

Development and characterization of glass-ceramic sealants in the (CaO-Al2O3-SiO2-B2O3) system for Solid Oxide Electrolyzer Cells

International Nuclear Information System (INIS)

Khedim, Hichem; Nonnet, Helene; Mear, Francois O.

2012-01-01

The efficiency of glass-ceramic sealants plays a crucial role in Solid Oxide Electrolyzer Cell performance and durability. In order to develop suitable sealants, operating around 800 degrees C, two parent glass compositions, CAS1B and CAS2B, from the CaO-Al 2 O 3 -SiO 2 -B 2 O 3 system were prepared and explored. The thermal and physicochemical properties of the glass ceramics and their crystallization behavior were investigated by HSM. DTA and XRD analyses. The microstructure and chemical compositions of the crystalline phases were investigated by microprobe analysis. Bonding characteristic as well as chemical interactions of the parent glass with yttria-stabilized zirconia (YSZ) electrolyte and ferritic steel-based interconnect (Crofere (R)) were also investigated. The preliminary results revealed the superiority of CAS2B glass for sealing application in SOECs. The effect of minor additions of V 2 O 5 , K 2 O and TiO 2 on the thermal properties was also studied and again demonstrated the advantages of the CAS2B glass composition. Examining the influence of heat treatment on the seal behavior showed that the choice of the heating rate is a compromise between delaying the crystallization process and delaying the viscosity drop. The thermal Expansion Coefficients (TEC) obtained for the selected glass ceramic are within the desired range after the heat treatment of crystallization. The crystallization kinetic parameters of the selected glass composition were also determined under non-isothermal conditions by means of differential thermal analysis (DTA) and using the formal theory of transformations for heterogeneous nucleation. (authors)

Quantifying silica reactivity in subsurface environments: Reaction affinity and solute matrix controls on quartz and SiO2 glass. 1997 annual progress report

International Nuclear Information System (INIS)

Dove, P.M.

1997-01-01

'The author reports the preliminary results of the experiments on the dissolution behavior of vitreous silica (v-SiO 2 ) into aqueous solutions of variable pH and ionic strength. The experiments are being conducted in mixed flow reactors with a high circulation rate that simulates constant-stirred conditions, the efficacy of which the authors discuss below. The preliminary results indicate that v-SiO 2 dissolves into aqueous solutions approximately two orders of magnitude more quickly than crystalline silica (e.g., quartz). With additional experiments, they will utilize the dissolution rate data as a framework for understanding the behavior of waste glass compositions in the subsurface. In other work related to the studies of glass reactivity, the author has written one book chapter that will be published as part of a proceedings for the CEA/VALRHO international nuclear waste disposal conference held in Mejannes le Clap, France. In separate work, she is presently writing a second book chapter for the volume entitled Adsorption on Silica Surfaces.'

The properties and structure of Sn---Ca---P---O---F glasses

International Nuclear Information System (INIS)

Ding, J.Y.; Shih, P.Y.; Yung, S.W.; Hsu, K.L.; Chin, T.S.

2003-01-01

Low melting modified calcium stannous fluorophosphate glasses based on a basic composition 40P 2 O 5 -25SnO-30SnF 2 -5CaF 2 (in mol%) with glass transition temperature T g ranging 220-240 deg. C have been prepared. The effect of Al(OH) 3 or SiO 2 addition on the properties of these glasses has also been determined. Aluminum and silicon compounds decrease the dissolution rate in water and thermal expansion coefficient while increase the density, T g and softening temperature. The effect of Al(OH) 3 addition on the increase of chemical durability is better for these glasses, due to the partial crystallization effect in stannous calcium silicofluorophosphate glasses. With an addition of 4 wt.% Al(OH) 3 , the dissolution rate of the glass in 30 deg. C water decreases from 1.0x10 -5 to 1.3x10 -7 g cm -2 min. The structure of Al(OH) 3 added glasses was studied by 27 Al and 31 P MAS NMR and Fourier transform IR (FTIR) spectroscopies to explain the relationship between glass properties and composition. The 27 Al spectra show three different aluminum environments [Al(OP) 6 , Al(OP) 5 and Al(OP) 4 ], and Al(OP) 6 species seem to be predominant in these glasses. The formation of P---O-Al covalent bond and more strongly ionic bonds increase the strength of the glass network in stannous calcium aluminofluorophosphate glasses. FTIR spectra indicate the presence of P--F bond in the short range glass structure

Controlled dissolution of silicon dioxide layers for depth resolved multielement analysis by inductively coupled plasma-mass spectrometry

International Nuclear Information System (INIS)

Lorge, Susan E.; Houk, R.S.

2009-01-01

Dissolution procedures were developed to control the number of surface layers removed, in an attempt to achieve depth resolved analysis by inductively coupled plasma-mass spectrometry (ICP-MS). NIST 612 glass was chosen because it is a homogeneous material with many elements at interesting concentrations, ∼ 50 ppm. Varying dissolution time and HF concentration resulted in the reproducible removal of SiO 2 layers as thin as 70 A deep. Dissolved trace metals were determined after dilution by inductively coupled plasma-mass spectrometry (ICP-MS) with a magnetic sector instrument. The amount removed was determined from the concentration of a major element, Ca. With the exception of Zn, trace metal concentrations agreed reasonably well with their certified values for removal depths of 500, 300 and 150 A. Zinc concentration was significantly high in all dissolutions indicating either a contamination problem or that Zn is removed at a faster rate than Ca. For the dissolutions that removed 70 A of SiO 2 , Cr, Mn, Co, Sr, Cd, Ce, Dy, Er, Yb and U recovery results agreed with their certified values (∼ 50 ppm); Ti, As, Mo, Ba, and Th could not be determined because net intensities were below 3σ of the blank; and measured concentrations for Cu, Pb and Zn were well above the certified values.

The effect of TiO2 on nucleation and crystallization of a Li2O-Al2O3-SiO2 glass investigated by XANES and STEM.

Science.gov (United States)

Kleebusch, Enrico; Patzig, Christian; Krause, Michael; Hu, Yongfeng; Höche, Thomas; Rüssel, Christian

2018-02-13

Glass ceramics based on Li 2 O/Al 2 O 3 /SiO 2 are of high economic importance, as they often show very low coefficients of thermal expansion. This enables a number of challenging applications, such as cooktop panels, furnace windows or telescope mirror blanks. Usually, the crystallization of the desired LAS crystal phases within the glasses must be tailored by a careful choice of crystallization schedule and type of nucleation agents to be used. The present work describes the formation of nanocrystalline TiO 2 within an LAS base composition that contains solely TiO 2 as nucleating agent. Using a combination of scanning transmission electron microscopy as well as X-ray absorption spectroscopy, it is found that a mixture of four- and six-fold coordinated Ti 4+ ions exists already within the glass. Heating of the glass to 740 °C immediately changes this ratio towards a high content of six-fold coordinated Ti, which accumulates in liquid-liquid phase-separation droplets. During the course of thermal treatment, these droplets eventually evolve into nanocrystalline TiO 2 precipitations, in which Ti 4+ is six-fold coordinated. Thus, it is shown that the nucleation of nanocrystalline TiO 2 is initiated by a gradual re-arrangement of the Ti ions in the amorphous, glassy matrix, from a four-fold towards a six-fold coordination.

In Vitro Human Umbilical Vein Endothelial Cells Response to Ionic Dissolution Products from Lithium-Containing 45S5 Bioactive Glass

Science.gov (United States)

Haro Durand, Luis A.; Vargas, Gabriela E.; Vera-Mesones, Rosa; Baldi, Alberto; Zago, María P.; Fanovich, María A.; Boccaccini, Aldo R.; Gorustovich, Alejandro

2017-01-01

Since lithium (Li+) plays roles in angiogenesis, the localized and controlled release of Li+ ions from bioactive glasses (BGs) represents a promising alternative therapy for the regeneration and repair of tissues with a high degree of vascularization. Here, microparticles from a base 45S5 BG composition containing (wt %) 45% SiO2, 24.5% Na2O, 24.5% CaO, and 6% P2O5, in which Na2O was partially substituted by 5% Li2O (45S5.5Li), were obtained. The results demonstrate that human umbilical vein endothelial cells (HUVECs) have greater migratory and proliferative response and ability to form tubules in vitro after stimulation with the ionic dissolution products (IDPs) of the 45S5.5Li BG. The results also show the activation of the canonical Wnt/β-catenin pathway and the increase in expression of proangiogenic cytokines insulin like growth factor 1 (IGF1) and transforming growth factor beta (TGFβ). We conclude that the IDPs of 45S5.5Li BG would act as useful inorganic agents to improve tissue repair and regeneration, ultimately stimulating HUVECs behavior in the absence of exogenous growth factors. PMID:28773103

Preparation of orthophosphate glasses in the MgO-CaO-SiO2-Nb2O5-P2O5 system.

Science.gov (United States)

Lee, Sungho; Ueda, Kyosuke; Narushima, Takayuki; Nakano, Takayoshi; Kasuga, Toshihiro

2017-01-01

Niobia/magnesia-containing orthophosphate invert glasses were successfully prepared in our earlier work. Orthophosphate groups in the glasses were cross-linked by tetrahedral niobia (NbO4) and magnesia. The aim of this work is to prepare calcium orthophosphate invert glasses containing magnesia and niobia, incorporating silica, and to evaluate their structures and releasing behaviors. The glasses were prepared by melt-quenching, and their structures and ion-releasing behaviors were evaluated. 31P solid-state nuclear magnetic resonance (NMR) and Raman spectroscopies showed the glasses consist of orthophosphate (PO4), orthosilicate (SiO4), and NbO4 tetrahedra. NbO4 and MgO in the glasses act as network formers. By incorporating SiO2 into the glasses, the chemical durability of the glasses was slightly improved. The glasses reheated at 800°C formed the orthophosphate crystalline phases, such as β-Ca3(PO4)2, Mg3(PO4)2 and Mg3Ca3(PO4)4 in the glasses. The chemical durability of the crystallized glasses was slightly improved. Orthosilicate groups and NbO4 in the glasses coordinated with each other to form Si-O-Nb bonds. The chemical durability of the glasses was slightly improved by addition of SiO2, since the field strength of Si is larger than that of Ca or Mg.

Investigation of gamma ray shielding, structural and dissolution rate properties of Bi2O3-BaO-B2O3-Na2O glass system

Science.gov (United States)

Dogra, Mridula; Singh, K. J.; Kaur, Kulwinder; Anand, Vikas; Kaur, Parminder; Singh, Prabhjot; Bajwa, B. S.

2018-03-01

In the present study, quaternary system of the composition (0.45 + x) Bi2O3-(0.25 - x) BaO-0.15 B2O3-0.15 Na2O (where 0 ≤ x ≤ 0.2 mol fraction) has been prepared by using melt-quenching technique for investigation of gamma ray shielding properties. Mass attenuation coefficients and half value layer parameters have been determined experimentally at 662 keV by using 137Cs source. It has been found that experimental results of these parameters hold good agreement with theoretical values. The density, molar volume, XRD, FTIR, Raman and UV-visible studies have been used to determine structural properties of the prepared glass samples. Dissolution rate of the samples has also been measured to check their utility as long term durable glasses.

Predicting bioactive glass properties from the molecular chemical composition: glass transition temperature.

Science.gov (United States)

O'Donnell, Matthew D

2011-05-01

The glass transition temperature (T(g)) of inorganic glasses is an important parameter than can be used to correlate with other glass properties, such as dissolution rate, which governs in vitro and in vivo bioactivity. Seven bioactive glass compositional series reported in the literature (77 in total) were analysed here with T(g) values obtained by a number of different methods: differential thermal analysis, differential scanning calorimetry and dilatometry. An iterative least-squares fitting method was used to correlate T(g) from thermal analysis of these compositions with the levels of individual oxide and fluoride components in the glasses. When all seven series were fitted a reasonable correlation was found between calculated and experimental values (R(2)=0.89). When the two compositional series that were designed in weight percentages (the remaining five were designed in molar percentage) were removed from the model an improved fit was achieved (R(2)=0.97). This study shows that T(g) for a wide range in compositions (e.g. SiO(2) content of 37.3-68.4 mol.%) can be predicted to reasonable accuracy enabling processing parameters to be predicted such as annealing, fibre-drawing and sintering temperatures. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Synthesis and optical properties of SiO2–Al2O3–MgO–K2CO3–CaO ...

Indian Academy of Sciences (India)

Synthesis and optical properties of SiO 2 –Al 2 O 3 –MgO–K 2 CO 3 –CaO–MgF 2 –La 2 O 3 glasses. C R GAUTA. Volume 39 Issue 3 June 2016 pp 677-682 ... Author Affiliations. C R GAUTA1. Advanced Glass and Glass Ceramic Research Laboratory, Department of Physics, University of Lucknow, Lucknow 226007, India ...

Visible Light Excited Catalysis and Reusability Performances of TiO2@Pr:Y2SiO5 Upconversion Materials

Directory of Open Access Journals (Sweden)

Yan Jiao

2017-01-01

Full Text Available To get high efficiency photodegradation on pollutants under visible light, Pr(III doped Y2SiO5 upconversion materials and anatase TiO2 nanofilm coated Pr:Y2SiO5 composite have been prepared by using a sol-gel method. XRD and SEM test results indicated that TiO2 nanofilm was well coated on Pr:Y2SiO5 to form TiO2@Pr:Y2SiO5 composite particles with the sizes of 0.5–1.0 μm. To avoid secondary pollution resulting from incomplete recovery of catalyst particles, TiO2@Pr:Y2SiO5 was loaded on the glass fiber filters by using a dip-coating method. It is found that the catalyst particles were embedded into the carrier firmly, even after having been reused for 6 times. The luminescence intensities of TiO2@Pr:Y2SiO5 were getting down sharply with the coating contents of TiO2 increased, which was attributed to the adsorption of the luminescence by the TiO2 film in situ. As a result, TiO2@Pr:Y2SiO5 with 4% TiO2, which presented lowest luminescence intensity, showed the highest efficiency on the photodegradation of nitrobenzene wastewater. The catalysts loaded on glass fiber filters showed excellent reusability on the photodegradation of nitrobenzene and presented a photodegradation rate of 95% at the first time and up to 75.9% even after 6 times of reusing by the treatment time of 12 h.

Neutron-irradiation effects on SiO2 and SiO2-based glass ceramics

International Nuclear Information System (INIS)

Porter, D.L.; Pascucci, M.R.; Olbert, B.H.

1981-01-01

A preliminary data base to assess the radiation-damage resistance of some glass ceramic materials has been gathered. These are rather complex materials, both in structure and composition, but possess many of those properties required for structural, insulator applications in fusion-reactor design. Property measurements were made after fast (E > 0.1 MeV) neutron irradiations of approx. 2.4 x 10 22 n/cm 2 at 400 0 C and 550 0 C. The results have shown general resistance to changes in thermal expansion and most did not eperience severe loss of mechanical integrity. The maximum volume expansion occurred in several of the fluorophlogapite-based glass ceramics (approx. 3.0%). Several observations demonstrated differences between the effects of neutron and electron irradiation; irradiation conditions proptotypic of projected reactor uses need be considered for optimum materials selection

First-order dissolution rate law and the role of surface layers in glass performance assessment

Science.gov (United States)

Grambow, B.; Müller, R.

2001-09-01

The first-order dissolution rate law is used for nuclear waste glass performance predictions since 1984. A first discussion of the role of saturation effects was initiated at the MRS conference that year. In paper (1) it was stated that "For glass dissolution A* (the reaction affinity) cannot become zero since saturation only involves the reacting surface while soluble elements still might be extracted from the glass" [B. Grambow, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 15]. Saturation of silica at the surface and condensation of surface silanol groups was considered as being responsible for the slow down of reaction rates by as much as a factor of 1000. Precipitation of Si containing secondary phases such as quartz was invoked as a mechanism for keeping final dissolution affinities higher than zero. Another (2) paper [A.B. Barkatt, P.B. Macedo, B.C. Gibson, C.J. Montrose, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 3] stated that "… under repository conditions the extent of glass dissolution will be moderate due to saturation with respect to certain major elements (in particular, Si, Al and Ca). Consequently, the concentration levels of the more soluble glass constituents in the aqueous medium are expected to fall appreciable below their solubility limit." The formation of dense surface layers was considered responsible for explaining the saturation effect. The mathematical model assumed stop of reaction in closed systems, once solubility limits were achieved. For more than 15 years the question of the correctness of one or the other concept has seldom been posed and has not yet been resolved. The need of repository performance assessment for validated rate laws demands a solution, particularly since the consequences of the two concepts and research requirements for the long-term glass behavior are quite different. In concept (1) the stability of the `equilibrium surface region' is not relevant because, by definition, this region is stable chemically and after a

Nanocrystal in Er3+-doped SiO2-ZrO2 Planar Waveguide with Yb3+ Sensitizer

International Nuclear Information System (INIS)

Razaki, N. Iznie; Jais, U. Sarah; Abd-Rahman, M. Kamil; Bhaktha, S. N. B.; Chiasera, A.; Ferrari, M.

2010-01-01

Higher doping of Er 3+ in glass ceramic waveguides would cause concentration and pair-induced quenching which lead to inhomogeneous line-width of luminescence spectrum thus reduce output intensity. Concentration quenching can be overcome by introducing ZrO 2 in the glass matrix while co-doping with Yb 3+ which acts as sensitizer would improve the excitation efficiency of Er 3+ . In this study, SiO 2 -ZrO 2 planar waveguides having composition in mol percent of 70SiO 2 -30ZrO 2 doped with Er 3+ and co-doped with Yb 3+ , were prepared via sol-gel route. Narrower and shaper peaks of PL and XRD shows the formation of nanocrystals. Intensity is increase with addition amount of Yb 3+ shows sensitizing effect on Er 3+ .

Glass-ceramic nuclear waste forms obtained by crystallization of SiO 2-Al 2O 3-CaO-ZrO 2-TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th): Study of the crystallization from the surface

Science.gov (United States)

Loiseau, P.; Caurant, D.

