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Sample records for r7t7-type nuclear glass

  1. Simulated alteration tests on non-radioactive SON 68 nuclear glass in the presence of corrosion products and environmental materials

    NASA Astrophysics Data System (ADS)

    Jollivet, Patrick; Minet, Yves; Nicolas, Michèle; Vernaz, Étienne

    2000-10-01

    Alteration tests with non-radioactive French SON 68 (R7T7-type) nuclear glass in the presence of simulated metal canister corrosion products (CP) or environmental materials (EM) were simulated using the LIXIVER2 computer code. The code incorporates hypotheses concerning glass alteration in aqueous media based on the first-order kinetic law for total silicon with variable silicon retention in the gel and silicon diffusion in the gel interstitial water, coupled with silicon adsorption and diffusion in the materials in contact with the glass. The canister CP are considered as a localized medium with a mass adsorption capacity Rad, while the EM are considered as a porous medium with a diffusion coefficient Dp and a distribution coefficient Kd. L IXIVER2 simulates these media in one-dimensional Cartesian geometry. The Kd values determined by simulating alteration tests logically increase with the aggressiveness of the materials with respect to the glass.

  2. Turning nuclear waste into glass

    SciTech Connect

    Pegg, Ian L.

    2015-02-15

    Vitrification has emerged as the treatment option of choice for the most dangerous radioactive waste. But dealing with the nuclear waste legacy of the Cold War will require state-of-the-art facilities and advanced glass formulations.

  3. Alteration kinetics of the glass-ceramic zirconolite and role of the alteration film Comparison with the SON68 glass

    NASA Astrophysics Data System (ADS)

    Martin, C.; Ribet, I.; Frugier, P.; Gin, S.

    2007-06-01

    The glass-ceramic zirconolite is being considered for specific conditioning of plutonium or the minor actinides. The actinides are distributed throughout the zirconolite crystals and the residual glass phase. Since zirconolite alteration is extremely limited, actinide release from the glass-ceramic material is mainly attributable to alteration of the residual glass. Specimens corresponding to the residual glass phase alone were therefore altered under different conditions to compare their kinetics with the one of the SON68 glass (inactive R7T7 type glass). Glass-ceramic zirconolite presents a more important rate decrease occuring more rapidly and that induces a quantity of glass altered at least 10 times as small as for SON68 glass. This slowdown of the alteration rate is attributed to the formation of an alteration film that has been the subject of a specific study. We have in particular identified a dense phase enriched in titanium and neodymium that probably influences deeply the kinetics.

  4. Natural analogues of nuclear waste glass corrosion.

    SciTech Connect

    Abrajano, T.A. Jr.; Ebert, W.L.; Luo, J.S.

    1999-01-06

    This report reviews and summarizes studies performed to characterize the products and processes involved in the corrosion of natural glasses. Studies are also reviewed and evaluated on how well the corrosion of natural glasses in natural environments serves as an analogue for the corrosion of high-level radioactive waste glasses in an engineered geologic disposal system. A wide range of natural and experimental corrosion studies has been performed on three major groups of natural glasses: tektite, obsidian, and basalt. Studies of the corrosion of natural glass attempt to characterize both the nature of alteration products and the reaction kinetics. Information available on natural glass was then compared to corresponding information on the corrosion of nuclear waste glasses, specifically to resolve two key questions: (1) whether one or more natural glasses behave similarly to nuclear waste glasses in laboratory tests, and (2) how these similarities can be used to support projections of the long-term corrosion of nuclear waste glasses. The corrosion behavior of basaltic glasses was most similar to that of nuclear waste glasses, but the corrosion of tektite and obsidian glasses involves certain processes that also occur during the corrosion of nuclear waste glasses. The reactions and processes that control basalt glass dissolution are similar to those that are important in nuclear waste glass dissolution. The key reaction of the overall corrosion mechanism is network hydrolysis, which eventually breaks down the glass network structure that remains after the initial ion-exchange and diffusion processes. This review also highlights some unresolved issues related to the application of an analogue approach to predicting long-term behavior of nuclear waste glass corrosion, such as discrepancies between experimental and field-based estimates of kinetic parameters for basaltic glasses.

  5. Production of Synthetic Nuclear Melt Glass.

    PubMed

    Molgaard, Joshua J; Auxier, John D; Giminaro, Andrew V; Oldham, Colton J; Gill, Jonathan; Hall, Howard L

    2016-01-01

    Realistic surrogate nuclear debris is needed within the nuclear forensics community to test and validate post-detonation analysis techniques. Here we outline a novel process for producing bulk surface debris using a high temperature furnace. The material developed in this study is physically and chemically similar to trinitite (the melt glass produced by the first nuclear test). This synthetic nuclear melt glass is assumed to be similar to the vitrified material produced near the epicenter (ground zero) of any surface nuclear detonation in a desert environment. The process outlined here can be applied to produce other types of nuclear melt glass including that likely to be formed in an urban environment. This can be accomplished by simply modifying the precursor matrix to which this production process is applied. The melt glass produced in this study has been analyzed and compared to trinitite, revealing a comparable crystalline morphology, physical structure, void fraction, and chemical composition. PMID:26779720

  6. Systems approach to nuclear waste glass development

    SciTech Connect

    Jantzen, C M

    1986-01-01

    Development of a host solid for the immobilization of nuclear waste has focused on various vitreous wasteforms. The systems approach requires that parameters affecting product performance and processing be considered simultaneously. Application of the systems approach indicates that borosilicate glasses are, overall, the most suitable glasses for the immobilization of nuclear waste. Phosphate glasses are highly durable; but the glass melts are highly corrosive and the glasses have poor thermal stability and low solubility for many waste components. High-silica glasses have good chemical durability, thermal stability, and mechanical stability, but the associated high melting temperatures increase volatilization of hazardous species in the waste. Borosilicate glasses are chemically durable and are stable both thermally and mechanically. The borosilicate melts are generally less corrosive than commercial glasses, and the melt temperature miimizes excessive volatility of hazardous species. Optimization of borosilicate waste glass formulations has led to their acceptance as the reference nuclear wasteform in the United States, United Kingdom, Belgium, Germany, France, Sweden, Switzerland, and Japan.

  7. THERMOCHEMICAL MODELING OF NUCLEAR WASTE GLASS

    EPA Science Inventory

    The development of assessed and consistent phase equilibria and thermodynamic data for major glass constituents used to incorporate high-level nuclear waste is discussed in this paper. The initial research has included the binary Na{sub 2}O-SiO{sub 2}, Na{sub 2}O-Al{sub 2}O{sub ...

  8. Glass produced by underground nuclear explosions. [Rainier

    SciTech Connect

    Schwartz, L.; Piwinskii, A.; Ryerson, F.; Tewes, H.; Beiriger, W.

    1983-01-01

    Detonation of an underground nuclear explosive produces a strong shock wave which propagates spherically outward, vaporizing the explosive and nearby rock and melting, the surrounding rock. The vaporized material expands adiabatically, forming a cavity. As the energy is dissipated during the cavity formation process, the explosive and rock debris condense and mix with the melted rock. The melt flows to the bottom of the cavity where it is quenched by fractured rock fragments falling from above as the cavity collapses. Measurements indicate that about 740 tonnes of rock and/or soil are melted for every kiloton (10/sup 12/ calories) of explosive energy, or about 25% of the explosive energy goes to melting rock. The resulting glass composition reflects the composition of the unaltered rock with explosive debris. The appearance ranges from white pumice to dense, dark lava. The bulk composition and color vary with the amount of explosive iron incorporated into the glass. The refractory explosion products are mixed with the solidified melt, although the degree of mixing is variable. Electron microprobe studies of glasses produced by Rainier in welded tuff have produced the following results: glasses are dehydrated relative to the host media, glasses are extremely heterogeneous on a 20 ..mu..m scale, a ubiquitous feature is the presence of dark marble-cake regions in the glass, which were locally enriched in iron and may be related to the debris, optically amorphous regions provide evidence of shock melting, only limited major element redistribution and homogenization occur within the cavity.

  9. Factors influencing chemical durability of nuclear waste glasses

    SciTech Connect

    Feng, Xiangdong; Bates, J.K.

    1993-03-01

    A short summary is given of our studies on the major factors that affect the chemical durability of nuclear waste glasses. These factors include glass composition, solution composition, SA/V (ratio of glass surface area to the volume of solution), radiation, and colloidal formation. These investigations have enabled us to gain a better understanding of the chemical durability of nuclear waste glasses and to accumulate.a data base for modeling the long-term durability of waste glass, which will be used in the risk assessment of nuclear waste disposal. This knowledge gained also enhances our ability to formulate optimal waste glass compositions.

  10. Factors influencing chemical durability of nuclear waste glasses

    SciTech Connect

    Feng, Xiangdong; Bates, J.K.

    1993-01-01

    A short summary is given of our studies on the major factors that affect the chemical durability of nuclear waste glasses. These factors include glass composition, solution composition, SA/V (ratio of glass surface area to the volume of solution), radiation, and colloidal formation. These investigations have enabled us to gain a better understanding of the chemical durability of nuclear waste glasses and to accumulate.a data base for modeling the long-term durability of waste glass, which will be used in the risk assessment of nuclear waste disposal. This knowledge gained also enhances our ability to formulate optimal waste glass compositions.

  11. Thermodynamic model of natural, medieval and nuclear waste glass durability

    SciTech Connect

    Jantzen, C.M.; Plodinec, M.J.

    1983-01-01

    A thermodynamic model of glass durability based on hydration of structural units has been applied to natural glass, medieval window glasses, and glasses containing nuclear waste. The relative durability predicted from the calculated thermodynamics correlates directly with the experimentally observed release of structural silicon in the leaching solution in short-term laboratory tests. By choosing natural glasses and ancient glasses whose long-term performance is known, and which bracket the durability of waste glasses, the long-term stability of nuclear waste glasses can be interpolated among these materials. The current Savannah River defense waste glass formulation is as durable as natural basalt from the Hanford Reservation (10/sup 6/ years old). The thermodynamic hydration energy is shown to be related to the bond energetics of the glass. 69 references, 2 figures, 1 table.

  12. Compositional threshold for Nuclear Waste Glass Durability

    SciTech Connect

    Kruger, Albert A.; Farooqi, Rahmatullah; Hrma, Pavel R.

    2013-04-24

    Within the composition space of glasses, a distinct threshold appears to exist that separates "good" glasses, i.e., those which are sufficiently durable, from "bad" glasses of a low durability. The objective of our research is to clarify the origin of this threshold by exploring the relationship between glass composition, glass structure and chemical durability around the threshold region.

  13. Spectroscopic investigation of U, Np and Th in nuclear glasses

    NASA Astrophysics Data System (ADS)

    Calas, G.; Galoisy, L. V.; Petit-Maire, D.

    2011-12-01

    Vitrification of high-level radioactive waste in borosilicate glasses is currently used on an industrial scale in several countries. The fundamental properties of the waste forms are their chemical and mechanical durability against the forcing conditions represented by chemical alteration or internal/external irradiation. The waste immobilized in glass is composed of over 30 different nuclear fission and activation products, as well as minor actinides. The oxidation state and local atomic coordination of long-lived radionuclides are important parameters to understand the long-term evolution of the glass. We present an overview of the local structure around actinides in glasses similar to the French nuclear glass. X-Ray absorption spectroscopy has been used to probe the local environment around uranium, neptunium and thorium in these glasses. It is combined with with UV-visible spectroscopy, used to get selective information on the surrounding of U(IV), U(V) and U(VI) in glasses. Our spectroscopic data show that U, Np and Th occur in nuclear glasses in a peculiar surrounding showing significant differences with the crystal chemistry of these elements in crystalline compounds. Element speciation may be used as a pertinent parameter to follow the long-term stability of nuclear glasses, either under irradiation or during the alteration of the glass.

  14. Chemical durability of simulated nuclear glasses containing water

    SciTech Connect

    Li, H.; Tomozawa, M.

    1995-04-01

    The chemical durability of simulated nuclear waste glasses having different water contents was studied. Results from the product consistency test (PCT) showed that glass dissolution increased with water content in the glass. This trend was not observed during MCC-1 testing. This difference was attributed to the differences in reactions between glass and water. In the PCT, the glass network dissolution controlled the elemental releases, and water in the glass accelerated the reaction rate. On the other hand, alkali ion exchange with hydronium played an important role in the MCC-1. For the latter, the amount of water introduced into a leached layer from ion-exchange was found to be much greater than that of initially incorporated water in the glass. Hence, the initial water content has no effect on glass dissolution as measured by the MCC-1 test.

  15. Control of Nepheline Crystallization in Nuclear Waste Glass

    SciTech Connect

    Fox, Kevin

    2008-07-01

    Glass frits with a high B{sub 2}O{sub 3} concentration have been designed which, when combined with high-alumina concentration nuclear waste streams, will form glasses with durabilities that are acceptable for repository disposal and predictable using a free energy of hydration model. Two glasses with nepheline discriminator values closest to 0.62 showed significant differences in normalized boron release between the quenched and heat treated versions of each glass. X-ray diffraction confirmed that nepheline crystallized in the glass with the lowest nepheline discriminator value, and nepheline may also exist in the second glass as small nanocrystals. The high-B{sub 2}O{sub 3} frit was successful in producing simulated waste glasses with no detectable nepheline crystallization at waste loadings of up to 45 wt%. The melt rate of this frit was also considerably better than other frits with increased concentrations of Na{sub 2}O.