2010-07-01

Glass-ceramic materials containing zirconolite (nominally CaZrTi 2O 7) crystals in their bulk can be envisaged as potential waste forms for minor actinides (Np, Am, Cm) and Pu immobilization. In this study such matrices are synthesized by crystallization of SiO 2-Al 2O 3-CaO-ZrO 2-TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th) as surrogates. A thin partially crystallized layer containing titanite and anorthite (nominally CaTiSiO 5 and CaAl 2Si 2O 8, respectively) growing from glass surface is also observed. The effect of the nature and concentration of surrogates on the structure, the microstructure and the composition of the crystals formed in the surface layer is presented in this paper. Titanite is the only crystalline phase able to significantly incorporate trivalent lanthanides whereas ThO 2 precipitates in the layer. The crystal growth thermal treatment duration (2-300 h) at high temperature (1050-1200 °C) is shown to strongly affect glass-ceramics microstructure. For the system studied in this paper, it appears that zirconolite is not thermodynamically stable in comparison with titanite growing form glass surface. Nevertheless, for kinetic reasons, such transformation (i.e. zirconolite disappearance to the benefit of titanite) is not expected to occur during interim storage and disposal of the glass-ceramic waste forms because their temperature will never exceed a few hundred degrees.

Glass–water interaction: Effect of high-valence cations on glass structure and chemical durability

Energy Technology Data Exchange (ETDEWEB)

Hopf, J.; Kerisit, Sebastien N.; Angeli, F.; Charpentier, Thibault M.; Icenhower, Jonathan P.; McGrail, Bernard P.; Windisch, Charles F.; Burton, Sarah D.; Pierce, Eric M.

2016-05-15

Borosilicate glass is a durable solid, but it dissolves when in contact with aqueous fluids. The dissolution mechanism, which involves a variety of sequential reactions that occur at the solid-fluid interface, has important implications for the corrosion resistance of industrial and nuclear waste glasses. In this study, spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high–valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na2O–Al2O3–B2O3–HfO2–SiO2 system (e.g., Na/[Al+B] = 1.0 and HfO2/SiO2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N4 (tetrahedral boron/total boron) and increases the amount of Si—O—Hf moieties in the glass. Results from flow–through experiments conducted under dilute and near–saturated conditions show a decrease of approximately 100× or more in the dissolution rate over the series from 0 to 20 mol% HfO2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveals a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the stronger binding of Si sites that deposit on the surface from the influent when Hf is present in the glass. As a result, the residence time at the glass surface of these newly-formed Si sites is longer in the presence of Hf, which increases the density of anchor sites from which altered layers

Modeling the dissolution behavior of defense waste glass in a salt repository environment

International Nuclear Information System (INIS)

McGrain, B.P.

1988-02-01

A mechanistic model describing a dynamic mass balance between the production and consumption of dissolved silica was found to describe the dissolution behavior of SRL-165 defense waste glass in a high-magnesium brine (PBB3) at a temperature of 90 0 C. The synergistic effect of the waste package container on the glass dissolution rate was found to depend on a precipitation reaction for a ferrous silicate mineral. The model predicted that the ferrous silicate precipitate should be variable in composition where the iron/silica stoichiometry depended on the metal/glass surface area ratio used in the experiment. This prediction was confirmed experimentally by the variable iron/silica ratios observed in filtered leachates. However, the interaction between dissolved silica and iron corrosion products needs to be much better understood before the model can be used with confidence in predicting radionuclide release rates for a salt repository. 25 refs., 4 figs., 1 tab

Dependence of glass-forming ability on starting compositions in Y2O3–Al2O3–SiO2 system

OpenAIRE

Yixiang Chen; Zengchao Yang; Bin He; Guanghua Liu; Jiangtao Li; Liang Wu

2011-01-01

The dependence of glass-forming ability on starting compositions in Y2O3–Al2O3–SiO2 (YAS) system has been investigated by melting experiment. Transparent YAS glasses have been prepared under the condition of furnace cooling instead of quenching. It is found that, in the YAS ternary phase diagram, the compositions on the Y3Al5O12–SiO2 line and with 52-68 mol% SiO2 have a higher glass-forming ability to produce pure glass. For the compositions with too much or less SiO2 or with Y/Al = 5/3, 1/1,...

Sol–gel hybrid membranes loaded with meso/macroporous SiO2, TiO2–P2O5 and SiO2–TiO2–P2O5 materials with high proton conductivity

International Nuclear Information System (INIS)

Castro, Yolanda; Mosa, Jadra; Aparicio, Mario; Pérez-Carrillo, Lourdes A.; Vílchez, Susana; Esquena, Jordi; Durán, Alicia

2015-01-01

In this work, highly conductive hybrid organic–inorganic membranes loaded with SiO 2 , TiO 2 –P 2 O 5 and SiO 2 –TiO 2 –P 2 O 5 meso/macroporous particles were prepared via a sol–gel process. Meso/macroporous particles were incorporated to hybrid membranes, for improving water retention and enhancing electrochemical performance. These particles with a polymodal pore size distribution were prepared by templating in highly concentrated emulsions, the particles showed a specific surface area between 50 m 2 /g (TiO 2 –P 2 O 5 ) and 300 m 2 /g (SiO 2 –TiO 2 –P 2 O 5 ). The particles were dispersed in a hybrid silica sol and further sprayed onto glass paper. The films were polymerized and sintered; those loaded with meso/macroporous particles had a homogenous distribution. High temperature proton conductivity measurements confirmed a high water retention. Conductivity of these materials is higher than that of Nafion ® at higher temperatures (120 °C) (2·10 −2  S/cm). This study provides processing guideline to achieve hybrid electrolytes for efficient conduction of protons due to their high surface area and porous structure. - Highlights: • Hybrid electrolyte with meso/macroporous particles were synthesized by sol–gel. • Depositions of hybrid solutions by spraying onto glass substrates were performed. • Proton conductivity was evaluated as a function of composition and porous structure

Irradiation-induced hardening/softening in SiO2 studied with instrumented indentation

International Nuclear Information System (INIS)

Nakano, Shinsuke; Muto, Shunsuke; Tanabe, Tetsuo

2005-01-01

To understand the plastic deformation mechanism of SiO 2 polytypes, we measured the mechanical parameters of He + -irradiated crystalline SiO 2 (α-quartz, c-SiO 2 ) and vitreous SiO 2 (silica glass, v-SiO 2 ) as functions of the irradiation dose, by using the instrumented indentation method combined with a finite-element analysis. We extracted the effects of local rotation and bending of the SiO 4 framework (the degree of local structural freedom), which play key roles in the plastic deformation, and expressed the hardness change with a simple formula. For v-SiO 2 , the changes in the density and the number of broken bonds correlated well with the change in the degree of freedom. In contrast, for c-SiO 2 the present formulation was insufficient to fully express the hardness change in the structural disordering regime. The structure change by irradiation peculiar to this material is discussed, based on the theoretical formulation

SiO2 stabilized Pt/C cathode catalyst for proton exchange membrane fuel cells

International Nuclear Information System (INIS)

Zhu Tong; Du Chunyu; Liu Chuntao; Yin Geping; Shi Pengfei

2011-01-01

This paper describes the preparation of SiO 2 stabilized Pt/C catalyst (SiO 2 /Pt/C) by the hydrolysis of alkoxysilane, and examines the possibility that the SiO 2 /Pt/C is used as a durable cathode catalyst for proton exchange membrane fuel cells (PEMFCs). TEM and XRD results revealed that the hydrolysis of alkoxysilane did not significantly change the morphology and crystalline structure of Pt particles. The SiO 2 /Pt/C catalyst exhibited higher durability than the Pt/C one, due to the facts that the silica layers covered were beneficial for reducing the Pt aggregation and dissolution as well as increasing the corrosion resistance of supports, although the benefit of silica covering was lower than the case of Pt/CNT catalyst. Also, it was observed that the activity of the SiO 2 /Pt/C catalyst for the oxygen reduction reaction was somewhat reduced compared to the Pt/C one after the silica covering. This reduction was partially due to the low oxygen kinetics as revealed by the rotating-disk-electrode measurement. Silica covering by hydrolysis of only 3-aminopropyl trimethoxysilane is able to achieve a good balance between the durability and activity, leading to SiO 2 /Pt/C as a promising cathode catalyst for PEMFCs.

Conversion of plutonium-containing materials into borosilicate glass using the glass material oxidation and dissolution system

International Nuclear Information System (INIS)

Forsberg, C.W.; Beahm, E.C.; Parker, G.W.

1996-01-01

The end of the cold war has resulted in excess plutonium-containing materials (PCMs) in multiple chemical forms. Major problems are associated with the long-term management of these materials: safeguards and nonproliferation issues; health, environment, and safety concerns; waste management requirements; and high storage costs. These issues can be addressed by conversion of the PCMs to glass: however, conventional glass processes require oxide-like feed materials. Conversion of PCMs to oxide-like materials followed by vitrification is a complex and expensive process. A new vitrification process has been invented, the Glass Material Oxidation and Dissolution System (GMODS) to allow direct conversion of PCMs to glass. GMODS directly converts metals, ceramics, and amorphous solids to glass; oxidizes organics with the residue converted to glass; and converts chlorides to borosilicate glass and a secondary sodium chloride stream. Laboratory work has demonstrated the conversion of cerium (a plutonium surrogate), uranium (a plutonium surrogate), Zircaloy, stainless steel, multiple oxides, and other materials to glass. Equipment options have been identified for processing rates between 1 and 100,000 t/y. Significant work, including a pilot plant, is required to develop GMODS for applications at an industrial scale

Structure change of soda-silicate glass by mechanical milling

International Nuclear Information System (INIS)

Iwao, M; Okuno, M

2010-01-01

Structure change of ground soda-silicate glass (SiO 2 -Na 2 O binary systems) was investigated using X-ray diffraction (XRD) and infrared spectroscopy. The measurement results were discussed comparison to that of SiO 2 glass. With increasing Na 2 O concentrations, the XRD intensity around 2θ = 22 0 decreased and the intensity around 32 0 increased. The intensity around 22 0 and 32 0 maybe attributed to SiO 2 glass structure unit and soda-silicate glass unit, respectively. The peaks of Na 2 CO 3 crystal for 2SiO 2 -Na 2 O glass were observed with increasing milling time. This crystallization was suggested that Na + ion on 2SiO 2 -Na 2 O glass surface connected CO 2 in air. The intensity around 22 0 and 32 0 decreased and the intensity around 30 0 increased with increasing milling time. These may indicate that SiO 2 glass structure unit and soda-silicate glass structure unit were mixed by milling. In addition, IR absorption band near v = 1100 cm -1 was separated to two bands near 940 cm -1 and 1070 cm -1 with increasing Na 2 O concentrations. The band near 940 cm -1 decreased and the band near 1070 cm -1 increased with increasing milling time. These spectra changes were suggested due to decrease of Na 2 O concentrations in 2SiO 2 -Na 2 O glass with Na 2 CO 3 crystallization.

Long term effects of bioactive glass particulates on dental pulp stem cells in vitro

Directory of Open Access Journals (Sweden)

Gholami Sanaz

2017-12-01

Full Text Available Bioactive glasses (BG are known for their ability to induce bone formation by the action of their dissolution products. Glasses can deliver active ions at a sustained rate, determined by their composition and surface area. Nanoporous sol-gel derived BGs can biodegrade rapidly, which can lead to a detrimental burst release of ions and a pHrise. The addition of phosphate into the glass can buffer the pH during dissolution. Here, dissolution of BG with composition 60 mol% SiO2, 28 mol% CaO and 12 mol% P2O5 at 600 μg/ml were investigated. Initially, the dissolution and apatite formation of the BG particulates were examined in simulated body fluid using FTIR and XRD. BG particulates were indirectly exposed to dental pulp stem cells, and the effect of 14 days continuous ion release on human dental pulp stem cells (hDPSC viability and differentiation was evaluated. Alamar blue assay showed that cell proliferation was not inhibited by the continuous release of Ca, P and soluble silica. In fact, hDPSC in the presence of BG particulate displayed a higher density of mineralized nodules than untreated cells, as assessed by Alizarin red. The results will have a great contribution to the in vivo application of this particular BG.

Vibrational mode frequencies of silica species in SiO2-H2O liquids and glasses from ab initio molecular dynamics.

Science.gov (United States)

Spiekermann, Georg; Steele-MacInnis, Matthew; Schmidt, Christian; Jahn, Sandro

2012-04-21

Vibrational spectroscopy techniques are commonly used to probe the atomic-scale structure of silica species in aqueous solution and hydrous silica glasses. However, unequivocal assignment of individual spectroscopic features to specific vibrational modes is challenging. In this contribution, we establish a connection between experimentally observed vibrational bands and ab initio molecular dynamics (MD) of silica species in solution and in hydrous silica glass. Using the mode-projection approach, we decompose the vibrations of silica species into subspectra resulting from several fundamental structural subunits: The SiO(4) tetrahedron of symmetry T(d), the bridging oxygen (BO) Si-O-Si of symmetry C(2v), the geminal oxygen O-Si-O of symmetry C(2v), the individual Si-OH stretching, and the specific ethane-like symmetric stretching contribution of the H(6)Si(2)O(7) dimer. This allows us to study relevant vibrations of these subunits in any degree of polymerization, from the Q(0) monomer up to the fully polymerized Q(4) tetrahedra. Demonstrating the potential of this approach for supplementing the interpretation of experimental spectra, we compare the calculated frequencies to those extracted from experimental Raman spectra of hydrous silica glasses and silica species in aqueous solution. We discuss observed features such as the double-peaked contribution of the Q(2) tetrahedral symmetric stretch, the individual Si-OH stretching vibrations, the origin of the experimentally observed band at 970 cm(-1) and the ethane-like vibrational contribution of the H(6)Si(2)O(7) dimer at 870 cm(-1).

Sodium Is Not Essential for High Bioactivity of Glasses

Science.gov (United States)

Chen, Xiaojing; Chen, Xiaohui; Brauer, Delia S.; Wilson, Rory M.; Law, Robert V.; Hill, Robert G.; Karpukhina, Natalia

2017-01-01

This study aims to demonstrate that excellent bioactivity of glass can be achieved without the presence of an alkali metal component in glass composition. In vitro bioactivity of two sodium-free glasses based on the quaternary system SiO2-P2O5-CaO-CaF2 with 0 and 4.5 mol% CaF2 content was investigated and compared with the sodium containing glasses with equivalent amount of CaF2. The formation of apatite after immersion in Tris buffer was followed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), 31P and 19F solid state MAS-NMR. The dissolution study was completed by ion release measurements in Tris buffer. The results show that sodium free bioactive glasses formed apatite at 3 hours of immersion in Tris buffer, which is as fast as the corresponding sodium containing composition. This signifies that sodium is not an essential component in bioactive glasses and it is possible to make equally degradable bioactive glasses with or without sodium. The results presented here also emphasize the central role of the glass compositions design which is based on understanding of structural role of components and/or predicting the network connectivity of glasses. PMID:29271977

Luminescence of Eu(3+) doped SiO2 Thin Films and Glass Prepared by Sol-gel Technology

Science.gov (United States)

Castro, Lymari; Jia, Weiyi; Wang, Yanyun; Santiago, Miguel; Liu, Huimin

1998-01-01

Trivalent europium ions are an important luminophore for lighting and display. The emission of (5)D0 to (7)F2 transition exhibits a red color at about 610 nm, which is very attractive and fulfills the requirement for most red-emitting phosphors including lamp and cathode ray phosphorescence materials. Various EU(3+) doped phosphors have been developed, and luminescence properties have been extensively studied. On the other hand, sol-gel technology has been well developed by chemists. In recent years, applications of this technology to optical materials have drawn a great attention. Sol-gel technology provides a unique way to obtain homogeneous composition distribution and uniform doping, and the processing temperature can be very low. In this work, EU(3+) doped SiO2 thin films and glasses were prepared by sol-gel technology and their spectroscopic properties were investigated.

Development of an oxidation resistant glass-ceramic composite coating on Ti-47Al-2Cr-2Nb alloy

Science.gov (United States)

Li, Wenbo; Zhu, Shenglong; Chen, Minghui; Wang, Cheng; Wang, Fuhui

2014-02-01

Three glass-ceramic composite coatings were prepared on Ti-47Al-2Cr-2Nb alloy by air spraying technique and subsequent firing. The aim of this work is to study the reactions between glass matrix and inclusions and their effects on the oxidation resistance of the glass-ceramic composite coating. The powders of alumina, quartz, or both were added into the aqueous solution of potassium silicate (ASPS) to form slurries used as the starting materials for the composite coatings. The coating formed from an ASPS-alumina slurry was porous, because the reaction between alumina and potassium silicate glass resulted in the formation of leucite (KAlSi2O6), consuming substantive glass phase and hindering the densification of the composite coating. Cracks were observed in the coating prepared from an ASPS-quartz slurry due to the larger volume shrinkage of the coating than that of the alloy. In contrast, an intact and dense SiO2-Al2O3-glass coating was successfully prepared from an ASPS-alumina-silica slurry. The oxidation behavior of the SiO2-Al2O3-glass composite coating on Ti-47Al-2Cr-2Nb alloy was studied at 900 °C. The SiO2-Al2O3-glass composite coating acted as an oxygen diffusion barrier, and prevented the inward diffusion of the oxygen from the air to the coating/alloy interface, therefore, decreasing the oxidation rate of the Ti-47Al-2Cr-2Nb alloy significantly.

Understanding the magnetic behavior of heat treated CaO-P2O5-Na2O-Fe2O3-SiO2 bioactive glass using electron paramagnetic resonance studies

Science.gov (United States)

Shankhwar, Nisha; Kothiyal, G. P.; Srinivasan, A.