  16. Iron Phosphate Glasses: An Alternative for Vitrifying Certain Nuclear Wastes

    SciTech Connect

    Delbert E. Day; Chandra S. Ray; Cheol-Woon Kim

    2004-12-28

    Vitrification of nuclear waste in a glass is currently the preferred process for waste disposal. DOE currently approves only borosilicate (BS) type glasses for such purposes. However, many nuclear wastes, presently awaiting disposal, have complex and diverse chemical compositions, and often contain components that are poorly soluble or chemically incompatible in BS glasses. Such problematic wastes can be pre-processed and/or diluted to compensate for their incompatibility with a BS glass matrix, but both of these solutions increases the wasteform volume and the overall cost for vitrification. Direct vitrification using alternative glasses that utilize the major components already present in the waste is preferable, since it avoids pre-treating or diluting the waste, and, thus, minimizes the wasteform volume and overall cost.

  17. Nuclear Waste Glasses: Continuous Melting and Bulk Vitrification

    SciTech Connect

    Hrma, Pavel R.; Kruger, Albert A.

    2008-02-25

    This contribution addresses various aspects of nuclear waste vitrification. Nuclear wastes have a variety of components and composition ranges. For each waste composition, the glass must be formulated to possess acceptable processing and product behavior defined in terms of physical and chemical properties that guarantee that the glass can be easily made and resist environmental degradation. Glass formulation is facilitated by developing property-composition models, and the strategy of model development and application is reviewed. However, the large variability of waste compositions presents numerous additional challenges: insoluble solids and molten salts may segregate; foam may hinder heat transfer and slow down the process; molten salts may accumulate in container refractory walls; on cooling, the glass may precipitate crystalline phases. These problems need targeted exploratory research. Examples of specific problems and their possible solutions are discussed.

  18. NUCLEAR WASTE GLASSES CONTINUOUS MELTING AND BULK VITRIFICAITON

    SciTech Connect

    KRUGER AA; HRMA PR

    2008-03-24

    This contribution addresses various aspects of nuclear waste vitrification. Nuclear wastes have a variety of components and composition ranges. For each waste composition, the glass must be formulated to possess acceptable processing and product behavior defined in terms of physical and chemical properties that guarantee the glass can be easily made and resist environmental degradation. Glass formulation is facilitated by developing property-composition models, and the strategy of model development and application is reviewed. However, the large variability of waste compositions presents numerous additional challenges: insoluble solids and molten salts may segregate; foam may hinder heat transfer and slow down the process; molten salts may accumulate in container refractory walls; the glass on cooling may precipitate crystalline phases. These problems need targeted exploratory research. Examples of specific problems and their possible solutions are discussed.

  19. Nuclear waste glass product consistency test (PCT), Version 5. 0

    SciTech Connect

    Jantzen, C.M.; Bibler, N.E.; Beam, D.C.; Ramsey, W.G.; Waters, B.J.

    1992-06-01

    Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass. The glass will be produced in the Defense Waste Processing Facility (DWPF), poured into stainless steel canisters, and eventually disposed of in a geologic repository. In order to comply with the Waste Acceptance Preliminary Specifications (WAPS), the durability of the glass needs to be measured during production to assure its long term stability and radionuclide release properties. A durability test, designated the Produce Consistency Test (PCT), was developed for DWPF glass in order to meet the WAPS requirements. The response of the PCT procedure was based on extensive testing with glasses of widely different compositions. The PCT was determined to be very reproducible, to yield reliable results rapidly, and to be easily performed in shielded cell facilities with radioactive samples. Version 5.0 of the PCT procedure is attached.

  20. Nuclear waste glass Product Consistency Test (PCT), Version 3. 0

    SciTech Connect

    Jantzen, C.M.; Bibler, N.E.

    1990-11-01

    Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass. The glass will be produced in the Defense Waste Processing Facility (DWPF), poured into stainless steel canisters, and eventually disposed of in a geologic repository. In order to comply with the Waste Acceptance Preliminary Specifications (WAPS), the durability of the glass needs to be measured during production to assure its long term stability and radionuclide release properties. A durability test, designated the Product Consistency Test (PCT), was developed for DWPF glass in order to meet the WAPS requirements. The response of the PCT procedure was based on extensive testing with glasses of widely different compositions. The PCT was determined to be very reproducible, to yield reliable results rapidly, and to be easily performed in shielded cell facilities with radioactive samples.

  1. Natural glass analogues to alteration of nuclear waste glass: A review and recommendations for further study

    SciTech Connect

    McKenzie, W.F.

    1990-01-01

    The purpose of this report is to review previous work on the weathering of natural glasses; and to make recommendations for further work with respect to studying the alteration of natural glasses as it relates quantifying rates of dissolution. the first task was greatly simplified by the published papers of Jercinovic and Ewing (1987) and Byers, Jercinovic, and Ewing (1987). The second task is obviously the more difficult of the two and the author makes no claim of completeness in this regard. Glasses weather in the natural environment by reacting with aqueous solutions producing a rind of secondary solid phases. It had been proposed by some workers that the thickness of this rind is a function of the age of the glass and thus could be used to estimate glass dissolution rates. However, Jercinovic and Ewing (1987) point out that in general the rind thickness does not correlate with the age of the glass owing to the differences in time of contact with the solution compared to the actual age of the sample. It should be noted that the rate of glass dissolution is also a function of the composition of both the glass and the solution, and the temperature. Quantification of the effects of these parameters (as well as time of contact with the aqueous phase and flow rates) would thus permit a prediction of the consequences of glass-fluid interactions under varying environmental conditions. Defense high- level nuclear waste (DHLW), consisting primarily of liquid and sludge, will be encapsulated by and dispersed in a borosilicate glass before permanent storage in a HLW repository. This glass containing the DHLW serves to dilute the radionuclides and to retard their dispersion into the environment. 318 refs.

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

    SciTech Connect

    Hagen, D.A.; Altstetter, C.J.; Brown, S.D.

    1988-05-01

    High level nuclear waste is commonly incorporated into glass for disposal. Therefore the long term aqueous durability of the waste glass is important. The leaching behavior of three simulated nuclear waste glasses (AH10, AH165, and Frit 165) and a natural glass (tektite) were examined using nuclear reaction analysis, leachate solution analysis, and microscopy. The three simulated waste glasses developed hydrated layers which increased in thickness by t/sup /1/2//. The hydrated layer in Frit 165 reached a constant thickness of about one micron. Alkali were preferentially removed from the Frit 165 and AH10. The tektite corroded by slow uniform dissolution. 94 refs., 68 figs., 13 tabs.

  3. Spectroscopic investigations on glasses, glass-ceramics and ceramics developed for nuclear waste immobilization

    NASA Astrophysics Data System (ADS)

    Caurant, D.