2014-09-01

Bioactive glass of composition 41CaO-44SiO2-4P2O5-8Fe2O3-3Na2O has been heat treated in the temperature (TA) range of 750-1150 °C for time periods (tA) ranging from 1 h to 3 h to yield magnetic bioactive glass ceramics (MBCs). X-ray diffraction studies indicate the presence of bone mineral (hydroxyapatite and wollastonite) and magnetic (magnetite and α-hematite) phases in nanocrystalline form in the MBCs. Electron paramagnetic resonance (EPR) study was carried out to understand the variation in saturation magnetization and coercivity of the MBCs with TA and tA. These studies reveal the nature and amount of iron ions present in the MBCs and their interaction in the glassy oxide matrix as a function of annealing parameters. The deterioration in the magnetic properties of the glass heat treated above 1050 °C is attributed to the crystallization of the non-magnetic α-hematite phase. These results are expected to be useful in the application of these MBCs as thermoseeds in hyperthermia treatment of cancer.

Thermal conductivities of some lead and bismuth glasses

NARCIS (Netherlands)

Velden, P.F. van

1965-01-01

Thermal conductivities have been measured, mainly at 40°C, of glasses within the systems PbO-Bi2O3-SiO2, PbO-Bi2O3-Al2O3-SiO2, and BaO- (Bi2O3 or PbO) -SiO2. Aiming at lowest thermal conductivity, preference was given to glasses of low silica and low alumina contents. Glass formation persists at

A general model for the dissolution of nuclear waste glasses in salt brine

International Nuclear Information System (INIS)

McGrail, B.P.; Strachan, D.M.

1988-07-01

A mechanistic model describing a dynamic mass balance between the production and consumption of dissolved silica was found to describe the dissolution of SRL-165 defense waste glass in a high-magnesium (PBB3) brine at a temperature of 90/degree/C. The synergetic effect of the waste package container on the glass dissolution rate was found to depend on a precipitation reaction for a ferrous silicate mineral. The model predicted that the ferrous silicate precipitate should be variable in composition where the iron-silica ratio depended on the metal-to-glass surface area ratio used in the experiment. This prediction was confirmed experimentally by the variable iron-silica ratios observed in filtered leachates. However, the interaction between dissolved silica and iron corrosion products needs to be much better understood before the model could be used with confidence in predicting radionuclide release rates for a salt repository. If the deleterious effects of the iron corrosion products can be shown to be transient, and the fracturing of the glass can be minimized, it appears that the performance of SRL-165 defense waste glass will be near the NRC regulatory criterion for fraction release of one part in 100,000 in PBB3 brine at 90/degree/C under silica-saturated conditions. 47 refs., 6 figs., 1 tab

Preparation and Characterization of PbO-SrO-Na2O-Nb2O5-SiO2 Glass Ceramics Thin Film for High-Energy Storage Application

Science.gov (United States)

Tan, Feihu; Zhang, Qingmeng; Zhao, Hongbin; Wei, Feng; Du, Jun

2018-03-01

PbO-SrO-Na2O-Nb2O5-SiO2 (PSNNS) glass ceramic thin films were prepared by pulsed laser deposition technology on heavily doped silicon substrates. The influence of annealing temperatures on microstructures, dielectric properties and energy storage performances of the as-prepared films were investigated in detail. X-ray diffraction studies indicate that Pb2Nb2O7 crystallizes at 800°C and disappears at 900°C, while NaNbO3 and PbNb2O6 are formed at the higher temperature of 900°C. The dielectric properties of the glass ceramics thin films have a strong dependence on the phase assemblages that are developed during heat treatment. The maximum dielectric constant value of 171 was obtained for the film annealed at 800°C, owing to the high electric breakdown field strength, The energy storage densities of the PSNNS films annealed at 800°C were as large as 36.9 J/cm3, These results suggest that PSNNS thin films are promising for energy storage applications.

Evaluation of glass leaching as nutrient source for microalgae growth

International Nuclear Information System (INIS)

Grabska, N.; Tamayo, A.; Mazo, M. A.; Pascual, L.; Rubio, J.

2015-01-01

Three glasses with an elemental composition similar to the nutrient ratio required for Spirulina platensis growth and with different SiO 2 content have been prepared. The glasses were crushed and sieved into 2 different fractions and the effect of the particle size has been studied in terms of the leaching kinetics of each element. The chemical analysis of the leaching water was used for obtaining the dissolution rate curves for each element taking part of the glass composition. From the calculation of the leaching rate constant and the exponential constant of the lixiviation reaction, it has been evaluated the Spirulina platensis growth in ambient normal conditions of light, temperature and pH of the growing media. It has been concluded that, either from the modification of the chemical composition of the glass or its particle size, it is possible to tune the delivery of the nutrients to match the growth rate of Spirulina platensis. (Author)

A comparative study on omnidirectional anti-reflection SiO2 nanostructure films coating by glancing angle deposition

Science.gov (United States)

Prachachet, R.; Samransuksamer, B.; Horprathum, M.; Eiamchai, P.; Limwichean, S.; Chananonnawathorn, C.; Lertvanithphol, T.; Muthitamongkol, P.; Boonruang, S.; Buranasiri, P.

2018-02-01

Fabricated omnidirectional anti-reflection nanostructure films as a one of the promising alternative solar cell applications have attracted enormous scientific and industrial research benefits to their broadband, effective over a wide range of incident angles, lithography-free and high-throughput process. Recently, the nanostructure SiO2 film was the most inclusive study on anti-reflection with omnidirectional and broadband characteristics. In this work, the three-dimensional silicon dioxide (SiO2) nanostructured thin film with different morphologies including vertical align, slant, spiral and thin films were fabricated by electron beam evaporation with glancing angle deposition (GLAD) on the glass slide and silicon wafer substrate. The morphological of the prepared samples were characterized by field-emission scanning electron microscope (FE-SEM) and high-resolution transmission electron microscope (HRTEM). The transmission, omnidirectional and birefringence property of the nanostructure SiO2 films were investigated by UV-Vis-NIR spectrophotometer and variable angle spectroscopic ellipsometer (VASE). The spectrophotometer measurement was performed at normal incident angle and a full spectral range of 200 - 2000 nm. The angle dependent transmission measurements were investigated by rotating the specimen, with incidence angle defined relative to the surface normal of the prepared samples. This study demonstrates that the obtained SiO2 nanostructure film coated on glass slide substrate exhibits a higher transmission was 93% at normal incident angle. In addition, transmission measurement in visible wavelength and wide incident angles -80 to 80 were increased in comparison with the SiO2 thin film and glass slide substrate due to the transition in the refractive index profile from air to the nanostructure layer that improve the antireflection characteristics. The results clearly showed the enhanced omnidirectional and broadband characteristic of the three dimensional SiO

Luminescence and circularly polarized luminescence of macrocyclic Eu(III) and Tb(III) complexes embedded in xerogel and sol-gel SiO2 glasses

International Nuclear Information System (INIS)

Morita, M.; Rau, D.; Kai, T.

2002-01-01

Luminescence, time-resolved luminescence, circularly polarized luminescence (CPL) and decay profiles of Ln(III)(15-crownether-5) (Ln=Ce, Sm, Eu, Tb) and Tb(III)-(R),(S)-cyclen derivative complexes doped in xerogel and sol-gel silica glasses are measured at temperatures down to 10 K to characterize luminescence properties and the electronic structure in the excited states. Luminescence spectral profiles and calculation of crystal field parameters (B 0 (2) ,B 2 (2) ) in the 5 D 0 → 7 F J (J=1,2) transition give evidence of the fact that the pentagonal and planar structure of Eu(III) (15-crownether-5) does hold in xerogel and sol-gel glasses prepared at temperatures below 100 deg. C. As annealing temperatures are increased from 80 deg. C to 750 deg. C, Eu(III) complexes in sol-gel glasses are found to decompose gradually to SiO 2 :Eu 3+ . Tb(III)-(R) and (S)-cyclen derivative complexes in xerogel reveal at room temperature and 10 K sharp CPL spectra with luminescence dissymmetry factors g lum =-0.1 and 0.1, respectively. These complexes doped in sol-gel glasses represent luminescence characteristics of rare earth ions encapsulated in the nano-porous host

Sodium diffusion in boroaluminosilicate glasses

DEFF Research Database (Denmark)

Smedskjaer, Morten M.; Zheng, Qiuju; Mauro, John C.

2011-01-01

of isothermal sodium diffusion in BAS glasses by ion exchange, inward diffusion, and tracer diffusion experiments. By varying the [SiO2]/[Al2O3] ratio of the glasses, different structural regimes of sodium behavior are accessed. We show that the mobility of the sodium ions decreases with increasing [SiO2]/[Al2O......Understanding the fundamentals of alkali diffusion in boroaluminosilicate (BAS) glasses is of critical importance for advanced glass applications, e.g., the production of chemically strengthened glass covers for personal electronic devices. Here, we investigate the composition dependence...

Bismuth silicate glass: A new choice for 2 μm fiber lasers

Science.gov (United States)

Ding, Jia; Zhao, Guoying; Tian, Ying; Chen, Wei; Hu, Lili

2012-11-01

We report on a new Yb3+/Tm3+/Ho3+ co-doped bismuth silicate glass: SiO2-Bi2O3-R2O (R = Li, Na, K) for 2 μm fiber lasers. Bi2O3 was introduced into alkali silicate glass to optimize 2 μm emission properties. Physical, chemical and spectroscopic properties of Yb3+/Tm3+/Ho3+ co-doped SiO2-Bi2O3-R2O (SBR) glass were presented. The Yb3+/Tm3+/Ho3+ co-doped SBR glass shows excellent thermal stability (ΔT = 162 °C), an intense 2.0 μm emission pumped by 980 nm LD with a lifetime of 1.33 ms and width of 168 nm, large maximum emission cross section of Ho3+ (5.3 × 10-21 cm2), thus large σemτ product (7.049 × 10-24 cm2 s), which suggest its application in 2 μm fiber lasers.

Optical and dielectric properties of isothermally crystallized nano-KNbO3 in Er3+-doped K2O-Nb2O5-SiO2 glasses.

Science.gov (United States)

Chaliha, Reenamoni Saikia; Annapurna, K; Tarafder, Anal; Tiwari, V S; Gupta, P K; Karmakar, Basudeb

2010-01-01

Precursor glass of composition 25K(2)O-25Nb(2)O(5)-50SiO(2) (mol%) doped with Er(2)O(3) (0.5 wt% in excess) was isothermally crystallized at 800 degrees C for 0-100 h to obtain transparent KNbO(3) nanostructured glass-ceramics. XRD, FESEM, TEM, FTIRRS, dielectric constant, refractive index, absorption and fluorescence measurements were carried out to analyze the morphology, dielectric, structure and optical properties of the glass-ceramics. The crystallite size of KNbO(3) estimated from XRD and TEM is found to vary in the range 7-23 nm. A steep rise in the dielectric constant of glass-ceramics with heat-treatment time reveals the formation of ferroelectric nanocrystalline KNbO(3) phase. The measured visible photoluminescence spectra have exhibited green emission transitions of (2)H(11/2), (4)S(3/2)-->(4)I(15/2) upon excitation at 377 nm ((4)I(15/2)-->(4)G(11/2)) absorption band of Er(3+) ions. The near infrared (NIR) emission transition (4)I(13/2)-->(4)I(15/2) is detected around 1550 nm on excitation at 980 nm ((4)I(15/2)-->(4)I(11/2)) of absorption bands of Er(3+) ions. It is observed that photoluminescent intensity at 526 nm ((2)H(11/2)-->(4)I(15/2)), 550 nm ((4)S(3/2)-->(4)I(15/2)) and 1550 nm ((4)I(13/2)-->(4)I(15/2)) initially decrease and then gradually increase with increase in heat-treatment time. The measured lifetime (tau(f)) of the (4)I(13/2)-->(4)I(15/2) transition also possesses a similar trend. The measured absorption and fluorescence spectra reveal that the Er(3+) ions gradually enter into the KNbO(3) nanocrystals. Copyright 2009 Elsevier B.V. All rights reserved.

Effect of concentration variation on 2.0 µm emission of Ho3+-doped SiO2-Al2O3-Na2CO3-SrF2-CaF2 oxyfluorosilicate glasses

Science.gov (United States)

Gelija, Devarajulu; Borelli, Deva Prasad Raju

2018-02-01

The concentration variation of Ho3+ ion-doped SiO2-Al2O3-Na2CO3-SrF2-CaF2 glasses has been prepared by conventional melt quenching method. The thermal stability of 1 mol % of Ho3+-doped oxyfluorosilicate glass has been calculated using the differential thermal analysis (DTA) spectra. The phenomenological Judd-Ofelt intensity parameters Ωλ ( λ = 2, 4 and 6) were calculated for all concentrations of Ho3+ ions. The luminescence spectra in visible region of Ho3+ ion-doped glasses were recorded under the excitation wavelength of 452 nm. The spectra consists of several intense emission bands (5F4, 5S2) → 5I8 (547 nm), 5F3 → 5I8 (647 nm), 5F5 → 5I7 (660 nm) and (5F4, 5S2) → 5I7 (750 nm) in the range 500-780 nm. The fluorescence emission at ˜2.0 µm (5I7 → 5I8) was observed under the excitation of 488 nm Ar-ion laser. The stimulated emission cross section for 5I7 → 5I8 transition (˜2.0 µm) varies from 8.46 to 9.52 × 10-21 cm2, as calculated by the Fuchtbauer-Ladenburg (FL) theory. However, Mc-Cumber theory was used to calculate emission cross section values about 4.24-5.75 × 10-21 cm2 for the 5I7 → 5I8 transition in all concentrations of Ho3+-doped oxyfluorosilicate glasses. Therefore, these results reveal that the 0.5 mol % of Ho3+-doped oxyfluorosilicate glasses, exhibiting higher emission cross section, has potentially been used for laser applications at ˜ 2.0 µm.

Kinetic model for quartz and spinel dissolution during melting of high-level-waste glass batch

International Nuclear Information System (INIS)

Pokorny, Richard; Rice, Jarrett A.; Crum, Jarrod V.; Schweiger, Michael J.; Hrma, Pavel

2013-01-01

The dissolution of quartz particles and the growth and dissolution of crystalline phases during the conversion of batch to glass potentially affects both the glass melting process and product quality. Crystals of spinel exiting the cold cap to molten glass below can be troublesome during the vitrification of iron-containing high-level wastes. To estimate the distribution of quartz and spinel fractions within the cold cap, we used kinetic models that relate fractions of these phases to temperature and heating rate. Fitting the model equations to data showed that the heating rate, apart from affecting quartz and spinel behavior directly, also affects them indirectly via concurrent processes, such as the formation and motion of bubbles. Because of these indirect effects, it was necessary to allow one kinetic parameter (the pre-exponential factor) to vary with the heating rate. The resulting kinetic equations are sufficiently simple for the detailed modeling of batch-to-glass conversion as it occurs in glass melters. The estimated fractions and sizes of quartz and spinel particles as they leave the cold cap, determined in this study, will provide the source terms needed for modeling the behavior of these solid particles within the flow of molten glass in the melter

FY2016 ILAW Glass Corrosion Testing with the Single-Pass Flow-Through Method

Energy Technology Data Exchange (ETDEWEB)

Neeway, James J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Asmussen, Robert M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Parruzot, Benjamin PG [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cordova, Elsa [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Williams, Benjamin D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Leavy, Ian I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Stephenson, John R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McElroy, Erin M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2017-04-21

The inventory of immobilized low-activity waste (ILAW) produced at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) will be disposed of at the near-surface, on-site Integrated Disposal Facility (IDF). When groundwater comes into contact with the waste form, the glass will corrode and radionuclides will be released into the near-field environment. Because the release of the radionuclides is dependent on the dissolution rate of the glass, it is important that the performance assessment (PA) model accounts for the dissolution rate of the glass as a function of various chemical conditions. To accomplish this, an IDF PA model based on Transition State Theory (TST) can be employed. The model is able to account for changes in temperature, exposed surface area, and pH of the contacting solution as well as the effect of silicon concentrations in solution, specifically the activity of orthosilicic acid (H4SiO4), whose concentration is directly linked to the glass dissolution rate. In addition, the IDF PA model accounts for the alkali-ion exchange process as sodium is leached from the glass and into solution. The effect of temperature, pH, H4SiO4 activity, and the rate of ion-exchange can be parameterized and implemented directly into the PA rate law model. The rate law parameters are derived from laboratory tests with the single-pass flow-through (SPFT) method. To date, rate law parameters have been determined for seven ILAW glass compositions, thus additional rate law parameters on a wider range of compositions will supplement the existing body of data for PA maintenance activities. The data provided in this report can be used by ILAW glass scientists to further the understanding of ILAW glass behavior, by IDF PA modelers to use the rate law parameters in PA modeling efforts, and by Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program.

Influence of cell culture medium composition on in vitro dissolution behavior of a fluoride-containing bioactive glass.

Science.gov (United States)

Shah, Furqan A; Brauer, Delia S; Wilson, Rory M; Hill, Robert G; Hing, Karin A

2014-03-01

Bioactive glasses are used clinically for bone regeneration, and their bioactivity and cell compatibility are often characterized in vitro, using physiologically relevant test solutions. The aim of this study was to show the influence of varying medium characteristics (pH, composition, presence of proteins) on glass dissolution and apatite formation. The dissolution behavior of a fluoride-containing bioactive glass (BG) was investigated over a period of one week in Eagle's Minimal Essential Medium with Earle's Salts (MEM), supplemented with either, (a) acetate buffer, (b) 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer, (c) HEPES + carbonate, or (d) HEPES + carbonate + fetal bovine serum. Results show pronounced differences in pH, ion release, and apatite formation over 1 week: Despite its acidic pH (pH 5.8 after BG immersion, as compared to pH 7.4-8.3 for HEPES-containing media), apatite formation was fastest in acetate buffered (HEPES-free) MEM. Presence of carbonate resulted in formation of calcite (calcium carbonate). Presence of serum proteins, on the other hand, delayed apatite formation significantly. These results confirm that the composition and properties of a tissue culture medium are important factors during in vitro experiments and need to be taken into consideration when interpreting results from dissolution or cell culture studies. Copyright © 2013 Wiley Periodicals, Inc.

Effects of MgO on short and long term stabilities in water of R7T7 and M7 nuclear waste glasses

Energy Technology Data Exchange (ETDEWEB)

Advocat, T; Vernaz, E; Dussossoy, J [CEA Centre d` Etudes de la Vallee du Rhone, 30 - Marcoule (France). Dept. des Procedes de Retraitement; Crovisier, J L [Centre National de la Recherche Scientifique (CNRS), 67 - Strasbourg (France)

1993-12-31

Magnesium oxide was added to the standard R7T7 and M7 glass compositions developed for containment of fission product solutions. M7 differs from the R7T7 reference glass mainly by a larger proportion of network modifier elements and a correspondingly lower proportion of glass network forming elements. The percentage of fission products, simulated in this study by inactive elements, was the same in both cases. Increasing the MgO content of the glass compositions by 2 to 5 wt% resulted in significant variations in the aqueous leaching resistance at 90 and 100 deg C. Experimental findings demonstrated that the initial dissolution rate measured at 100 deg C in a Soxhlet apparatus was proportional to the MgO content and inversely proportional to the network former content (mainly SiO2). This was confirmed by a glass hydration model based on the thermodynamic stability of the glass matrix components. Aqueous corrosion tests were also conducted at 90 deg C under static conditions at various SA/V ratios to simulate the progress of the reaction. Under these conditions, the glass dissolution rate diminished more slowly in time when the initial magnesium content was high and the network former content was low. This may be due primarily to a variation in the glass silica solubility limit related to the glass composition; it may also be related to the formation of secondary silica and magnesia alteration products controlling the glass dissolution reaction affinity.

Highly transparent and UV-resistant superhydrophobic SiO2-coated ZnO nanorod arrays

KAUST Repository

Gao, Yangqin; Gereige, Issam; El Labban, Abdulrahman; Cha, Dong Kyu; Isimjan, Tayirjan T.; Beaujuge, Pierre

2014-01-01

Highly transparent and UV-resistant superhydrophobic arrays of SiO 2-coated ZnO nanorods are prepared in a sequence of low-temperature (<150 C) steps on both glass and thin sheets of PET (2 × 2 in. 2), and the superhydrophobic nanocomposite

Modeling the Onset of Phase Separation in CaO-SiO2-CaCl2 Chlorine-Containing Silicate Glasses.

Science.gov (United States)

Swansbury, Laura A; Mountjoy, Gavin; Chen, Xiaojing; Karpukhina, Natalia; Hill, Robert

2017-06-08

The addition of chlorine into a bioactive glass composition is expected to reduce its abrasiveness and increase its bioactivity, which is important for dental applications such as toothpastes. There is a lack of information and understanding regarding the structural role of chlorine in chlorine-containing bioactive silicate glasses. This has prompted classical core-shell model molecular dynamics simulations of (50 - x/2)CaO-(50 - x/2)SiO 2 -xCaCl 2 glasses to be performed, where x ranges from x = 0.0 to 43.1 mol % CaCl 2 . These ternary glasses are advantageous for a fundamental study because they do not have additional network formers (e.g., phosphorus pentoxide) or modifiers (e.g., sodium) typically found in bioactive glass compositions. The (50 - x/2)CaO-(50 - x/2)SiO 2 -xCaCl 2 glasses were seen to become phase-separated around the x = 16.1 mol % CaCl 2 composition, and chlorine predominantly coordinated with calcium. These findings provide a solid foundation for further computational modeling work on more complex chlorine-containing bioactive glass compositions.

Crystallization behaviour of nanostructured hybrid SiO2-TiO2 gel glasses to nanocomposites.

Science.gov (United States)

Tsvetelina, Gerganova; Yordanka, Ivanova; Yuliya, Vueva; Miranda, Salvado Isabel M; Helena, Fernandes Maria

2010-04-01

The crystallization behaviour of hybrid SiO2-TiO2 nanocomposites derived from titanosiloxanes by sol-gel method has been investigated depending on the type of siloxane precursor and the pirolysis temperature. The resulting hybrid titanosiloxanes, crosslinked with trimethylsilil isocyanate (nitrogen-modified) or methyltrietoxisilane (carbon-modified), were pirolyzed in an inert atmosphere in the temperature range between 600 to 1100 degrees C in order to form C-(N)-Si-O-TiO2 nanocomposites. By means of XRD, FTIR, 29Si NMR, SEM, TEM and AFM investigations have been established that the transformation of the nanostructured SiO2-TiO2 hybrid materials into nanocomposites as well as the crystalline size depend on the titanium content and the type of cross-linking agents used in the synthesizes.

Micro-ion beam analysis of physico-chemical reactions in vitro induced by nano-structured sol-gel derived bioactive glasses

International Nuclear Information System (INIS)

Lao, J.

2007-07-01

The study of bioactive glasses is a multi-field area of research aiming at a major goal: the development of new generation biomaterials that would be able to bond with host tissues through the formation of a strong interfacial bond, together with helping the body heal itself through the stimulation of specific cellular responses. Thus clinical applications of bioactive glasses mainly concern dental surgery and orthopedics, for filling osseous defects. For this purpose, we have elaborated bioactive glasses in the binary SiO 2 -CaO system, ternary SiO 2 -CaO-P 2 O 5 system, and for the first time, to our knowledge, strontium-doped SiO 2 -CaO-SrO and SiO 2 -CaO-P 2 O 5 -SrO glasses. The materials were elaborated using the sol-gel process, which allowed the synthesis of nano-porous materials with great purity and homogeneity. The bio-activity of the glasses was clearly demonstrated in vitro: in contact with biological fluids, the whole lot of mate-rials were able to induce the formation of a Ca-P-Mg layer a few microns thick at their surface. Our work is characterized by the use of PIXE-RBS nuclear microprobes to study the bioactive glass/biological fluids interface. Thanks to these methods we obtained chemical maps that made possible the analysis of major and trace elements concentrations at the interface. Moreover, quantitative information regarding the local reactivity of glasses were acquired. These data are important to evaluate the kinetics and amplitude of the physico-chemical reactions involved in the bio-activity process. Thus, we highlighted that the binary glass is the highest reactive regarding the dissolution of the glassy matrix as well as the first appearance of the Ca-P rich layer. However the Ca/P atomic ratio calculated at the glass/biological fluids interface decreases slowly, indicating that the Ca-P-Mg layer encounters difficulties to be changed into a more stable apatitic phase. For the P-containing glasses, the de-alkalinization of the matrix and

Bioactivity of Y2O3 and CeO2 doped SiO2-SrO-Na2O glass-ceramics.

Science.gov (United States)

Placek, L M; Keenan, T J; Wren, A W

2016-08-01

The bioactivity of yttrium and cerium are investigated when substituted for Sodium (Na) in a 0.52SiO2-0.24SrO-0.24-xNa2O-xMO glass-ceramics (where x = 0.08 and MO = Y2O3 or CeO2). Bioactivity is monitored through pH and inductively coupled plasma-optical emission spectrometry where pH of simulated body fluid ranged from 7.5 to 7.6 and increased between 8.2 and 10.0 after 14-day incubation with the glass-ceramic disks. Calcium (Ca) and phosphorus (P) levels in simulated body fluid after incubation with yttrium and cerium containing disks show a continual decline over the 14-day period. In contrast, Con disks (not containing yttrium or cerium) caused the elimination of Ca in solution after 1 day and throughout the incubation period, and initially showed a decline in P levels followed by an increase at 14 days. Scanning electron microscopy and energy dispersive spectroscopy confirmed the presence of Ca and P on the surface of the simulated body fluid-incubated disks and showed precipitates on Con and HCe (8 mol% cerium) samples. Cell viability of MC3T3 osteoblasts was not significantly affected at a 9% extract concentration. Optical microscopy after 24 h cell incubation with disks showed that Con samples do not support osteoblast or Schwann cell growth, while all yttrium and cerium containing disks have direct contact with osteoblasts spread across the wells. Schwann cells attached in all wells, but only showed spreading with the HY-S (8 mol% yttrium, heated to sintering temperature) and YCe (4 mol% yttrium and cerium) disks. Scanning electron microscopy of the compatible disks shows osteoblast and sNF96.2 Schwann cells attachment and spreading directly on the disk surfaces. © The Author(s) 2016.

SiO2–CaO–P2O5

Indian Academy of Sciences (India)

its ability to treat bone infection. Keywords. ... high physiological interests in the biomedical field. These .... causes severe hospital-acquired infections, especially in immune .... control the dissolution rate of the silica glass through the for-.

GLAMOR - Or How We Achieved A Common Understanding On The Decrease Of Glass Dissolution Kinetics Through International Cooperation

International Nuclear Information System (INIS)

Van Iseghem, Pierre; Aerstens, Marc; Gin, Stephane; Grambow, Bernd; Strachan, Denis M.; McGrail, B. Peter; Wicks, George G.; McMenamin, Thomas

2011-01-01

The objective of the EC funded GLAMOR project was to achieve a common understanding of the processes that control the decrease of the dissolution rate of high-level waste glass in water when silica becomes saturated. Is affinity control or a protective layer dominating? The following steps were taken: (1) review of the literature, (2) selection ofselect an experimental dataset, and selection of the models r(t) and GM2003, and (3) application apply by the GLAMOR partners of the models to the datasets. The main focus has beenwas on dissolution tests in pure water at different values of surface-to-volume and pH. Some of the main conclusions were: (1) both affinity and protective layer concepts must be considered in the interpretation of the rate decreasing stage, (2) the residual dissolution rate observed beyond the silica saturation stage is far more important in view of the long-term performance of the glass, and deserves more attention in future R and D. In the GLAMOR final report, we also discussed in detail the modeling parameters, such as the silica saturation concentration, the silica diffusion coefficient, the silica retention factor in the reaction layer, and the water diffusion coefficient.

Crack-resistant Al2O3–SiO2 glasses

Science.gov (United States)

Rosales-Sosa, Gustavo A.; Masuno, Atsunobu; Higo, Yuji; Inoue, Hiroyuki

2016-01-01

Obtaining “hard” and “crack-resistant” glasses have always been of great important in glass science and glass technology. However, in most commercial glasses both properties are not compatible. In this work, colorless and transparent xAl2O3–(100–x)SiO2 glasses (30 ≤ x ≤ 60) were fabricated by the aerodynamic levitation technique. The elastic moduli and Vickers hardness monotonically increased with an increase in the atomic packing density as the Al2O3 content increased. Although a higher atomic packing density generally enhances crack formation in conventional oxide glasses, the indentation cracking resistance increased by approximately seven times with an increase in atomic packing density in binary Al2O3–SiO2 glasses. In particular, the composition of 60Al2O3•40SiO2 glass, which is identical to that of mullite, has extraordinary high cracking resistance with high elastic moduli and Vickers hardness. The results indicate that there exist aluminosilicate compositions that can produce hard and damage-tolerant glasses. PMID:27053006

Comprehensive study of electronic polarizability and band gap of B2O3–Bi2O3–ZnO–SiO2 glass network

Directory of Open Access Journals (Sweden)

Iskandar Shahrim Mustafa

2017-10-01

Full Text Available Quaternary glasses were successfully fabricated using melt quenching technique based on the chemical compound composition (xBi2O3–(0.5−x ZnO–(0.2B2O3–(0.3SiO2, where (x=0.1, 0.2, 0.3, 0.4, 0.45 mole. The sources of SiO2 was produced from rice husk ash (RHA at 99.36% of SiO2. The Urbach energy was increased from 0.16eV to the 0.29eV as the mole of Bi2O3 increased in the glass structure. The indirect energy band gap is indicated in decrement pattern with 3.15eV towards 2.51eV. The results of Urbach energy and band gap energy that were obtained are due to the increment of Bi3+ ion in the glass network. The refractive indexes for the prepared glasses were evaluated at 2.36 to 2.54 based on the Lorentz–Lorentz formulation which correlated to the energy band gap. The calculated of molar polarizability, electronic polarizability and optical basicity exemplify fine complement to the Bi2O3 addition in the glass network. The glass sample was indicated in amorphous state.

Permanently densified SiO2 glasses: a structural approach.

Science.gov (United States)

Martinet, C; Kassir-Bodon, A; Deschamps, T; Cornet, A; Le Floch, S; Martinez, V; Champagnon, B

2015-08-19

Densified silica can be obtained by different pressure and temperature paths and for different stress conditions, hydrostatic or including shear. The density is usually the macroscopic parameter used to characterize the different compressed silica samples. The aim of our present study is to compare structural modifications for silica glass, densified from several routes. For this, densified silica glasses are prepared from cold and high temperature (up to 1020 °C) compressions. The different densified glasses obtained in our study are characterized by micro-Raman spectroscopy. Intertetrahedral angles from the main band relative to the bending mode decrease and their values are larger for densified samples from high temperature compression than those samples from cold compression. The relative amount of 3-membered rings deduced from the D2 line area increases as a function of density for cold compression. The temperature increase during the compression process induces a decrease of the 3 fold ring population. Moreover, 3 fold rings are more deformed and stressed for densified samples at room temperature at the expense of those densified at high temperature. Temperature plays a main role in the reorganization structure during the densification and leads to obtaining a more relaxed structure with lower stresses than glasses densified from cold compression. The role of hydrostatic or non-hydrostatic applied stresses on the glass structure is discussed. From the Sen and Thorpe central force model, intertetrahedral angle average value and their distribution are estimated.

Thermodynamic and structural models compared with the initial dissolution rates of open-quotes SONclose quotes glass samples

International Nuclear Information System (INIS)

Tovena, I.; Advocat, T.; Ghaleb, D.; Vernaz, E.; Larche, F.

1994-01-01

The experimentally determined initial dissolution rate R 0 of nuclear glass was correlated with thermodynamic parameters and structural parameters. The initial corrosion rates of six open-quotes R7T7close quotes glass samples measured at 100 degrees C in a Soxhlet device were correlated with the glass free hydration energy and the glass formation enthalpy. These correlations were then tested with a group of 26 SON glasses selected for their wide diversity of compositions. The thermodynamic models provided a satisfactory approximation of the initial dissolution rate determined under Soxhlet conditions for SON glass samples that include up to 15 wt% of boron and some alumina. Conversely, these models are inaccurate if the boron concentration exceeds 15 wt% and the glass contains no alumina. Possible correlations between R 0 and structural parameters, such as the boron coordination number and the number of nonbridging oxygen atoms, were also investigated. The authors show that R 0 varies inversely with the number of 4-coordinate boron atoms; conversely, the results do not substantiate published reports of a correlation between R 0 and the number of nonbridging oxygen atoms

Effect of concentration variation on 2.0 μm emission of Ho3+-doped SiO2-Al2O3-Na2CO3-SrF2-CaF2 oxyfluorosilicate glasses

International Nuclear Information System (INIS)

Gelija, Devarajulu; Borelli, Deva Prasad Raju

2018-01-01

The concentration variation of Ho 3+ ion-doped SiO 2 -Al 2 O 3 -Na 2 CO 3 -SrF 2 -CaF 2 glasses has been prepared by conventional melt quenching method. The thermal stability of 1 mol % of Ho 3+ -doped oxyfluorosilicate glass has been calculated using the differential thermal analysis (DTA) spectra. The phenomenological Judd-Ofelt intensity parameters Ω λ (λ = 2, 4 and 6) were calculated for all concentrations of Ho 3+ ions. The luminescence spectra in visible region of Ho 3+ ion-doped glasses were recorded under the excitation wavelength of 452 nm. The spectra consists of several intense emission bands ( 5 F 4 , 5 S 2 ) → 5 I 8 (547 nm), 5 F 3 → 5 I 8 (647 nm), 5 F 5 → 5 I 7 (660 nm) and ( 5 F 4 , 5 S 2 ) → 5 I 7 (750 nm) in the range 500-780 nm. The fluorescence emission at ∝ 2.0 μm ( 5 I 7 → 5 I 8 ) was observed under the excitation of 488 nm Ar-ion laser. The stimulated emission cross section for 5 I 7 → 5 I 8 transition (∝ 2.0 μm) varies from 8.46 to 9.52 x 10 -21 cm 2 , as calculated by the Fuchtbauer-Ladenburg (FL) theory. However, Mc-Cumber theory was used to calculate emission cross section values about 4.24-5.75 x 10 -21 cm 2 for the 5 I 7 → 5 I 8 transition in all concentrations of Ho 3+ -doped oxyfluorosilicate glasses. Therefore, these results reveal that the 0.5 mol % of Ho 3+ -doped oxyfluorosilicate glasses, exhibiting higher emission cross section, has potentially been used for laser applications at ∝ 2.0 μm. (orig.)

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

Science.gov (United States)

Sato, K; Hatta, T

2015-03-07

Momentum distributions associated with ortho-positronium (o-Ps) pick-off annihilation photon are often influenced by light elements, as, e.g., carbon, oxygen, and fluorine. This phenomenon, so-called element specificity of o-Ps pick-off annihilation, has been utilized for studying the elemental environment around the open spaces. To gain an insight into the element specificity of o-Ps pick-off annihilation, the chemical shift of oxygen 1s binding energy and the momentum distributions associated with o-Ps pick-off annihilation were systematically investigated for alkali-metal loaded SiO2 glasses by means of X-ray photoelectron spectroscopy and positron-age-momentum correlation spectroscopy, respectively. Alkali metals introduced into the open spaces surrounded by oxygen atoms cause charge transfer from alkali metals to oxygen atoms, leading to the lower chemical shift for the oxygen 1s binding energy. The momentum distribution of o-Ps localized into the open spaces is found to be closely correlated with the oxygen 1s chemical shift. This correlation with the deepest 1s energy level evidences that the element specificity of o-Ps originates from pick-off annihilation with orbital electrons, i.e., dominantly with oxygen 2p valence electrons and s electrons with lower probability.