    2014-05-01

    Highly radioactive nuclear waste must be immobilized in very durable matrices such as glasses, glass-ceramics and ceramics in order to avoid their dispersion in the biosphere during their radioactivity decay. In this paper, we present various examples of spectroscopic investigations (optical absorption, Raman, NMR, EPR) performed to study the local structure of different kinds of such matrices used or envisaged to immobilize different kinds of radioactive wastes. A particular attention has been paid on the incorporation and the structural role of rare earths—both as fission products and actinide surrogates—in silicate glasses and glass-ceramics. An example of structural study by EPR of a ceramic (hollandite) irradiated by electrons (to simulate the effect of the β-irradiation of radioactive cesium) is also presented.

  4. Expeditious dissolution dynamic nuclear polarization without glassing agents.

    PubMed

    Lama, Bimala; Collins, James H P; Downes, Daniel; Smith, Adam N; Long, Joanna R

    2016-03-01

    The hyperpolarization of metabolic substrates at low temperature using dynamic nuclear polarization (DNP), followed by rapid dissolution and injection into an MRSI or NMR system, allows in vitro or in vivo observation and tracking of biochemical reactions and metabolites in real time. This article describes an elegant approach to sample preparation which is broadly applicable for the rapid polarization of aqueous small-molecule substrate solutions and obviates the need for glassing agents. We demonstrate its utility for solutions of sodium acetate, pyruvate and butyrate. The polarization behavior of substrates prepared using rapid freezing without glassing agents enabled a 1.5-3-fold time savings in polarization buildup, whilst removing the need for toxic glassing agents used as standard for dissolution DNP. The achievable polarization with fully aqueous substrate solutions was equal to that observed using standard approaches and glassing agents. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26915792

  5. Redox reaction and foaming in nuclear waste glass melting

    SciTech Connect

    Ryan, J.L.

    1995-08-01

    This document was prepared by Pacific Northwest Laboratory (PNL) and is an attempt to analyze and estimate the effects of feed composition variables and reducing agent variables on the expected chemistry of reactions occurring in the cold cap and in the glass melt in the nuclear waste glass Slurry-fed, joule-heated melters as they might affect foaming during the glass-making process. Numerous redox reactions of waste glass components and potential feed additives, and the effects of other feed variables on these reactions are reviewed with regard to their potential effect on glass foaming. A major emphasis of this report is to examine the potential positive or negative aspects of adjusting feed with formic acid as opposed to other feed modification techniques including but not limited to use of other reducing agents. Feed modification techniques other than the use of reductants that should influence foaming behavior include control of glass melter feed pH through use of nitric acid. They also include partial replacement of sodium salts by lithium salts. This latter action (b) apparently lowers glass viscosity and raises surface tension. This replacement should decrease foaming by decreasing foam stability.

  6. Radiation and Thermal Ageing of Nuclear Waste Glass

    SciTech Connect

    Weber, William J

    2014-01-01

    The radioactive decay of fission products and actinides incorporated into nuclear waste glass leads to self-heating and self-radiation effects that may affect the stability, structure and performance of the glass in a closed system. Short-lived fission products cause significant self-heating for the first 600 years. Alpha decay of the actinides leads to self-radiation damage that can be significant after a few hundred years, and over the long time periods of geologic disposal, the accumulation of helium and radiation damage from alpha decay may lead to swelling, microstructural evolution and changes in mechanical properties. Four decades of research on the behavior of nuclear waste glass are reviewed.

  7. Observations of Nuclear Explosive Melt Glass Textures and Surface Areas

    SciTech Connect

    Kersting, A B; Smith, D K

    2006-01-17

    This memo report summarizes our current knowledge of the appearance of melt glass formed and subsequently deposited in the subsurface after an underground nuclear test. We have collected archived pictures and melt glass samples from a variety of underground nuclear tests that were conducted at the Nevada Test Site (NTS) during the U.S. nuclear testing program. The purpose of our work is to better determine the actual variation in texture and surface area of the melt glass material. This study is motivated by our need to better determine the rate at which the radionuclides incorporated in the melt glass are released into the subsurface under saturated and partially saturated conditions. The rate at which radionuclides are released from the glass is controlled by the dissolution rate of the glass. Glass dissolution, in turn, is a strong function of surface area, glass composition, water temperature and water chemistry (Bourcier, 1994). This work feeds into an ongoing experimental effort to measure the change in surface area of analog glasses as a function of dissolution rate. The conclusions drawn from this study help bound the variation in the textures of analog glass samples needed for the experimental studies. The experimental work is a collaboration between Desert Research Institute (DRI) and Earth and Environmental Sciences-Lawrence Livermore National Laboratory (EES-LLNL). On March 4, 1999 we hosted a meeting at LLNL to present and discuss our findings. The names of the attendees appear at the end of this memo. This memo report further serves to outline and summarize the conclusions drawn from our meeting. The United States detonated over 800 underground nuclear tests at the NTS between 1951 and 1992. In an effort to evaluate the performance of the nuclear tests, drill-back operations were carried out to retrieve samples of rock in the vicinity of the nuclear test. Drill-back samples were sent to Los Alamos National Laboratory (LANL) and Lawrence Livermore

  8. IRON PHOSPHATE GLASSES: AN ALTERNATIVE FOR VITRIFYING CERTAIN NUCLEAR WASTES

    SciTech Connect

    Day, Delbert E.; Kim, Cheol-Woon

    2004-06-28

    The unusual properties and beneficial characteristics of iron phosphate glasses, as viewed from the standpoint of alternative glasses for vitrifying nuclear and hazardous wastes (which contain components that make them poorly suited for vitrification in borosilicate glass), have been investigated by the University of Missouri-Rolla with support from the Environmental Management Science Program (EMSP), DOE [DEFG07- 96ER45618]. During the past year, the corrosion resistance of Inconel 690 and 693 coupons submerged in an iron phosphate melt at 1050 C for up to 155 days has been investigated to determine whether iron phosphate glasses could be melted in a Joule Heated Melter (JHM) equipped with such electrodes in the same manner as now being used to melt borosilicate glass. Substituting iron phosphate glasses for borosilicate glasses could significantly reduce the time and cost for clean up due to the higher waste loading possible in iron phosphate glass. The iron phosphate melt, which contained 30 wt% of the Hanford Low Activity Waste (LAW), did not corrode the Inconel 690 to any greater extent than what has been reported for Inconel 690 electrodes in the borosilicate melt in the JHM at the Defense Waste Processing Facility. Furthermore, Inconel 693 appeared to be an even better candidate for use in iron phosphate melts since its corrosion rate (0.7 {micro}m/day) was only about one half that (1.3 {micro}m/day) of Inconel 690. In the past year, the results of the research on iron phosphate glasses have been described in nine technical papers and one report and have been presented at four international and national meetings.