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

Science.gov (United States)

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. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Synthesis and characterization of erbium-doped SiO2-TiO2 thin films prepared by sol-gel and dip-coating techniques onto commercial glass substrates as a route for obtaining active GRadient-INdex materials

International Nuclear Information System (INIS)

Gómez-Varela, Ana I.; Castro, Yolanda; Durán, Alicia; De Beule, Pieter A.A.; Flores-Arias, María T.; Bao-Varela, Carmen

2015-01-01

In this work, SiO 2 -TiO 2 films doped with erbium were prepared by dip-coating sol-gel process onto commercial glass substrates. The surface morphology of the films was characterized using atomic force microscopy, while thickness, refractive index, extinction coefficient and porosity of the films were determined by ellipsometric measurements in a wavelength region of 400-1000 nm. Optical constants and porosity were found to vary with erbium concentration. The proof of principle presented in this paper is applicable to systems of different nature by tailoring the sol-gel precursors in such a way that active GRadient-INdex media described by a complex, parabolic-like refractive index distribution for beam shaping purposes is obtained. - Highlights: • Sol-gel route for preparation of active GRadient-INdex materials is proposed. • SiO 2 -TiO 2 films doped with erbium were prepared by dipping onto commercial glasses. • Morphological and optical characterization of the samples was performed. • Optical constants and porosity were found to vary with erbium concentration. • Refractive index diminishes with dopant content; the contrary occurs for porosity

Effect of Callovo-Oxfordian clay rock on the dissolution rate of the SON68 simulated nuclear waste glass

Energy Technology Data Exchange (ETDEWEB)

Neeway, James J., E-mail: James.Neeway@pnnl.gov [SUBATECH, Unité Mixte de Recherche 6457, École des Mines de Nantes, CNRS/IN2P3, Université de Nantes, BP 20722, 44307 Nantes cedex 3 (France); Abdelouas, Abdesselam; Ribet, Solange; El Mendili, Yassine [SUBATECH, Unité Mixte de Recherche 6457, École des Mines de Nantes, CNRS/IN2P3, Université de Nantes, BP 20722, 44307 Nantes cedex 3 (France); Schumacher, Stéphan [ANDRA, Parc de la Croix Blanche, 1/7 rue Jean Monnet, 92298 Châtenay-Malabry (France); Grambow, Bernd [SUBATECH, Unité Mixte de Recherche 6457, École des Mines de Nantes, CNRS/IN2P3, Université de Nantes, BP 20722, 44307 Nantes cedex 3 (France)

2015-04-15

Long-term storage of high-level nuclear waste glass in France is expected to occur in an engineered barrier system (EBS) located in a subsurface Callovo-Oxfordian (COx) clay rock formation in the Paris Basin in northeastern France. Understanding the behavior of glass dissolution in the complex system is critical to be able to reliably model the performance of the glass in this complex environment. To simulate this multi-barrier repository scenario in the laboratory, several tests have been performed to measure glass dissolution rates of the simulated high-level nuclear waste glass, SON68, in the presence of COx claystone at 90 °C. Experiments utilized a High-Performance Liquid Chromatography (HPLC) pump to pass simulated Bure site COx pore water through a reaction cell containing SON68 placed between two COx claystone cores for durations up to 200 days. Silicon concentrations at the outlet were similar in all experiments, even the blank experiment with only the COx claystone (∼4 mg/L at 25 °C and ∼15 mg/L at 90 °C). The steady-state pH of the effluent, measured at room temperature, was roughly 7.1 for the blank and 7.3–7.6 for the glass-containing experiments demonstrating the pH buffering capacity of the COx claystone. Dissolution rates for SON68 in the presence of the claystone were elevated compared to those obtained from flow-through experiments conducted with SON68 without claystone in silica-saturated solutions at the same temperature and similar pH values. Additionally, through surface examination of the monoliths, the side of the monolith in direct contact with the claystone was seen to have a corrosion thickness 2.5× greater than the side in contact with the bulk glass powder. Results from one experiment containing {sup 32}Si-doped SON68 also suggest that the movement of Si through the claystone is controlled by a chemically coupled transport with a Si retention factor, K{sub d}, of 900 mL/g.

Mechanical Properties of Densified Tectosilicate Calcium-Aluminosilicate Glasses

DEFF Research Database (Denmark)

Johnson, Nicole; Lamberson, Lisa; Smedskjær, Morten Mattrup

Aluminosilicate glasses are widely used in applications such as LCD glass, touchscreens for hand held devices and car windows. We have shown that the tectosilicate compositions exhibit an interesting non-monotonic variation in hardness with increasing SiO2 content. From 40% to 85 mol% SiO2......, hardness and indentation modulus both decrease, consistent with the topological constraint theory. Above 85 mol% SiO2 , hardness increases rapidly with increasing SiO2 content while modulus continues to decrease. A switch from shear to densification based on the species present in the glass has been...... proposed to explain this behavior. To reduce densification and study shear deformation independently, a series of calcium aluminosilicate glasses with tectosilicate compositions were densified by isostatic compression in a gas pressure chamber at elevated temperatures. The compressed glasses have increased...

SON68 nuclear glass dissolution kinetics: Current state of knowledge and basis of the new GRAAL model

Energy Technology Data Exchange (ETDEWEB)

Frugier, P. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France)], E-mail: pierre.frugier@cea.fr; Gin, S.; Minet, Y.; Chave, T. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France); Bonin, B. [CEA Saclay, DEN/DIR/DS, 91191 Gif-sur-Yvette cedex (France); Godon, N.; Lartigue, J.-E.; Jollivet, P. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France); Ayral, A. [IEM/CNRS-ENSCM Universite Montpellier 2, CC 047, Place Eugene Bataillon, 34095 Montpellier cedex 5 (France); De Windt, L. [ENSMP, CG, 35 rue St Honore, 77305 Fontainebleau cedex (France); Santarini, G. [CEA Saclay HC/CAB, 91191 Gif-sur-Yvette cedex (France)

2008-10-15

This article summarizes the present state of knowledge concerning aqueous alteration of R7T7-type nuclear containment glasses, represented mainly by the inactive reference glass designated SON68. Based on this review, we propose to describe the glass alteration kinetics up to and including the final residual rate regime by means of a new mechanistic model known as GRAAL (glassreactivitywithallowanceforthealterationlayer). Phenomenological analysis findings are reviewed for the various glass alteration regimes: interdiffusion, initial rate, rate drop, residual rate and, under very particular circumstances, resumption of alteration. These alteration regimes are associated with predominant mechanisms. Published work interpreting and modeling these mechanisms was examined in detail. There is a broad consensus on the general mechanisms of the initial rate and even the interdiffusion regime, whereas the mechanisms controlling the rate drop remain a subject of dispute not only with regard to nuclear glasses but also for the dissolution of silicate minerals. The reaction affinity responsible for the rate drop is expressed differently by different authors and depending on the underlying theories. The disagreement concerns the nature of the phase (glass or gel) or the activated complex controlling the rate drop, which in turn determines the elements that must be taken into account in the overall affinity term. Progress in recent years, especially in identifying the mechanisms responsible for the residual rate, has shed new light on these issues, allowing us to propose new theoretical foundations for modeling the different kinetic regimes of SON68 nuclear glass dissolution. The GRAAL model considers that water diffusion in the passivating reaction zone (the gel formed under saturation conditions) is a rate-limiting step in the overall glass dissolution kinetics. Moreover, this passivation zone is a soluble phase whose stability is directly dependent on the nature of the

Extreme wettability of nanostructured glass fabricated by non-lithographic, anisotropic etching

Science.gov (United States)

Yu, Eusun; Kim, Seul-Cham; Lee, Heon Ju; Oh, Kyu Hwan; Moon, Myoung-Woon

2015-01-01

Functional glass surfaces with the properties of superhydrophobicity/or superhydrohydrophilicity, anti-condensation or low reflectance require nano- or micro-scale roughness, which is difficult to fabricate directly on glass surfaces. Here, we report a novel non-lithographic method for the fabrication of nanostructures on glass; this method introduces a sacrificial SiO2 layer for anisotropic plasma etching. The first step was to form nanopillars on SiO2 layer-coated glass by using preferential CF4 plasma etching. With continuous plasma etching, the SiO2 pillars become etch-resistant masks on the glass; thus, the glass regions covered by the SiO2 pillars are etched slowly, and the regions with no SiO2 pillars are etched rapidly, resulting in nanopatterned glass. The glass surface that is etched with CF4 plasma becomes superhydrophilic because of its high surface energy, as well as its nano-scale roughness and high aspect ratio. Upon applying a subsequent hydrophobic coating to the nanostructured glass, a superhydrophobic surface was achieved. The light transmission of the glass was relatively unaffected by the nanostructures, whereas the reflectance was significantly reduced by the increase in nanopattern roughness on the glass. PMID:25791414

Effects of SiO2 and TiO2 fillers on thermal and dielectric properties ...

Indian Academy of Sciences (India)

Administrator

eco-friendly bismuth glass microcomposites of plasma display panels. SHIV PRAKASH SINGH ... MS received 12 November 2008; revised 18 March 2009. Abstract. The effects .... In view of above, in this paper we report the effects of. SiO2 (amorphous) ..... mic Membrane Sections of this institute for carrying out the XRD and ...

Preparation and studies on surface modifications of calcium-silico-phosphate ferrimagnetic glass-ceramics in simulated body fluid

International Nuclear Information System (INIS)

Sharma, K.; Dixit, A.; Singh, Sher; Jagannath,; Bhattacharya, S.; Prajapat, C.L.; Sharma, P.K.; Yusuf, S.M.; Tyagi, A.K.; Kothiyal, G.P.

2009-01-01

The structure and magnetic behaviour of 34SiO 2 -(45 - x) CaO-16P 2 O 5 -4.5 MgO-0.5 CaF 2 - x Fe 2 O 3 (where x = 5, 10, 15, 20 wt.%) glasses have been investigated. Ferrimagnetic glass-ceramics are prepared by melt quench followed by controlled crystallization. The surface modification and dissolution behaviour of these glass-ceramics in simulated body fluid (SBF) have also been studied. Phase formation and magnetic behaviour have been studied using XRD and SQUID magnetometer. The room temperature Moessbauer study has been done to monitor the local environment around Fe cations and valence state of Fe ions. X-ray photoelectron spectroscopy (XPS) was used to study the surface modification in glass-ceramics when immersed in simulated body fluid. Formation of bioactive layer in SBF has been ascertained using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The SBF solutions were analyzed using an absorption spectrophotometer. The magnetic measurements indicated that all these glasses possess paramagnetic character and the [Fe 2+ /Fe 3+ ] ions ratio depends on the composition of glass and varied with Fe 2 O 3 concentration in glass matrix. In glass-ceramics saturation magnetization increases with increase in amount of Fe 2 O 3 . The nanostructure of hematite and magnetite is formed in the glass-ceramics with 15 and 20 wt.% Fe 2 O 3 , which is responsible for the magnetic property of these glass-ceramics. Introduction of Fe 2 O 3 induces several modifications at the glass-ceramics surface when immersed in SBF solution and thereby affecting the surface dissolution and the formation of the bioactive layer.

The hydrophobic and omnidirectional antireflection coating of SiO2 nanospheres with C18-TEOS

Science.gov (United States)

Hsu, Cheng-Chih; Lan, Wen-Lin; Chen, Nien-Po; Wu, Chyan-Chyi

2014-06-01

This paper demonstrates the antireflection coating of SiO2 nanospheres applied to cover glass by using the optimal spin-coating method. Because of the hydrolysis and condensation reactions between the SiO2 nanosphere antireflection (AR) coating and n-octadecyltriethoxysilane solution (C18-TEOS), the contact angle of the AR coating with hydrophobic treatment is improved approximately 38%, and the moisture-resistance remains unchanged, which preserved similar transmittance for six weeks. Furthermore, the AR coating with hydrophobic treatment exhibits approximately 3% and 7% improvement in the transmittance at normal and oblique incidence, respectively. The hydrophobic and omnidirectional AR coating with nanoscale SiO2 particles can be fabricated using the proposed simple and economical method.

Erbium-doped borosilicate glasses containing various amounts of P2O5 and Al2O3: Influence of the silica content on the structure and thermal, physical, optical and luminescence properties

International Nuclear Information System (INIS)

Bourhis, Kevin; Massera, Jonathan; Petit, Laeticia; Koponen, Joona; Fargues, Alexandre; Cardinal, Thierry; Hupa, Leena; Hupa, Mikko; Dussauze, Marc; Rodriguez, Vincent; Ferraris, Monica

2015-01-01

Highlights: • Er 3+ doped borosilicate glasses were processed with different compositions and characterizations. • An increase in the SiO 2 content leads to a silicate-rich environment around the Er 3+ site. • An increase in the SiO 2 content decreases the Er 3+ absorption cross-section at 980 nm. • Glasses with 60 mol% of SiO 2 exhibit a stronger emission intensity at 1530 nm than glasses with x = 50. • Highest 1.5 μm emission intensity was achieved for the Al and P containing glass with 60 mol% of SiO 2 . - Abstract: The influence of the silica content on several properties of Er-doped borosilicate glasses in the presence of various amounts of P 2 O 5 and Al 2 O 3 has been investigated. The introduction of P 2 O 5 and/or Al 2 O 3 are responsible for structural modifications in the glass network through a charge-compensation mechanism related to the formation of negatively-charged PO 4 and AlO 4 groups or through the formation of AlPO 4 -like structural units. In this paper, we show that an increase in the SiO 2 content leads to a silicate-rich environment around the Er 3+ site, resulting in an increased dependence of the Er 3+ ions optical and luminescence properties on the P 2 O 5 and/or Al 2 O 3 concentration. The highest emission intensity at 1.5 μm was achieved for the glass with an equal proportion of P and Al in the glass system with 60 mol% of SiO 2

Network structure and thermal stability study of high temperature seal glass

Science.gov (United States)

Lu, K.; Mahapatra, M. K.

2008-10-01

High temperature seal glass has stringent requirement on glass thermal stability, which is dictated by glass network structures. In this study, a SrO-La2O3-Al2O3-B2O3-SiO2 based glass system was studied using nuclear magnetic resonance, Raman spectroscopy, and x-ray diffraction for solid oxide cell application purpose. Glass structural unit neighboring environment and local ordering were evaluated. Glass network connectivity as well as silicon and boron glass former coordination were calculated for different B2O3:SiO2 ratios. Thermal stability of the borosilicate glasses was studied after thermal treatment at 850 °C. The study shows that high B2O3 content induces BO4 and SiO4 structural unit ordering, increases glass localized inhomogeneity, decreases glass network connectivity, and causes devitrification. Glass modifiers interact with either silicon- or boron-containing structural units and form different devitrified phases at different B2O3:SiO2 ratios. B2O3-free glass shows the best thermal stability among the studied compositions, remaining stable after thermal treatment for 200 h at 850 °C.

Influence of gel morphology on the corrosion kinetics of borosilicate glass: calcium and zirconium effect

International Nuclear Information System (INIS)

Cailleteau, C.

2008-12-01

This study is related to the question of the long-term behaviour of the nuclear waste confinement glass. A glass alteration layer (known as the 'gel'), formed at the glass surface in contact with water, can limit the exchanges between the glass and the solution. We studied five oxide based glasses SiO 2 -B 2 O 3 -Na 2 O-CaO-ZrO 2 . Two series of glasses were synthesized by substituting CaO for Na 2 O and ZrO 2 for SiO 2 . The leaching showed that the presence of Ca improves the reticulation of the vitreous network, inducing a decrease in the final degree of corrosion and the presence of Zr prevents the hydrolysis of silicon, which leads to a decrease of the initial dissolution rate. However, the introduction of Zr delays the drop of the alteration rate and leads to an increase in the alteration degree. In order to explain this unexpected behaviour, the gel morphology was investigated by small angle X-ray scattering. These experiments showed that the restructuring of porous network during the glass alteration process is limited by the increase of the Zr-content. Then, the restructuring of gel is at the origin of the major drop in the alteration rate observed for the low Zr-content glasses. Besides, both time-of-flight secondary-ion mass spectroscopy (ToF-SIMS) that provides an evaluation of extraneous element penetration into the gel pores and neutron scattering with index matching showed that the porosity closed during the corrosion in the glass without zirconia, but remained open in the high Zr-content glasses. These experiments, associated to simulations by a Monte Carlo method, establish a relationship between the morphologic transformations of gel and the alteration kinetics. (author)

Dissolution model for a glass having an adherent insoluble surface layer

International Nuclear Information System (INIS)

Harvey, K.B.; Larocque, C.A.B.

1990-01-01

Waste form glasses that contain substantial quantities of iron, manganese, and aluminum oxides, such as the Savannah River SRL TDS-131 glass, form a thick, hydrated surface layer when placed in contact with water. The dissolution of such a glass has been modeled with the Savannah River Model. The authors showed previously that the equations of the Savannah River Model could be fitted to published experimental data if a time-dependent diffusion coefficient was assumed for species of diffusing through the surface layer. The Savannah River Model assumes that all of the material dissolved from the glass enters solution, whereas it was observed that substantial quantities of material were retained in the surface layer. An alternative model, presented contains a mass balance equation that allows material either to enter solution or to be retained in the surface layer. It is shown that the equations derived using this model can be fitted to the published experimental data assuming a constant diffusion coefficient for species diffusing through the surface layer

Hardness properties and microscopic investigation of crack- crystal interaction in SiO(2)-MgO-Al(2)O(3)-K(2)O-B(2)O(3)-F glass ceramic system.

Science.gov (United States)

Roy, Shibayan; Basu, Bikramjit

2010-01-01

In view of the potential engineering applications requiring machinability and wear resistance, the present work focuses to evaluate hardness property and to understand the damage behavior of some selected glass-ceramics having different crystal morphologies with SiO(2)-MgO-Al(2)O(3)-K(2)O-B(2)O(3)-F composition, using static micro-indentation tests as well as dynamic scratch tests, respectively. Vickers hardness of up to 5.5 GPa has been measured in glass-ceramics containing plate like mica crystals. Scratch tests at a high load of 50 Nin artificial saliva were carried out in order to simulate the crack-microstructure interaction during real-time abrasion wear and machining operation. The experimental observations indicate that the novel "spherulitic-dendritic shaped "crystals, similar to the plate like crystals, have the potential to hinder the scratching induced crack propagation. In particular, such potential of the 'spherulitic-dendritic' crystals become more effective due to the larger interfacial area with the glass matrix as well as the dendritic structure of each mica plate, which helps in crack deflection and crack blunting, to a larger extent.While modest damage tolerant behavior is observed in case of 'spherulitic-dendritic' crystal containing material, severe brittle fracture of plate like crystals were noted, when both were scratched at 50 N load.

Investigating the solubility and cytocompatibility of CaO-Na2 O-SiO2 /TiO2 bioactive glasses.

Science.gov (United States)

Wren, Anthony W; Coughlan, Aisling; Smith, Courtney M; Hudson, Sarah P; Laffir, Fathima R; Towler, Mark R

2015-02-01

This study aims to investigate the solubility of a series of titanium (TiO2 )-containing bioactive glasses and their subsequent effect on cell viability. Five glasses were synthesized in the composition range SiO2 -Na2 O-CaO with 5 mol % of increments TiO2 substituted for SiO2 . Glass solubility was investigated with respect to (1) exposed surface area, (2) particle size, (3) incubation time, and (4) compositional effects. Ion release profiles showed that sodium (Na(+) ) presented high release rates after 1 day and were unchanged between 7 and 14 days. Calcium (Ca(2+) ) release presented a significant change at each time period and was also composition dependent, where a reduction in Ca(2+) release is observed with an increase in TiO2 concentration. Silica (Si(4+) ) release did not present any clear trends while no titanium (Ti(4+) ) was released. Cell numbers were found to increase up to 44%, compared to the growing control population, with a reduction in particle size and with the inclusion of TiO2 in the glass composition. © 2014 Wiley Periodicals, Inc.

Alkali depletion and ion-beam mixing in glasses

International Nuclear Information System (INIS)

Arnold, G.W.

1983-01-01

Ion-implantation-induced alkali depletion in simple alkali-silicate glasses (12M 2 O.88SiO 2 ) has been studied for implantations at room temperature and near 77K. Results are consistent with a mechanism for alkali removal, by heavy ion bombardment, based on radiation-enhanced migration and preferential removal of alkali from the outermost layers. Similar results were obtained for mixed-alkali glasses ((12-x)Cs 2 .O.xM 2 O.88SiO 2 ) where, in addition, a mixed-alkali effect may also be operative. Some preliminary experiments with ion implantation through thin Al films on SiO 2 glass and on a phosphate glass show that inter-diffusion takes place and suggest that this ion-mixing technique may be a useful method for altering the physical properties of glass surfaces

Composition-structure-property (Zn2+ and Ca2+ ion release) evaluation of Si-Na-Ca-Zn-Ce glasses: Potential components for nerve guidance conduits

International Nuclear Information System (INIS)

Zhang, X.F.; Kehoe, S.; Adhi, S.K.; Ajithkumar, T.G.; Moane, S.; O'Shea, H.; Boyd, D.

2011-01-01

Bioactive glasses have demonstrated tailored therapeutic ion release, primarily with respect to the augmentation of hard tissues. However, controlled degradation and release of therapeutic ions from biomaterials may also play an important role in soft tissue regeneration such as repair of peripheral nerve discontinuities. In this study, three silica based glasses (0.5SiO 2 -0.2CaO-0.13ZnO-XNa 2 O-(0.17-X) CeO 2 ) where, (0.04 29 Si isotope was probed for each glass using 29 Si MAS-NMR, whilst the thermal characteristics of each glass were examined using DTA. Following these analyses, ion release profiles for Ca 2+ and Zn 2+ were evaluated; an equivalent specific surface area of 1 m 2 of each glass powder was incubated (37 deg. C) in 10 ml of citric acid buffer and TRIS-HCI buffer solution (pH 3.0 and pH 7.4 respectively) for incubation periods of up to 30 days. The Zn 2+ concentration of each filtrate was analysed using flame Atomic Absorption Spectroscopy (Varian AA240FS Fast Sequential AAS) and the Ca 2+ concentration of each filtrate was determined using Inductively Coupled Plasma-Mass Spectrometer (Varian 820 ICP-MS). Results obtained from the 29 Si MAS-NMR spectra indicated Q 2 structures pervading the network. An analytical model was proposed to analyse the ion release profiles for each glass, and indicated heterogeneous dissolution of glass networks. The ion release data demonstrates that ion release in the range (19.26-3130 ppm) for Ca 2+ and in the range (5.97-4904 ppm) for Zn 2+ occurred. Release of such elements, at appropriate levels, from peripheral nerve guidance conduits may be advantageous with respect to the repair of peripheral nerve discontinuities.

Photoemission study on electrical dipole at SiO_2/Si and HfO_2/SiO_2 interfaces

International Nuclear Information System (INIS)

Fujimura, Nobuyuki; Ohta, Akio; Ikeda, Mitsuhisa; Makihara, Katsunori; Miyazaki, Seiichi

2017-01-01

Electrical dipole at SiO_2/Si and HfO_2/SiO_2 interfaces have been investigated by X-ray photoelectron spectroscopy (XPS) under monochromatized Al Kα radiation. From the analysis of the cut-off energy for secondary photoelectrons measured at each thinning step of a dielectric layer by wet-chemical etching, an abrupt potential change caused by electrical dipole at SiO_2/Si and HfO_2/SiO_2 interfaces has been clearly detected. Al-gate MOS capacitors with thermally-grown SiO_2 and a HfO_2/SiO_2 dielectric stack were fabricated to evaluate the Al work function from the flat band voltage shift of capacitance-voltage (C-V) characteristics. Comparing the results of XPS and C-V measurements, we have verified that electrical dipole formed at the interface can be directly measured by photoemission measurements. (author)

Effect of Na{sub 2}O on aqueous dissolution of nuclear waste glasses

Energy Technology Data Exchange (ETDEWEB)

Farooqi, Rahmat Ullah, E-mail: rufarooqi@live.com [Division of Advanced Nuclear Engineering, Pohang University of Science and Technology, 77 Cheongam-Ro, Nam-Gu, Pohang, Gyeongbuk 790-784 (Korea, Republic of); Hrma, Pavel [Division of Advanced Nuclear Engineering, Pohang University of Science and Technology, 77 Cheongam-Ro, Nam-Gu, Pohang, Gyeongbuk 790-784 (Korea, Republic of); Pacific Northwest National Laboratory, Richland, WA (United States)

2017-04-15

Sodium oxide is present in the majority of commercial and waste glasses as a viscosity-reducing component. In some nuclear waste glasses, its source is the waste itself. As such, it can limit the waste loading because of its deleterious effect on the resistance of the glass to attack by aqueous media. The maximum tolerable content of Na{sub 2}O in glass depends on the presence and concentration of components that interact with it. To assess the acceptability limits of Na{sub 2}O in the composition region of nuclear waste glasses, we formulated 11 baseline compositions by varying the content of oxides of Si, B, Al, Ca, Zr, and Li. In each of these compositions, we varied the Na{sub 2}O fraction from 8–16 mass% to 23–30 mass%. To each of 146 glasses thus formulated, we applied the seven-day Product Consistency Test (PCT) to determine normalized B and Na releases (r{sub i}, where i ≡ B or Na). Fitting approximation functions ln(r{sub i}/gm{sup −2}) = Σb{sub ij}g{sub j} to r{sub i} data (g{sub j} is the j-th component mass fraction and b{sub ij} the corresponding component coefficient), we showed that the r{sub B} (and, consequently, the initial glass alteration rate) was proportional to the glass component mass fractions in the order Al{sub 2}O{sub 3}2}2}2}O{sub 3}2}O2}O. No threshold was detected at which glass structure would fall apart or beyond which a continuous nondurable phase would be separated. Specific examples are given to demonstrate restrictions imposed on the boundary of the composition region of acceptable glasses by the maximum allowable r{sub B} and by the melt viscosity required for glass melter operation. Finally, the role that PCT data may play in understanding the evolution of the glass alteration process is discussed.

Influence of Y2O3 Addition on Crystallization, Thermal, Mechanical, and Electrical Properties of BaO-Al2O3-B2O3-SiO2 Glass-Ceramic for Ceramic Ball Grid Array Package

Science.gov (United States)

Li, Bo; Li, Wei; Zheng, Jingguo

2018-01-01

Y2O3 addition has a significant influence on the crystallization, thermal, mechanical, and electrical properties of BaO -Al2O3 -B2O3 -SiO2 (BABS) glass-ceramics. Semi-quantitative calculation based on x-ray diffraction demonstrated that with increasing Y2O3 content, both the crystallinity and the phase content of cristobalite gradually decreased. It is effective for the additive Y2O3 to inhibit the formation of cristobalite phase with a large coefficient of thermal expansion value. The flexural strength and the Young's modulus, thus, are remarkably increased from 140 MPa to 200 MPa and 56.5 GPa to 63.7 GPa, respectively. Also, the sintering kinetics of BABS glass-ceramics with various Y2O3 were investigated using the isothermal sintering shrinkage curve at different sintering temperatures. The sintering activation energy Q sharply decreased from 99.8 kJ/mol to 81.5 kJ/mol when 0.2% Y2O3 was added, which indicated that a small amount of Y2O3 could effectively promote the sintering procedure of BABS glass-ceramics.

Fiber-optic thermometer application of thermal radiation from rare-earth end-doped SiO2 fiber

International Nuclear Information System (INIS)

Katsumata, Toru; Morita, Kentaro; Komuro, Shuji; Aizawa, Hiroaki

2014-01-01

Visible light thermal radiation from SiO 2 glass doped with Y, La, Ce, Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu were studied for the fiber-optic thermometer application based on the temperature dependence of thermal radiation. Thermal radiations according to Planck's law of radiation are observed from the SiO 2 fibers doped with Y, La, Ce, Pr, Eu, Tb, and Lu at the temperature above 1100 K. Thermal radiations due to f-f transitions of rare-earth ions are observed from the SiO 2 fibers doped with Nd, Dy, Ho, Er, Tm, and Yb at the temperature above 900 K. Peak intensities of thermal radiations from rare-earth doped SiO 2 fibers increase sensitively with temperature. Thermal activation energies of thermal radiations by f-f transitions seen in Nd, Dy, Ho, Er, Tm, and Yb doped SiO 2 fibers are smaller than those from SiO 2 fibers doped with Y, La, Ce, Pr, Eu, Tb, and Lu. Thermal radiation due to highly efficient f-f transitions in Nd, Dy, Ho, Er, Tm, and Yb ions emits more easily than usual thermal radiation process. Thermal radiations from rare-earth doped SiO 2 are potentially applicable for the fiber-optic thermometry above 900 K

Microstructure, mechanical, and in vitro properties of mica glass-ceramics with varying fluorine content.

Science.gov (United States)

Molla, Atiar Rahaman; Basu, Bikramjit

2009-04-01

The design and development of glass ceramic materials provide us the unique opportunity to study the microstructure development with changes in either base glass composition or heat treatment conditions as well as to understand processing-microstructure-property (mechanical/biological) relationship. In the present work, it is demonstrated how various crystal morphology can develop when F(-) content in base glass (K(2)O-B(2)O(3)-Al(2)O(3)-SiO(2)-MgO-F) is varied in the range of 1.08-3.85% and when all are heat treated at varying temperatures of 1000-1120 degrees C. For some selected heat treatment temperature, the heat treatment time is also varied over 4-24 h. It was established that with increase in fluoride content in the glass composition, the crystal volume fraction of the glass-ceramic decreases. Using 1.08% fluoride, more than 80% crystal volume fraction could be achieved in the K(2)O-B(2)O(3)-Al(2)O(3)-SiO(2)-MgO-F system. It was observed that with lower fluoride content glass-ceramic, if heated at 1040 degrees C for 12 h, an oriented microstructure with 'envelop like' crystals can develop. For glass ceramics with higher fluorine content (2.83% or 3.85%), hexagonal-shaped crystals are formed. Importantly, high hardness of around 8 GPa has been measured in glass ceramics with maximum amount of crystals. The three-point flexural strength and elastic modulus of the glass-ceramic (heat treated at 1040 degrees C for 24 h) was 80 MPa and 69 GPa of the sample containing 3.85% fluorine, whereas, similar properties obtained for the sample containing 1.08% F(-) was 94 MPa and 57 GPa, respectively. Further, in vitro dissolution study of the all three glass-ceramic composition in artificial saliva (AS) revealed that leached fluoride ion concentration was 0.44 ppm, when the samples were immersed in AS for 8 weeks. This was much lower than the WHO recommended safety limits of 1.5 ppm. Among all the investigated glass-ceramic samples, the glass ceramic with 3.85% F

Effect of heat treatment on the properties of SiO2-CaO-MgO-P 2O 5 bioactive glasses.

Science.gov (United States)

Zhou, Yue; Li, Hongying; Lin, Kaili; Zhai, Wanying; Gu, Weiming; Chang, Jiang

2012-09-01

Since the invention of 45S5 Bioglass, researchers never stopped exploring new generation bioactive glass (BG) materials for wider applications in regenerative medicine, among which a novel SiO(2)-CaO-MgO-P(2)O(5) bioactive glass (BG20) is an excellent candidate. However, apart from their biocompatibility and bioactivity, a porous structure is also a must for a tissue engineering scaffold in successfully fixing bone defect. The porosity is the outcome of the high temperature (500-1,000 °C) treatment in the fabricating process of the bioglass scaffold. Under the high temperature, the amorphous glass material will become crystallized at certain percentage in the glass matrix, and possibly leading to consequent changes in the mechanical strength, biodegradability and bioactivity. To elucidate the effect of phase transition on the change of the properties of BG20, the experiments in this report were designed to fine-tuning the heat treating temperatures to fabricate a series of BG20 powders with different crystallization structures. X-ray diffraction revealed a positive correlation between the heating temperature and the crystallization, as well as the compressive strength of the materials. In vitro degradation and ion analysis by ICP-AES demonstrated a similar releasing behavior of different ions including Mg(2+), Ca(2+) and Si(4+), which in common is the tendency of decreasing of the ion concentration along with the increasing of the treating temperature. Cell proliferation assay using both mouse fibroblasts (NIH3T3) and bone marrow stromal cells (BMSCs) showed little toxicity of the ionic extract of the BG20 powders at all the treating temperatures, while fibroblasts demonstrated a significant promoting in the percentage of proliferation. Furthermore, reverse-transcription and polymerase chain reaction analysis on two representative marker genes for early osteogenesis and endochondral ossification, respectively, type I collagen alpha 1 and Indian Hedge-hog, showed

Annealing behavior of oxygen in-diffusion from SiO2 film to silicon substrate

International Nuclear Information System (INIS)

Abe, T.; Yamada-Kaneta, H.

2004-01-01

Diffusion behavior of oxygen at (near) the Si/SiO 2 interface was investigated. We first oxidized the floating-zone-grown silicon substrates, and then annealed the SiO 2 -covered substrates in an argon ambient. We examined two different conditions for oxidation: wet and dry oxidation. By the secondary-ion-mass spectrometry, we measured the depth profiles of the oxygen in-diffusion of these heat-treated silicon substrates: We found that the energy of dissolution (in-diffusion) of an oxygen atom that dominates the oxygen concentration at the Si/SiO 2 interface depends on the oxidation condition: 2.0 and 1.7 eV for wet and dry oxidation, respectively. We also found that the barrier heights for the oxygen diffusion in argon anneal were significantly different for different ambients adopted for the SiO 2 formation: 3.3 and 1.8 eV for wet and dry oxidation, respectively. These findings suggest that the microscopic behavior of the oxygen atoms at the Si/SiO 2 interface during the argon anneal depends on the ambient adopted for the SiO 2 formation

Laser ablation of silicate glasses doped with transuranic actinides

International Nuclear Information System (INIS)

Gibson, J.K.; Haire, R.G.

1998-01-01

Direct sampling laser ablation plasma mass spectrometry (DS-LAMS) was applied to silica glasses doped with 237 Np, 242 Pu or 241 Am using a unique instrument recently installed into a transuranic glovebox. The primary goal was to assess the utility of mass spectrometry of directly ablated ions for facile evaluation of actinide (An) constituents of silicate glass immobilization matrices used for encapsulation of radionuclides. The instrument and general procedures have been described elsewhere. Three high-purity silicate glasses prepared by a sol-gel process (SG) and one conventional high-temperature (HT; melting point ∼ 1,450 C) borosilicate glass were studied. These glasses comprised the following constituents, with compositions expressed in mass percentages: Np-HT ∼ 30% SiO 2 + 6% B 2 O 3 + 3% BaO + 13% Al 2 O 3 + 10% PbO + 30% La 2 O 3 + 8% 237 NpO 2 ; Np-SG ∼ 70% SiO 2 + 30% 237 NpO 2 ; Pu-SG ∼ 70% SiO 2 + 30% 242 PuO 2 ; Am-SG ∼ 85% SiO 2 + 15% 241 AmO 2

Cordierite Glass-Ceramics for Dielectric Materials

International Nuclear Information System (INIS)

Siti Mazatul Azwa Saiyed Mohd Nurddin; Selamat, Malek; Ismail, Abdullah

2007-01-01

The objective of this project is to examine the potential of using Malaysian silica sand deposit as SiO2 raw material in producing cordierite glass-ceramics (2MgO-2Al2O3-5SiO2) for dielectric materials. Upgraded silica sands from Terengganu and ex-mining land in Perak were used in the test-works. The glass batch of the present work has a composition of 45.00% SiO2, 24.00% Al2O3, 15.00% MgO and 8.50% TiO2 as nucleation agent. From the differential thermal analysis results, the crystallization temperature was found to start around 900 deg. C. The glass samples were heat-treated at 900 deg. C and 1000 deg. C. The X-ray diffraction analysis (XRD) results showed glass-ceramics from Terengganu samples containing mainly cordierite and minor β-quartz crystals. However, glass-ceramics from ex-mining land samples contained mainly α-quartz and minor cordierite crystals. Glass-ceramics with different crystal phases exhibit different mechanical, dielectric and thermal properties. Based on the test works, both silica sand deposits, can be potentially used to produce dielectric material component

Synthesis and Luminescence Properties of Yellow-emitting SiO2/Zn2SiO4: Mn Nanocomposite

Directory of Open Access Journals (Sweden)

Karim OMRI

2014-05-01

Full Text Available Yellow light emitting Mn2+-doped b-Zn2SiO4 phosphor nanoparticles embedded in SiO2 host matrix, were prepared by a simple solid-phase reaction under natural atmosphere at 1500 °C for 2 hours after the incorporation of manganese doped zinc oxide nanoparticles in silica using sol-gel method. The SiO2/Zn2SiO4:Mn nanocomposite was characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, scanning electron microscopy (SEM and photoluminescence (PL. The nanopowder was crystallized in triclinic b-Zn2SiO4 phase with a particles size varies between 70 nm and 84 nm. The SiO2/b-Zn2SiO4:Mn nanocomposite exhibited a broad yellow emission band at 575 nm under UV excitation light. The dependence of the intensity and energy position of the obtained PL band on measurement temperature and power excitation will be discussed.