  9. Helium solubility in SON68 nuclear waste glass

    SciTech Connect

    Fares, Toby; Peuget, Sylvain; Bouty, Olivier; Broudic, Veronique; Maugeri, Emilio; Bes, Rene; Jegou, Christophe; Chamssedine, Fadel; Sauvage, Thierry; Deschanels, Xavier

    2012-12-15

    Helium behavior in a sodium borosilicate glass (SON68) dedicated to the immobilization of high-level nuclear waste is examined. Two experimental approaches on nonradioactive glass specimens are implemented: pressurized helium infusion experiments and {sup 3}He ion implantation experiments. The temperature variation of helium solubility in SON68 glass was determined and analyzed with the harmonic oscillator model to determine values of the energy of interaction E(0) at the host sites (about -4000 J/mol), the vibration frequency (about 1.7 x 10{sup 11} s{sup -1}), and the density of solubility sites (2.2 x 10{sup 21} sites cm{sup -3}). The implantation experiments show that a non diffusive transport phenomenon (i.e., athermal diffusion) is involved in the material when the helium concentration exceeds 2.3 x 10{sup 21} He cm{sup -3}, and thus probably as soon as it exceeds the density of solubility sites accessible to helium in the glass. We propose that this transport mechanism could be associated with the relaxation of the stress gradient induced by the implanted helium profile, which is favored by the glass damage. Microstructural characterization by TEM and ESEM of glass specimens implanted with high helium concentrations showed a homogeneous microstructure free of bubbles, pores, or cracking at a scale of 10 nm. (authors)

  10. Resumption of nuclear glass alteration: State of the art

    NASA Astrophysics Data System (ADS)

    Fournier, Maxime; Gin, Stéphane; Frugier, Pierre

    2014-05-01

    Studies of nuclear glass alteration kinetics have shown that after the beginning of a rate drop due to the approach of silica saturation of the solution and the formation of a passivating layer, a resumption of alteration is possible. This phenomenon corresponding to an acceleration of the glass dissolution rate is systematically associated with the precipitation of zeolites and, to a lesser extent, calcium silicate hydrates. Secondary phases which precipitate from the major glass network-forming elements (Si, Al) strongly impact the dissolution kinetics. The literature data are generally consistent and the results are reproducible, showing that the resumption of alteration is observed at high pH, temperature, and S/V ratio during laboratory experiments. The studies also show that the resumption of alteration is strongly dependent on the composition of the glass and the leaching solutions. The wide range of glass compositions studied (about 60 glasses in the articles reviewed) and the variable test conditions (temperature, pH, and solution composition) make it extremely difficult to compare and compile the data, or to decorrelate the effects of the composition on the time before the resumption of alteration and on its magnitude. The observations to date have led to a proposed macroscopic mechanism based on the loss of the passivating properties of the alteration layer after consumption of a fraction of the network-forming elements by precipitation of zeolites. No multiscale mechanistic approach exists, however, to account for the nucleation and growth of zeolites at the expense of the glass. For example, the effect of aluminum in the gel or in solution on the glass alteration kinetics is not sufficiently understood today. Although thermodynamic models have been proposed to delimit the ranges of glass compositions subject to a resumption of alteration, their development is hampered by inadequate knowledge of the newly formed phases and their nucleation

  11. MILLIMETER-WAVE MONITORING OF NUCLEAR WASTE GLASS MELTS - AN OVERVIEW

    EPA Science Inventory

    Molten glass characteristics of temperature, resistivity, and viscosity can be monitored reliably in the high temperature and chemically corrosive environment of nuclear waste glass melters using millimeter-wave sensor technology. Millimeter-waves are ideally suited for such meas...

  12. Lead iron phosphate glass as a containment medium for disposal of high-level nuclear waste

    DOEpatents

    Boatner, Lynn A.; Sales, Brian C.

    1989-01-01

    Lead-iron phosphate glasses containing a high level of Fe.sub.2 O.sub.3 for use as a storage medium for high-level radioactive nuclear waste. By combining lead-iron phosphate glass with various types of simulated high-level nuclear waste, a highly corrosion resistant, homogeneous, easily processed glass can be formed. For corroding solutions at 90.degree. C., with solution pH values in the range between 5 and 9, the corrosion rate of the lead-iron phosphate nuclear waste glass is at least 10.sup.2 to 10.sup.3 times lower than the corrosion rate of a comparable borosilicate nuclear waste glass. The presence of Fe.sub.2 O.sub.3 in forming the lead-iron phosphate glass is critical. Lead-iron phosphate nuclear waste glass can be prepared at temperatures as low as 800.degree. C., since they exhibit very low melt viscosities in the 800.degree. to 1050.degree. C. temperature range. These waste-loaded glasses do not readily devitrify at temperatures as high as 550.degree. C. and are not adversely affected by large doses of gamma radiation in H.sub.2 O at 135.degree. C. The lead-iron phosphate waste glasses can be prepared with minimal modification of the technology developed for processing borosilicate glass nuclear wasteforms.

  13. Development of glass vitrification at SRL as a waste treatment technique for nuclear weapon components

    SciTech Connect

    Coleman, J.T.; Bickford, D.F.

    1991-12-31

    This report discusses the development of vitrification for the waste treatment of nuclear weapons components at the Savannah River Site. Preliminary testing of surrogate nuclear weapon electronic waste shows that glass vitrification is a viable, robust treatment method.

  14. Development of glass vitrification at SRL as a waste treatment technique for nuclear weapon components

    SciTech Connect

    Coleman, J.T.; Bickford, D.F.

    1991-01-01

    This report discusses the development of vitrification for the waste treatment of nuclear weapons components at the Savannah River Site. Preliminary testing of surrogate nuclear weapon electronic waste shows that glass vitrification is a viable, robust treatment method.

  15. Final technical report: Effects of water on properties of the simulated nuclear waste glasses

    SciTech Connect

    Li, H.; Tomozawa, M.

    1996-02-01

    For isolation of nuclear wastes through the vitrification process, waste slurry is mixed with borosilicate based glass and remelted at high temperature. During these processes, water can enter into the final waste glass. It is known that water in silica and silicate glasses changes various glass properties, such as chemical durability, viscosity and electrical conductivity. These properties are very important for processing and assuring the quality and safety controls of the waste glasses. The objective of this project was to investigate the effect of water in the simulated nuclear waste glasses on various glass properties, including chemical durability, glass transition temperature, liquidus temperature, viscosity and electrical conductivity. This report summarizes the results of this investigation conducted at Rensselaer during the past one year.

  16. Aged Nuclear Explosive Melt Glass: Radiography and Scanning Electron Microscope Analyses Documenting Both Radionuclide Distribution and Glass Alteration

    SciTech Connect

    Eaton, G.F.; Smith, D.K.