Magnetic susceptibility of sodium disilicate glasses containing PuO2

International Nuclear Information System (INIS)

Aldred, A.T.

1979-01-01

A solubility limit of approx. 6 mol % PuO 2 in sodium disilicate (Na 2 O.2SiO 2 ) glass has been determined. Magnetic susceptibility measurements on these glasses yield approximate Curie-Weiss behavior, in contrast to the temperature-independent susceptibility of crystalline PuO 2 . This result is interpreted to indicate that the local site symmetry around the Pu ion in the sodium disilicate glass is much different than in crystalline PuO 2 . The effective paramagnetic moments determined from the temperature dependence of the susceptibility are found to be consistent with calculated free-ion values based on the most likely 5f electron configurations

Infrared Spectroscopic Study For Structural Investigation Of Lithium Lead Silicate Glasses

International Nuclear Information System (INIS)

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

2011-01-01

Lithium lead silicate glasses with composition 30Li 2 O·(70-x)PbO·xSiO 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 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 2 content changes from 6.0 to 0.4. The observed absorption band around 450-510 cm -1 in IR spectra of these glasses indicates the presence of network forming PbO 4 tetrahedral units in glass structure. The increase in intensity with increasing SiO 2 content (upto x = 30 mol %) suggests superposition of Pb-O and Si-O bond vibrations in absorption band around 450-510 cm -1 . The values of optical basicity in these glasses were found to be dependent directly on PbO/SiO 2 ratio.

A study of low threshold and high gain Nd3+ ions doped SiO2-B2O3-Na2CO3-NaF-CaF2 glasses for NIR laser applications

Science.gov (United States)

Megala, Rajesh; Gowthami, T.; John Sushma, N.; Kamala, S.; Deva Prasad Raju, B.

2018-05-01

Fluoroborosilicate glasses of composition 35SiO2-25B2O3-10Na2CO3-15NaF-15CaF2-xNd2O3 (where x = 0.1, 0.5. 1.0, 2.0 mol%) were prepared by melt quenching technique and various physical properties have been calculated. From the absorption spectra J-O Intensity parameters Ωλ (λ = 2, 4, 6) and radiative properties are evaluated by using J-O theory. The high values of Ω2 = 4.213 × 10-20 cm2, Ω4 = 5.345 × 10-20 cm2, Ω6 = 5.526 × 10-20 cm2 suggest that among the prepared glasses 0.5 mol% Nd glass is more asymmetric, more covalent and rigid in nature. The emission spectra were recorded with 808 nm laser as excitation source. The strong NIR emissions were observed at 876 nm, 1056 nm, 1328 nm corresponding to the transitions 4F3/2 → 4I9/2, 4F3/2 → 4I11/2, 4F3/2 → 4I13/2 respectively. Stimulated emission cross -section (σemi) and Gain bandwidth (σemi × Δλeff) were calculated. For 0.5 mol% Nd these values are found to be 3.30 × 10-20 cm2, 11 × 10-26 cm2. From the decay curve analysis the lifetime values for 4F3/2 level have been determined and these values are decreased with increase in Nd3+ ions concentration. These results may suggest that the prepared SBNCNd05 (Nd = 0.5 mol%) glass could be useful for 1056 nm laser applications.

The structure of MgO-SiO2 glasses at elevated pressure.

Science.gov (United States)

Wilding, Martin; Guthrie, Malcolm; Kohara, Shinji; Bull, Craig L; Akola, Jaakko; Tucker, Matt G

2012-06-06

The magnesium silicate system is an important geophysical analogue and neutron diffraction data from glasses formed in this system may also provide an initial framework for understanding the structure-dependent properties of related liquids that are important during planetary formation. Neutron diffraction data collected in situ for a single composition (38 mol% SiO(2)) magnesium silicate glass sample shows local changes in structure as pressure is increased from ambient conditions to 8.6 GPa at ambient temperature. A method for obtaining the fully corrected, total structure factor, S(Q), has been developed that allows accurate structural characterization as this weakly scattering glass sample is compressed. The measured S(Q) data indicate changes in chemical ordering with pressure and the real-space transforms show an increase in Mg-O coordination number and a distortion of the local environment around magnesium ions. We have used reverse Monte Carlo methods to compare the high pressure and ambient pressure structures and also compare the high pressure form with a more silica-poor glass (Mg(2)SiO(4)) that represents the approach to a more dense, void-free and topologically ordered structure. The Mg-O coordination number increases with pressure and we also find that the degree of continuous connectivity of Si-O bonds increases via a collapse of interstices.

Property/composition relationships for Hanford high-level waste glasses melting at 1150 degrees C volume 2: Chapters 12-16 and appendices A-K

International Nuclear Information System (INIS)

Hrma, P.R.; Piepel, G.F.

1994-12-01

A Composition Variation Study (CVS) is being performed within the Pacific Northwest Laboratory Vitrification Technology Development (PVTD) project in support of a future high-level nuclear waste vitrification plant at the Hanford site in Washington. From 1989 to 1994, over 120 nonradioactive glasses were melted and properties measured in five statistically-designed experimental phases. Glass composition is represented by the 10 components SiO 2 , B 2 O 3 , ZrO 2 , Na 2 O, Li 2 O, CaO, MgO, and Others (all remaining components). The properties measured include viscosity (η), electrical conductivity (ε), glass transition temperature (T g ), thermal expansion of solid glass (α s ) and molten glass (α m ), crystallinity (quenched and canister centerline cooled glasses), liquidus temperature (T L ), durability based on normalized elemental releases from the Materials Characterization Center-1 28-day dissolution test (MCC-1, r mi ) and the 7-day Product Consistency Test (PCT, r pi ), and solution pHs from MCC-1 and PCT. Amorphous phase separation was also evaluated. Empirical first- and second-order mixture models were fit using the CVS data to relate the various properties to glass composition. Equations for calculating the uncertainty associated with property values predicted by the models were also developed. The models were validated using both internal and external data. Other modeling approaches (e.g., non-bridging oxygen, free energy of hydration, phase-equilibria T L ) were investigated for specific properties. A preliminary Qualified Composition Region was developed to identify glass compositions with high confidence of being processable in a melter and meeting waste form acceptance criteria

Glass in the submarine section of the HSDP2 drill core, Hilo, Hawaii

Science.gov (United States)

Stolper, Edward; Sherman, Sarah; Garcia, Michael; Baker, Michael; Seaman, Caroline

2004-07-01

relationship between these magma types is that as the low-SiO2 magmas ascended from their sources, they interacted chemically and thermally with overlying peridotites, resulting in dissolution of orthopyroxene and clinopyroxene and precipitation of olivine, thereby generating high-SiO2 magmas. There are glasses with CaO, Al2O3, and SiO2 contents slightly elevated relative to most low-SiO2 samples; we suggest that these differences reflect involvement of pyroxene-rich lithologies in the petrogenesis of the CaO-Al2O3-enriched glasses. There is also a small group of low-SiO2 glasses distinguished by elevated K2O and CaO contents; the sources of these samples may have been enriched in slab-derived fluid/melts. Low-SiO2 glasses from the top of zone 3 (2233-2280 mbsl) are more alkaline, more fractionated, and incompatible-element-enriched relative to other glasses from zone 3. This excursion at the top of zone 3, which is abruptly overlain by more silica-rich tholeiitic magmas, is reminiscent of the end of Mauna Kea shield building higher in the core.

The chemical durability of alkali aluminosilicate glasses

International Nuclear Information System (INIS)

Tait, J.C.; Mandolesi, D.L.

1983-09-01

The aqueous durabilities of a series of glasses based on the sodium aluminosilicate system (Na 2 O-Al 2 O 3 -SiO 2 ) have been studied. The effects of molecular substitution of K 2 O or CaO for Na 2 O, and B 2 O 3 for Al 2 O 3 have been investigated. The temperature dependence of leaching in the Na 2 O-B 2 O 3 -Al 2 O 3 -SiO 2 system was studied with glasses containing 2 wt percent simulated UO 2 fuel recycle waste. The results confirm that aluminosilicate glasses are more durable than their borosilicate counterparts. The leaching results are explained in terms of glass structure and bonding, and a general leaching mechanism for aluminosilicate glasses is presented

Violet-green excitation for NIR luminescence of Yb3+ ions in Bi2O3-B2O3-SiO2-Ga2O3 glasses.

Science.gov (United States)

Li, Weiwei; Cheng, Jimeng; Zhao, Guoying; Chen, Wei; Hu, Lili; Guzik, Malgorzata; Boulon, Georges

2014-04-21

60Bi(2)O(3)-20B(2)O(3)-10SiO(2)-10Ga(2)O(3) glasses doped with 1-9 mol% Yb(2)O(3) were prepared and investigated mainly on their violet-green excitation for the typical NIR emission of Yb(3+), generally excited in the NIR. Two violet excitation bands at 365 nm and 405 nm are related to Yb(2+) and Bi(3+). 465 nm excitation band and 480 nm absorption band in the blue-green are assigned to Bi(0) metal nanoparticles/grains. Yb-content-dependence of the excitation and absorption means that Bi(0) is the reduced product of Bi(3+), but greatly competed by the redox reaction of Yb(2+) ↔ Yb(3+). It is proved that the violet-green excitations result in the NIR emission of Yb(3+). On the energy transfer, the virtual level of Yb(3+)-Yb(3+) as well as Bi(0) dimers probably plays an important role. An effective and controllable way is suggested to achieve nano-optical applications by Bi(0) metal nanoparticles/grains and Yb(3+).

Sol-Gel Glasses

Science.gov (United States)

Mukherjee, S. P.

1985-01-01

Multicomponent homogeneous, ultrapure noncrystalline gels/gel derived glasses are promising batch materials for the containerless glass melting experiments in microgravity. Hence, ultrapure, homogeneous gel precursors could be used to: (1) investigate the effect of the container induced nucleation on the glass forming ability of marginally glass forming compositions; and (2) investigate the influence of gravity on the phase separation and coarsening behavior of gel derived glasses in the liquid-liquid immiscibility zone of the nonsilicate systems having a high density phase. The structure and crystallization behavior of gels in the SiO2-GeO2 as a function of gel chemistry and thermal treatment were investigated. As are the chemical principles involved in the distribution of a second network former in silica gel matrix being investigated. The procedures for synthesizing noncrystalline gels/gel-monoliths in the SiO2-GeO2, GeO2-PbO systems were developed. Preliminary investigations on the levitation and thermal treatment of germania silicate gel-monoliths in the Pressure Facility Acoustic Levitator were done.

Effect of the size of nanoparticles on their dissolution within metal-glass nanocomposites under sustained irradiation

Energy Technology Data Exchange (ETDEWEB)

Vu, T. H. Y., E-mail: thi-hai-yen.vu@polytechnique.edu; Ramjauny, Y.; Rizza, G.; Hayoun, M. [Laboratoire des Solides Irradiés, École Polytechnique, CNRS, CEA, Université Paris-Saclay, F-91128 Palaiseau (France)

2016-01-21

We investigate the dissolution law of metallic nanoparticles (NPs) under sustained irradiation. The system is composed of isolated spherical gold NPs (4–100 nm) embedded in an amorphous silica host matrix. Samples are irradiated at room temperature in the nuclear stopping power regime with 4 MeV Au ions for fluences up to 8 × 10{sup 16 }cm{sup −2}. Experimentally, the dependence of the dissolution kinetics on the irradiation fluence is linear for large NPs (45–100 nm) and exponential for small NPs (4–25 nm). A lattice-based kinetic Monte Carlo (KMC) code, which includes atomic diffusion and ballistic displacement events, is used to simulate the dynamical competition between irradiation effects and thermal healing. The KMC simulations allow for a qualitative description of the NP dissolution in two main stages, in good agreement with the experiment. Moreover, the perfect correlation obtained between the evolution of the simulated flux of ejected atoms and the dissolution rate in two stages implies that there exists an effect of the size of NPs on their dissolution and a critical size for the transition between the two stages. The Frost-Russell model providing an analytical solution for the dissolution rate, accounts well for the first dissolution stage but fails in reproducing the data for the second stage. An improved model obtained by including a size-dependent recoil generation rate permits fully describing the dissolution for any NP size. This proves, in particular, that the size effect on the generation rate is the principal reason for the existence of two regimes. Finally, our results also demonstrate that it is justified to use a unidirectional approximation to describe the dissolution of the NP under irradiation, because the solute concentration is particularly low in metal-glass nanocomposites.

Initial dissolution rate of a Japanese simulated high-level waste glass P0798 as a function of pH and temperature measured by using micro-channel flow-through test method

International Nuclear Information System (INIS)

Inagaki, Yaohiro; Makigaki, Hikaru; Idemitsu, Kazuya; Arima, Tatsumi; Mitsui, Sei-ichiro; Noshita, Kenji

2012-01-01

Aqueous dissolution tests were performed for a Japanese type of simulated high-level waste (HLW) glass P0798 by using a newly developed test method of micro-channel flow-through (MCFT) method, and the initial dissolution rate of glass matrix, r 0 , was measured as a function of solution pH (3-11) and temperature (25-90degC) precisely and consistently for systematic evaluation of the dissolution kinetics. The MCFT method using a micro-channel reactor with a coupon shaped glass specimen has the following features to provide precise and consistent data on the glass dissolution rate: (1) any controlled constant solution condition can be provided over the test duration; (2) the glass surface area actually reacting with solution can be determined accurately; and (3) direct and totally quantitative analyses of the reacted glass surface can be performed for confirming consistency of the test results. The present test results indicated that the r 0 shows a 'V-shaped' pH dependence with a minimum at around pH 6 at 25degC, but it changes to a 'U-shaped' one with a flat bottom at neutral pH at elevated temperatures of up to 90degC. The present results also indicated that the r 0 increases with temperature according to an Arrhenius law at any pH, and the apparent activation energy evaluated from Arrhenius relation increases with pH from 54 kJ/mol at pH 3 to 76 kJ/mol at pH 10, which suggests that the dissolution mechanism changes depending on pH. (author)

Colorimetric determination of Fe2+/Fe3+ ratio in radioactive glasses

International Nuclear Information System (INIS)

Coleman, C.J.; Baumann, E.W.; Bibler, N.E.

1992-01-01

In the vitrification of nuclear wastes, the Fe 2+ /Fe 3+ ratio in the glass is a measure of the redox properties of the glass melt. It is necessary to measure this ratio to ensure that the melt redox properties are suitable for the glass melter. A colorimetric method for measuring the Fe 2+ /Fe 3+ ratio in highly radioactive glasses was developed and tested remotely in a shielded cell. The tests were performed on glasses similar in composition and radioactivity to those that will be produced in the Savannah River Site Defense Waste Processing Facility. The first step of the method is dissolution of finely crushed glass with a hydrofluoric/sulfuric acid mixture with ammonium vanadate added to preserve the Fe 2+ content of the glass during the dissolution. Boric acid is then added to complex fluoride and to destroy iron-fluoride complexes. After adjusting the solution to pH 5, FerroZine TM (trademark of the Hach Company, Loveland, CO) reagent is added to form a magenta-colored complex with Fe 2+ . The absorbance at 562 nm is measured by using a fiber optic-coupled photodiode array spectrophotometer. Ascorbic acid is then used to reduce all the iron in solution to Fe 2+ and the absorbance is again measured. The difference in absorbance measurements corresponds to the Fe 3+ in the sample and the Fe 2+ /Fe 3+ ratio can be calculated

Crystallization kinetics of bioactive glasses in the ZnO-Na2O-CaO-SiO2 system.

Science.gov (United States)

Malavasi, Gianluca; Lusvardi, Gigliola; Pedone, Alfonso; Menziani, Maria Cristina; Dappiaggi, Monica; Gualtieri, Alessandro; Menabue, Ledi

2007-08-30

The crystallization kinetics of Na(2)O.CaO.2SiO(2) (x = 0) and 0.68ZnO.Na(2)O.CaO.2SiO(2) (x = 0.68, where x is the ZnO stoichiometric coefficient in the glass formula) bioactive glasses have been studied using both nonisothermal and isothermal methods. The results obtained from isothermal XRPD analyses have showed that the first glass crystallizes into the isochemical Na(2)CaSi(2)O(6) phase, whereas the Na(2)ZnSiO(4) crystalline phase is obtained from the Zn-rich glass, in addition to Na(2)CaSi(2)O(6). The activation energy (Ea) for the crystallization of the Na(2)O.CaO.2SiO(2) glass is 193 +/- 10 and 203 +/- 5 kJ/mol from the isothermal in situ XRPD and nonisothermal DSC experiments, respectively. The Avrami exponent n determined from the isothermal method is 1 at low temperature (530 degrees C), and its value increases linearly with temperature increase up to 2 at 607 degrees C. For the crystallization of Na(2)CaSi(2)O(6) from the Zn-containing glass, higher values of both the crystallization temperature (667 and 661 degrees C) and Ea (223 +/- 10 and 211 +/- 5 kJ/mol) have been found from the isothermal and nonisothermal methods, respectively. The Na(2)ZnSiO(4) crystalline phase crystallizes at lower temperature with respect to Na(2)CaSi(2)O(6), and the Ea value is 266 +/- 20 and 245 +/- 15 kJ/mol from the isothermal and nonisothermal methods, respectively. The results of this work show that the addition of Zn favors the crystallization from the glass at lower temperature with respect to the Zn-free glass. In fact, it causes an increase of Ea for the Na diffusion process, determined using MD simulations, and consequently an overall increase of Ea for the crystallization process of Na(2)CaSi(2)O(6). Our results show good agreement between the Ea and n values obtained with the two different methods and confirm the reliability of the nonisothermal method applied to kinetic crystallization of glassy systems. This study allows the determination of the temperature

The dissolution rate of silicate glasses and minerals: an alternative model based on several activated complexes

International Nuclear Information System (INIS)

Berger, G.