    2000-03-28

    Assessment of the long-term performance of nuclear melt glass under saturated conditions provides insight into factors controlling radionuclide release into groundwater. Melt glass samples were collected from an underground nuclear detonation cavity at the Nevada Test Site that was in contact with groundwater for more than 10 years. The samples were made into thin sections and the distribution of alpha activity mapped using CR-39 plastic detectors. The melt glass is visually heterogeneous and the results of the alpha track radiography indicate that the highest alpha activity is associated with areas of dark colored glass. Analyses of the thin sections by alpha spectrometry show the prominent actinide species to be {sup 238}Pu, {sup 239}Pu and {sup 241}Am. Scanning electron microprobe analysis of the bulk glass shows conspicuous alteration layers lining internal vesicle surfaces in the glass. X-ray diffraction patterns for the alteration phases are consistent with clay mineral compositions. Glass dissolution models indicate these layers are too thick to have formed at ambient temperatures over the 10 year period in which they remained in a saturated environment. This implies the alteration layers likely formed at temperatures higher than ambient during cooling of the cavity following the underground detonation. Mobilization of this clay alteration layer as colloidal particles in groundwater represents a potential source of actinide release into the environment.

  17. Leaching behavior of glass ceramic nuclear waste forms

    NASA Astrophysics Data System (ADS)

    Lokken, R. O.

    1981-11-01

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

  18. Glass former composition and method for immobilizing nuclear waste using the same

    DOEpatents

    Cadoff, Laurence H.; Smith-Magowan, David B.

    1988-01-01

    An alkoxide glass former composition has silica-containing constituents present as solid particulates of a particle size of 0.1 to 0.7 micrometers in diameter in a liquid carrier phase substantially free of dissolved silica. The glass former slurry is resistant to coagulation and may contain other glass former metal constituents. The immobilization of nuclear waste employs the described glass former by heating the same to reduce the volume, mixing the same with the waste, and melting the resultant mixture to encapsulate the waste in the resultant glass.

  19. Nano-Continuum Modeling of a Nuclear Glass Specimen Altered for 25 Years

    SciTech Connect

    Steefel, Carl

    2014-01-06

    The purpose of this contribution is to report on preliminary nano-continuum scale modeling of nuclear waste glass corrosion. The focus of the modeling is an experiment involving a French glass SON68 specimen leached for 25 years in a granitic environment. In this report, we focus on capturing the nano-scale concentration profiles. We use a high resolution continuum model with a constant grid spacing of 1 nanometer to investigate the glass corrosion mechanisms.

  20. Nuclear Melt Glass Dissolution and Secondary Mineral Precipitation at 40 to 200C

    SciTech Connect

    Zavarin, M; Roberts, S; Viani, B; Pawloski, G; Rose, T

    2004-06-14

    Most long-lived radionuclides associated with an underground nuclear test are initially incorporated into melt glass and become part of the hydrologic source term (HST) only upon their release via glass dissolution (Pawloski et al., 2001). As the melt glass dissolves, secondary minerals precipitate. The types of secondary minerals that precipitate influence the water chemistry in and around the melt glass. The secondary minerals also provide a sorption sink to the released radionuclides. The changing water chemistry affects the rate of glass dissolution; it also affects the sorption behavior of the released radionuclides. This complex nature of glass dissolution and its important role in defining the HST requires a thorough understanding of glass dissolution and secondary mineral precipitation. The identity of secondary minerals formed at temperatures from 40 to 200 C are evaluated in this report to assist in that understanding.

  1. ASSESSMENT OF NEPHELINE PRECIPITATION IN NUCLEAR WASTE GLASS VIA THERMOCHEMICAL MODELING

    EPA Science Inventory

    A thermochemical representation of the Na-Al-Si-B-O system relevant for nuclear waste glass has been developed based on the associate species approach for the glass solution phase. Thermochemical data were assessed and associate species data determined for binary and ternary sub...

  2. The effect of chromium oxide on the properties of simulated nuclear waste glasses

    SciTech Connect

    Vojtech, O.; Sussmilch, J.; Urbanec, Z.

    1996-02-01

    A study of the effect of chromium on the properties of selected glasses was performed in the frame of a Contract between Battelle, Pacific Northwest Laboratories and Nuclear Research Institute, ReZ. In the period from July 1994 to June 1995 two borosilicate glasses of special composition were prepared according to the PNL procedure and their physical and structural characteristics of glasses were studied. This Final Report contains a vast documentation on the properties of all glasses studied. For the preparation of the respective technology more detailed study of physico-chemical properties and crystallinity of investigated systems would be desirable.

  3. Fracture during cooling of cast borosilicate glass containing nuclear wastes

    SciTech Connect

    Smith, P.K.; Baxter, C.A.

    1981-09-01

    Procedures and techniques were evaluated to mitigate thermal stress fracture in waste glass as the glass cools after casting. The two principal causes of fracture identified in small-scale testing are internal thermal stresses arising from excessive thermal gradients when cooled too fast, and shear fracturing in the surface of the glass because the stainless steel canister shrinks faster than the glass on cooling. Acoustic emission and ceramographic techniques were used to outline an annealing schedule that requires at least three weeks of controlled cooling below 550/sup 0/C to avoid excessive thermal gradients and corresponding stresses. Fracture arising from canister interactions cannot be relieved by slow cooling, but can be eliminated for stainless steel canisters by using ceramic paper, ceramic or graphite paste linings, or by choosing a canister material with a thermal expansion coefficient comparable to, or less than, that of the glass.

  4. Characterization of high-level nuclear waste glass using magnetic measurements

    SciTech Connect

    Senftle, F.E.; Thorpe, A.N.; Grant, J.R.; Barkatt, A.

    1994-12-31

    Magnetic measurements constitute a promising method for the characterization of nuclear waste glasses in view of their simplicity and small sample weight requirements. Initial studies of simulated high-level waste glasses show that the Curie constant is generally a useful indicator of the Fe{sup 2+}:Fe{sup 3+} ratio. Glasses produced by air-cooling in large vessels show systematic deviations between experimental and calcined values, which are indicative of the presence of small amounts of crystalline iron-containing phases. Most of the iron in these phases becomes dissolved in the glass upon re-heating and more rapid quenching. The studies further show that upon leaching the glass in water some of the iron in the surface regions of the glass is converted to a form which has high temperature-independent magnetic susceptibility.

  5. Corrosion of synthesized glasses and glazes as analogs for nuclear waste glass degradation

    SciTech Connect

    Vandiver, P.B.