1997-01-01

Most of the mineral reactions in natural water-rock systems progress at conditions close to the chemical equilibrium. The kinetics of these reactions, in particular the dissolution rate of the primary minerals, is a major constrain for the numerical modelling of diagenetic and hydrothermal processes. In the case of silicates, recent experimental studies have pointed out the necessity to better understand the elementary reactions which control the dissolution process. This article presents several models that have been proposed to account for the observed dissolution rate/chemical affinity relationships. The case of glasses (R7T7), feldspars and clays, in water, in near neutral pH aqueous solutions and in acid/basic media, are reviewed. (A.C.)

Geochemical modelling of the long-term dissolution behaviour of the French nuclear glass R7T7

International Nuclear Information System (INIS)

Michaux, L.; Mouche, E.; Petit, J.-C.; Fritz, B.

1992-01-01

The long-term dissolution behaviour of the French nuclear reference glass R7T7 was studied by means of the geochemical code DISSOL. New experimental data which support some of the assumptions of DISSOL are presented: namely, that the dissolution is congruent and that the altered layer can be considered as an assemblage of secondary phases. At 100 o C the main results of modelling are that the altered layer is essentially formed of a pure siliceous phase (amorphous silica or chalcedony) associated with smectites and zeolites. This sequence of secondary minerals is closely linked to the chemical composition of the glass. For high degrees of reaction, corresponding to high B concentration, the ionic strength reaches 1 and the pH varies from 9 to 10 depending on the CO 2 fugacity; B,Li and Na are essentially found in solution and their concentrations depend on the amount of dissolved glass. By contrast Fe,Al and Zn have low solution concentrations which are controlled by solubility products of secondary minerals. Silicon and Ca have an intermediate behaviour which depends on the choice of selected secondary minerals. The total volume of the secondary phases is always lower than that of the corresponding dissolved glass. The results of modelling compared to static leaching experimental results show only minor differences which can be explained by kinetic control or colloid formation. It is concluded that the altered layer is not a barrier to diffusion. The consequences of this work for actinide solubility are also discussed. (author)

Effect of SiO2/B2O3 Ratio on the Crystallization Behavior and Dielectric Properties of Barium Strontium Titanate Glass-Ceramics Prepared by Sol-Gel Process

Science.gov (United States)

Chen, Yongzhou; Zhang, Yong; Song, Xiaozhen; Shen, Ziqin; Zhang, Tianyuan

2018-05-01

Ferroelectric glass-ceramics, with a basic composition 90 wt.% (Ba0.65Sr0.35)TiO3-10 wt.% (B2O3-nSiO2) (n = 0.5, 1, 3, 5) were synthesized by the sol-gel method and their phase development and dielectric properties were investigated by differential thermal analysis, x-ray diffraction, field emission scanning electron microscopy, dielectric temperature curves and impedance spectroscopy. From the differential thermal analysis, glass transition and crystallization behavior can be observed. From the x-ray diffraction study, two crystalline phases (Ba,Sr)TiO3 and Ba2TiSi2O8 were formed over the entire composition range of the glass-ceramics. In addition, the main crystal phase has undergone a transformation from (Ba,Sr)TiO3 to Ba2TiSi2O8 with the increase of n. A typical structure in which the crystal phase was surrounded by a glassy matrix has been observed in the scanning electron microscope images. As a result of temperature dependent dielectric property measurements, the dielectric constant increased obviously with the increase of n from 0.5 to 1. Further increasing n led to a reduction of the dielectric constant, which is in coincidence with the variation of the intensity of (Ba,Sr)TiO3 phase with n. According to the impedance spectroscopy analysis and the activation energy calculation, the relaxation peak in both Z″ and M″ data should be attributed to the crystal-glass interface, and the change of conduction mechanism with the increase of SiO2/B2O3 ratio may be attributed to the corresponding transition of the main crystal phase.

CuO, MnO2 and Fe2O3 doped biomass ash as silica source for glass production in Thailand

Directory of Open Access Journals (Sweden)

N. Srisittipokakun

Full Text Available In this research, glass productions from rice husk ash (RHA and the effect of BaO, CuO, MnO2 and Fe2O3 on physical and optical properties were investigated. All properties were compared with glass made from SiO2 using same preparations. The results show that a higher density and refractive index of BaO, CuO, MnO2 and Fe2O3 doped in RHA glasses were obtained, compared with SiO2 glasses. The optical spectra show no significant difference between both glasses. The color of CuO glasses show blue from the absorption band near 800 nm (2B1g → 2B2g due to Cu2+ ion in octahedral coordination with a strong tetragonal distortion. The color of MnO2 glasses shows brown from broad band absorption at around 500 nm. This absorption band is assigned to a single allowed 5Eg → 5T2g transition which arises from the Mn3+ ions (3d4 configuration in octahedral symmetry. The yellow color derives from F2O3 glass due to the homogeneous distribution of Fe3+ (460 nm and Fe2+ (1050 nm ions in the glass matrices. Glass production from RHA is possible and is a new option for recycling waste from biomass power plant systems and air pollution reduction. Keywords: Rice husk ash, Glass, Optical, Physical

Paramagnetic centers in ternary coordinated oxygen in beryllium aluminosilicate glasses

International Nuclear Information System (INIS)

Blaginina, L.A.; Zatsepin, A.F.; Dmitriev, I.A.

1988-01-01

Glasses of the composition 3BeO-Al 2 O 3 -6SiO 2 containing a homogenizing additive of MgF 2 were synthesized. The ESR spectra of x-ray and gamma irradiated specimens were determined. A complex ESR spectrum arose in the original glass. The ESR spectrum of the gamma-irradiated polycrystalline Be 2 SiO 4 glass was almost identical to the crystallized glass. It was shown that the presence of beryllium atoms in the composition of silicate glasses created the conditions for the formation of structural fragments with ternary coordinated oxygen

Formation of SiO2/polytetrafluoroethylene hybrid superhydrophobic coating

International Nuclear Information System (INIS)

Zheng Yansheng; He Yi; Qing Yongquan; Zhuo Zhihao; Mo Qian

2012-01-01

Highlights: ► The coating showed the water contact angle of 165° and the water sliding angle of 6°. ► The hierarchical structure with the low surface energy leads to surface superhydrophobicity. ► We demonstrated a simple yet efficient approach to preparing superhydrophobic surface. - Abstract: Superhydrophobic coating has been fabricated on the glass substrates with modified SiO 2 sol and polytetrafluoroethylene emulsion through a sol–gel process. SiO 2 sol was modified with γ-glycidoxypropyl trimethoxysilane. The coatings were characterized by water contact angle measurement, Scanning electron microscope, Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy and thermal synthetic analysis. The experimental results show that coatings exhibited superhydrophobic and heat-resistant property with a water average contact angle of 156° and sliding angle of 6°, coating has a rough surface with both micro- and nanoscale structures, γ-glycidoxypropyl trimethoxysilane enhanced the hydrophobicity of the coatings. Low surface energy of polymer and special structure of the coatings were responsible for the hydrophobic of the surfaces.

Glass-ceramics frits for high mechanical resistance glazes

International Nuclear Information System (INIS)

Gajek, M.; Lis, J.; Partyka, J.; Wojczyk, M.

2004-01-01

The obtaining and application of glass-ceramics frits for glazes were discussed by many authors. This glazes are characterized by raised mechanical parameters and chemical resistance. Factors, that determines crystallization process are initial composition, heat treatment and nucleation agents. The kind of crystalline phases, crystal habit and the content of residual glass phase play the decisive role in the strengthening of the glaze. In this paper are shown results of investigation over controlled crystallization in the ternary systems; Li 2 O-Al 2 O 3 -SiO 2 , CaO-Al 2 O 3 -SiO 2 , ZnO-Al 2 O 3 -SiO 2 , MgO-Al 2 O 3 -SiO 2 , with or without nucleation agents. (author)

The ceramic SiO2 and SiO2-TiO2 coatings on biomedical Ti6Al4VELI titanium alloy

International Nuclear Information System (INIS)

Surowska, B.; Walczak, M.; Bienias, J.

2004-01-01

The paper presents the study of intermediate SiO 2 and SiO 2 -TiO 2 sol-gel coatings and dental porcelain coatings on Ti6Al4VELI titanium alloy. Surface microstructures and wear behaviour by pin-on-disc method of the ceramic coatings were investigated. The analysis revealed: (1) a compact, homogeneous SiO 2 and SiO 2 -TiO 2 coating and (2) that intermediate coatings may provide a durable joint between metal and porcelain, and (3) that dental porcelain on SiO 2 and TiO 2 coatings shows high wear resistance. (author)

Optical transitions of Ho(3+) in oxyfluoride glasses and upconversion luminescence of Ho(3+)/Yb(3+)-codoped oxyfluoride glasses.

Science.gov (United States)

Feng, Li; Wu, Yinsu

2015-05-05

Optical properties of Ho(3+)-doped SiO2-BaF2-ZnF2 glasses have been investigated on the basis of the Judd-Ofelt theory. Judd-Ofelt intensity parameters, radiative transition probabilities, fluorescence branching ratios and radiative lifetimes have been calculated for different glass compositions. Upconversion emissions were observed in Ho(3+)/Yb(3+)-codoped SiO2-BaF2-ZnF2 glasses under 980nm excitation. The effects of composition, concentration of the doping ions, and excitation pump power on the upconversion emissions were also systematically studied. Copyright © 2015 Elsevier B.V. All rights reserved.

Glass dissolution at 20, 40, 70 and 90 C: Short-term effects of solution chemistry and long-term Na release

International Nuclear Information System (INIS)

Bakel, A.J.; Ebert, W.L.; Strachan, D.M.

1996-01-01

The corrosion behavior of a borosilicate glass containing 20 mass 5 Na 2 O was assessed using static dissolution tests. This glass (LD6-5412) is representative of high Na glasses that may be used to stabilize Hanford low-level radioactive waste. The normalized mass loss (NL) decreases as NL(Na) ∼ NL(B) > NL(Si) in 20 and 40 C for tests conducted at glass surface area to leachant volume (S/V) ratio of 10 m -1 , and decreases as NL(Na) > NL(B) ∼ NL(Si) in 90 C tests conducted at 10 m -1 and in all tests conducted at higher S/V. The difference in the corrosion behavior is probably caused by the influence of dissolved glass components in the leachates. The NL(Na) is greater than the NL(B) or NL(Si) in all the tests conducted. Results from long-term tests at 2,000 m -1 show that the preferential release of Na persists for longer than one year at all temperatures and indicate that Na is released from this glass by an ion exchange process

Faster dissolution of PuO2 in nitrous media by means of electrolytic oxidation

International Nuclear Information System (INIS)

Baumgaertner, F.; Kim, J.I.; Luckner, N.; Brueckl, N.; Lieberer, E.

1984-03-01

The contribution shows that the dissolution of PuO 2 in HNO 3 can be accelerated considerably by means of electrolytic oxidation. A glass apparatus has been developed which uses platinum electrodes providing for sufficient contact between electrodes and solids. Increase of temperature, acid concentration, and electrode current density, and a good contact between electrode and metal oxide will improve the dissolution kinetics. The reaction could be made even faster by addition of Ce 4+ . (orig.) [de

High-temperature mass spectrometric study of the vaporization processes and thermodynamic properties of melts in the PbO-B2O3-SiO2 system.

Science.gov (United States)

Stolyarova, V L; Lopatin, S I; Shilov, A L; Shugurov, S M

2013-07-15

The unique properties of the PbO-B2O3-SiO2 system, especially its extensive range of glass-forming compositions, make it valuable for various practical applications. The thermodynamic properties and vaporization of PbO-B2O3-SiO2 melts are not well established so far and the data obtained on these will be useful for optimization of technology and thermodynamic modeling of glasses. High-temperature Knudsen effusion mass spectrometry was used to study vaporization processes and to determine the partial pressures of components of the PbO-B2O3-SiO2 melts. Measurements were performed with a MS-1301 mass spectrometer. Vaporization was carried out using two quartz effusion cells containing the sample under study and pure PbO (reference substance). Ions were produced by electron ionization at an energy of 25 eV. To facilitate interpretation of the mass spectra, the appearance energies of ions were also measured. Pb, PbO and O2 were found to be the main vapor species over the samples studied at 1100 K. The PbO activities as a function of the composition of the system were derived from the measured PbO partial pressures. The B2O3 and SiO2 activities, the Gibbs energy of formation, the excess Gibbs energy of formation and mass losses in the samples studied were calculated. Partial pressures of the vapor species over PbO-B2O3-SiO2 melts were measured at 1100 K in the wide range of compositions using the Knudsen mass spectrometric method. The data enabled the PbO, B2O3, and SiO2 activities in these melts to be derived and provided evidence of their negative deviations from ideal behavior. Copyright © 2013 John Wiley & Sons, Ltd.

Structural Dependence of Physical Properties in Sodium Boroaluminosilicate Glasses

DEFF Research Database (Denmark)

Zheng, Qiuju; Potuzak, Marcel; Mauro, John C.

Boroaluminosilicate glasses have found applications in many fields. The extent and nature of the mixing of network formers like SiO2, B2O3, and Al2O3 play an important role in controlling the macroscopic properties. To understand the structure-property correlations in these glasses, we study...... a series of sodium boroaluminosilicate glasses with various [Al2O3]/[SiO2] ratios to access different regimes of sodium behavior. We determine dynamic properties, elastic moduli, and hardness of these glasses. The results reveal an existence of local minimum for density, fragility index, Young’s and shear...

Short and medium range order in two-component silica glasses by positron annihilation spectroscopy

International Nuclear Information System (INIS)

Inoue, K.; Kataoka, H.; Nagai, Y.; Hasegawa, M.; Kobayashi, Y.

2014-01-01

The dependence of chemical composition on the average sizes of subnanometer-scale intrinsic structural open spaces surrounded by glass random networks in two-component silica-based glasses was investigated systematically using positronium (Ps) confined in the open spaces. The average sizes of the open spaces for SiO 2 -B 2 O 3 and SiO 2 -GeO 2 glasses are only slightly dependent on the chemical compositions because the B 2 O 3 and GeO 2 are glass network formers that are incorporated into the glass network of the base SiO 2 . However, the open space sizes for all SiO 2 -R 2 O (R = Li, Na, K) glasses, where R 2 O is a glass network modifier that occupies the open spaces, decrease rapidly with an increase in the R 2 O concentration. Despite the large difference in the ionic radii of the alkali metal (R) atoms, the open space sizes decrease similarly for all the alkali metal atoms studied. This dependence of the chemical composition on the open space sizes in SiO 2 -R 2 O observed by Ps shows that the alkali metal atoms do not randomly occupy the structural open spaces, but filling of the open spaces by R 2 O proceeds selectively from the larger to the smaller open spaces as the R 2 O concentrations are increased.

Nuclear waste glass corrosion mechanisms

International Nuclear Information System (INIS)

Jantzen, C.M.

1987-04-01

Dissolution of nuclear waste glass occurs by corrosion mechanisms similar to those of other solids, e.g., metallurgical and mineralogic systems. Metallurgical phenomena such as active corrosion, passivation and immunity have been observed to be a function of the glass composition and the solution pH. Hydration thermodynamics was used to quantify the role of glass composition and its effect on the solution pH during dissolution. A wide compositional range of natural, lunar, medieval, and nuclear waste glasses, as well as some glass-ceramics were investigated. The factors observed to affect dissolution in deionized water are pertinent to the dissolution of glass in natural environments such as the groundwaters anticipated to interact with nuclear waste glass in a geologic repository. The effects of imposed pH and oxidation potential (Eh) conditions existing in natural environments on glass dissolution is described in the context of Pourbaix diagrams, pH potential diagrams, for glass

Glass Dissolution Parameters: Update for Entsorgungsnachweis

International Nuclear Information System (INIS)

Curti, E.

2003-11-01

This document provides updated long-term corrosion rates for borosilicate glasses used in Switzerland as a matrix for high-level radioactive waste. The new rates are based on long-term leaching experiments conducted at PSI and are corroborated by recent investigations. The asymptotic rates have been determined through weighted linear regressions of the normalised mass losses, directly calculated from B and Li concentrations in the leaching solutions. Special attention was given to the determination of the analytical uncertainty of the mass losses. The sensitivity of the corrosion rates to analytical uncertainties and to other criteria (e.g. the choice of data points for the regressions) was also studied. A major finding was that the uncertainty of the corrosion rate mainly depends on the uncertainty of the specific glass surface area. The reference rates proposed for safety assessment calculations are 1.5 mg m -2 d -1 for BNFL glasses and 0.2 mg m -2 d -1 for Cogema glasses. The relevance of the proposed corrosion rates for repository conditions is shown based on the analysis of processes and parameters currently known to affect the long-term kinetics of silicate glasses. Specifically, recent studies indicate that potentially detrimental effects, notably the removal of silica from solution through adsorption on clay minerals, are transitory and will not affect the long-term corrosion rate of the Swiss reference glasses. Iron corrosion products are also known to bind silica, but present data are not sufficient to quantify their influence on the long-term rate. (author)