    1994-12-31

    Synthesized glasses provide an opportunity to study natural corrosion processes which are intermediate in time span between geological examples of natural glasses, such as obsidians and tektites, and relatively short term laboratory tests lasting a few hours to several decades. In addition, synthesized glasses can usually be tracked to particular archaeological find sites with known dates of production and often burial. Environmental conditions are routinely measured at archaeological sites as a part of the excavation-process, such that information is available on the yearly cycling of temperature and relative humidity, sometimes at the depth at which the artifact was found. Whether the artifacts were excavated in an air enclosure, such as a tomb, or in the soil can also be reconstructed, such that one can determine whether aqueous or atmospheric corrosion was involved in the degradation process. For instance, so-called {open_quotes}Roman glass{close_quotes} may span a time period of production of 800 years and a geographical range from Germany to North Africa and from Britain to Afghanistan. One example is the storage during World War II of glass from the British Museum in underground metro stations. Some of these glasses have been in collections for over 100 years. Thus, populations of glasses can be chosen for experimentation which compare variations in bulk composition, dopants, microstructure, heat treatment, ground vs. fire polished surfaces, aqueous vs. atmospheric corrosion, geographic, geological as well as recent storage conditions. Glasses in museums are generally considered to have had their corrosion arrested and be stable because changes in visual appearance are not obvious. However, if we attempt to measure the range of surface water content in these glasses using Fourier transform infrared analysis, a considerable variability is found, as shown.

  6. A comparison of the performance of nuclear waste glasses by modeling

    SciTech Connect

    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/sub 4/SiO/sub 4/. As a concentration of H/sub 4/SiO/sub 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/sub 4/SiO/sub 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.

  7. THE IMPACT OF KINETICS ON NEPHELINE FORMATION IN NUCLEAR WASTE GLASSES

    SciTech Connect

    Amoroso, J.

    2011-03-07

    Sixteen glass compositions were selected to study the potential impacts of the kinetics of nepheline formation in high-level nuclear waste (HLW) glass. The chosen compositions encompassed a relatively large nepheline discriminator (ND) range, 0.40-0.66, and included a relatively broad range, and amount of, constituents including high aluminum and high boron concentrations. All glasses were fabricated in the laboratory and subsequently exposed to six different cooling treatments. The cooling treatments consisted of three 'stepped' profiles and their corresponding 'smooth' profiles. Included in the cooling treatment was the Defense Waste Processing Facility (DWPF) canister centerline cooling (CCC) profile in addition to a 'faster' and a 'slower' total cooling line. After quenching and heat treating, x-ray diffraction confirmed the type and amount of any resultant crystallization. The target compositions were shown to be consistent with the measured compositions. Two quenched glasses and several treated glasses exhibited minor amounts of spinel and spinel-like phases. Nepheline was not observed in any of the quenched glasses but was observed in many of the treated glasses. The amount of nepheline ranged from approximately 2wt% to 30wt% for samples cooled over shorter times and longer times respectively. Differences were observed in the amount of nepheline crystallization after smooth and stepped cooling and increased with total cooling time. In some glasses, nepheline crystallization appeared to be directly proportional to total cooling time while the total amount of nepheline crystallization varied, suggesting that the nepheline crystallization rate was independent of (or at least faster than) cooling rate but, varied depending on the glass composition. On the contrary, in another glass, nepheline crystallization appeared to be inversely proportional to cooling rate. The high alumina glasses, predicted to form nepheline according to the ND, did not precipitate

  8. Overview of chemical modeling of nuclear waste glass dissolution

    SciTech Connect

    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.

  9. Production and dissolution of nuclear explosive melt glasses at underground test sites in the Pacific Region

    SciTech Connect

    Bourcier, W.L.; Smith, D.K.

    1998-11-06

    From 1975 to 1996 the French detonated 140 underground nuclear explosions beneath the atolls of Mururoa and Fangataufa in the South Pacific; from 1965 to 1971 the United States detonated three high yield nuclear tests beneath Amchitka Island in the Aleutian chain. Approximately 800 metric tons of basalt is melted per kiloton of nuclear yield; almost lo7 metric tons of basalt were melted in these tests. Long-lived and toxic radionuclides are partitioned into the melt glass at the time of explosion and are released by dissolution with seawater under saturated conditions. A glass dissolution model predicts that nuclear melt glasses at these sites will dissolve in lo6 to lo7 yea

  10. Iron Phosphate Glasses for Vitrifying DOE High Priority Nuclear Wastes

    SciTech Connect

    Kim, C.W.; Day, D.E.

    2004-03-29

    Iron phosphate glasses have been studied as an alternative glass for vitrifying Department of Energy (DOE) high priority wastes. The high priority wastes were the Low Activity Waste (LAW) and the High Level Waste (HLW) with high chrome content stored at Hanford, WA, and the Sodium Bearing Waste (SBW) stored at the Idaho National Engineering and Environmental Laboratory. These wastes were recommended by Tanks Focus Area since they were expected to require special attention when vitrified in borosilicate glasses. All three of these wastes have been successfully vitrified in iron phosphate glasses at waste loadings ranging from a low of 32 wt% for the high sulfate LAW to 40 wt% for the SBW to a high of 75 wt% for the high chrome HLW. In addition to these desirable high waste loadings, the iron phosphate glasses were easily melted, typically between 950 and 1200 C, in less than 4 hours in commercial refractory oxide containers. It is noteworthy that the chemical durability of both glassy and deliberately crystallized iron phosphate wasteforms not only met, but significantly exceeded, all current DOE chemical durability requirements as measured by the Product Consistency Test (PCT) and Vapor Hydration Test (VHT). The high waste loading, low melting temperature, rapid furnace throughput (short melting time) and their outstanding chemical durability could significantly accelerate the clean up effort and reduce the time and cost of vitrifying these high priority wastes.

  11. Self-healing capacity of nuclear glass observed by NMR spectroscopy

    PubMed Central

    Charpentier, Thibault; Martel, Laura; Mir, Anamul H.; Somers, Joseph; Jégou, Christophe; Peuget, Sylvain

    2016-01-01

    Safe management of high level nuclear waste is a worldwide significant issue for which vitrification has been selected by many countries. There exists a crucial need for improving our understanding of the ageing of the glass under irradiation. While external irradiation by ions provides a rapid simulation of damage induced by alpha decays, short lived actinide doping is more representative of the reality. Here, we report radiological NMR experiments to compare the damage in International Simplified Glass (ISG) when irradiated by these two methods. In the 0.1 mole percent 244Cm doped glass, accumulation of high alpha decay only shows small modifications of the local structure, in sharp contrast to heavy ion irradiation. These results reveal the ability of the alpha particle to partially repair the damage generated by the heavy recoil nuclei highlighting the radiation resistance of nuclear glass and the difficulty to accurately simulate its behaviour by single ion beam irradiations. PMID:27149700

  12. Self-healing capacity of nuclear glass observed by NMR spectroscopy.

    PubMed

    Charpentier, Thibault; Martel, Laura; Mir, Anamul H; Somers, Joseph; Jégou, Christophe; Peuget, Sylvain

    2016-01-01

    Safe management of high level nuclear waste is a worldwide significant issue for which vitrification has been selected by many countries. There exists a crucial need for improving our understanding of the ageing of the glass under irradiation. While external irradiation by ions provides a rapid simulation of damage induced by alpha decays, short lived actinide doping is more representative of the reality. Here, we report radiological NMR experiments to compare the damage in International Simplified Glass (ISG) when irradiated by these two methods. In the 0.1 mole percent (244)Cm doped glass, accumulation of high alpha decay only shows small modifications of the local structure, in sharp contrast to heavy ion irradiation. These results reveal the ability of the alpha particle to partially repair the damage generated by the heavy recoil nuclei highlighting the radiation resistance of nuclear glass and the difficulty to accurately simulate its behaviour by single ion beam irradiations. PMID:27149700

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

    SciTech Connect

    Zapol, Peter; Bourg, Ian; Criscenti, Louise Jacqueline; Steefel, Carl I.; 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.

  14. Self-healing capacity of nuclear glass observed by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Charpentier, Thibault; Martel, Laura; Mir, Anamul H.; Somers, Joseph; Jégou, Christophe; Peuget, Sylvain

    2016-05-01

    Safe management of high level nuclear waste is a worldwide significant issue for which vitrification has been selected by many countries. There exists a crucial need for improving our understanding of the ageing of the glass under irradiation. While external irradiation by ions provides a rapid simulation of damage induced by alpha decays, short lived actinide doping is more representative of the reality. Here, we report radiological NMR experiments to compare the damage in International Simplified Glass (ISG) when irradiated by these two methods. In the 0.1 mole percent 244Cm doped glass, accumulation of high alpha decay only shows small modifications of the local structure, in sharp contrast to heavy ion irradiation. These results reveal the ability of the alpha particle to partially repair the damage generated by the heavy recoil nuclei highlighting the radiation resistance of nuclear glass and the difficulty to accurately simulate its behaviour by single ion beam irradiations.

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

    SciTech Connect

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

    2011-12-31

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

  16. Nuclear waste glass product consistency test (PCT), Version 5.0. Revision 2

    SciTech Connect

    Jantzen, C.M.; Bibler, N.E.; Beam, D.C.; Ramsey, W.G.; Waters, B.J.

    1992-06-01

    Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass. The glass will be produced in the Defense Waste Processing Facility (DWPF), poured into stainless steel canisters, and eventually disposed of in a geologic repository. In order to comply with the Waste Acceptance Preliminary Specifications (WAPS), the durability of the glass needs to be measured during production to assure its long term stability and radionuclide release properties. A durability test, designated the Produce Consistency Test (PCT), was developed for DWPF glass in order to meet the WAPS requirements. The response of the PCT procedure was based on extensive testing with glasses of widely different compositions. The PCT was determined to be very reproducible, to yield reliable results rapidly, and to be easily performed in shielded cell facilities with radioactive samples. Version 5.0 of the PCT procedure is attached.

  17. Effects of composition on properties in an 11-component nuclear waste glass system

    SciTech Connect

    Chick, L.A.; Piepel, G.F.; Mellinger, G.B.; May, R.P.; Gray, W.J.; Buckwalter, C.Q.

    1981-09-01

    Ninety simplified nuclear waste glass compositions within an 11-component oxide composition matrix were tested for crystallinity, viscosity, volatility, and chemical durability. Empirical models of property response as a function of glass composition were developed using statistical experimental design and modeling techniques. A new statistical technique was developed to calculate the effects of oxide components on each property. Independent melts were used to check the prediction accuracy of the models.

  18. Measurement of leaching from simulated nuclear-waste glass using radiotracers

    SciTech Connect

    Bates, J.K.; Jardine, L.J.; Steindler, M.J.

    1982-09-01

    The use of radiotracer spiking as a method of measuring the leaching from simulated nuclear-waste glass is shown to give results comparable with other analytical detection methods. The leaching behavior of /sup 85/Sr, /sup 106/Ru, /sup 133/Ba, /sup 137/Cs, /sup 141/Ce, /sup 152/Eu, and other isotopes is measured for several defense waste glasses. These tests show that radiotracer spiking is a sensitive, multielement technique that can provide leaching data, for actual waste elements, that are difficult to obtain by other methods. Additionally, a detailed procedure is described that allows spiked glass to be prepared with a suitable distribution of radionuclides.

  19. An international initiative on long-term behavior of high-level nuclear waste glass

    SciTech Connect

    Gin, Stephane; Criscenti, Louise J.; Ebert, W. L.; Ferrand, Karine; Geisler, Thorsten; Harrison, Mike T.; Inagaki, Yaohiro; Mitsui, Seiichiro; Mueller, Karl T.; Marra, James C.; Pantano, Carlo G.; Pierce, Eric M.; Ryan, Joseph V.; Schofield, James M.; Steefel, Carl I.; Vienna, John D.

    2013-06-01

    Nations producing borosilicate glass as an immobilization material for radioactive wastes resulting from spent nuclear fuel reprocessing have reinforced scientific collaboration to obtain consensus on mechanisms controlling the long-term dissolution rate of glass. This goal is deemed to be crucial for the development of reliable performance assessment models for geological disposal. The collaborating laboratories all conduct fundamental and/or applied research with modern materials science techniques. The paper briefly reviews the radioactive waste vitrification programmes of the six participant nations and summarizes the state-of-the-art of glass corrosion science, emphasizing common scientific needs and justifications for on-going initiatives.

  20. Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

    NASA Astrophysics Data System (ADS)

    Pacold, J. I.; Lukens, W. W.; Booth, C. H.; Shuh, D. K.; Knight, K. B.; Eppich, G. R.; Holliday, K. S.

    2016-05-01

    Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.

  1. Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

    DOE PAGESBeta

    Pacold, J. I.; Lukens, W. W.; Booth, C. H.; Shuh, D. K.; Knight, K. B.; Eppich, G. R.; Holliday, K. S.

    2016-05-18

    We report that nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. Wemore » find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. Lastly, the resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.« less

  2. Secondary phases formed during nuclear waste glass-water interactions: Thermodynamic and derived properties

    SciTech Connect

    McKenzie, W.F.

    1992-08-01

    The thermodynamic properties of secondary phases observed to form during nuclear waste glass-water interactions are of particular interest as it is with the application of these properties together with the thermodynamic properties of other solid phases, fluid phases, and aqueous species that one may predict the environmental consequences of introducing radionuclides contained in the glass into groundwater at a high-level nuclear waste repository. The validation of these predicted consequences can be obtained from laboratory experiments and field observations at natural analogue sites. The purpose of this report is to update and expand the previous compilation (McKenzie, 1991) of thermodynamic data retrieved from the literature and/or estimated for secondary phases observed to form (and candidate phases from observed chemical compositions) during nuclear waste glass-water interactions. In addition, this report includes provisionally recommended thermodynamic data of secondary phases.

  3. Predicting liquid immiscibility in multicomponent nuclear waste glasses

    SciTech Connect

    Peeler, D.K.; Hrma, P.R.

    1994-04-01

    Taylor`s model for predicting amorphous phase separation in complex, multicomponent systems has been applied to high-level (simulated) radioactive waste glasses at the US Department of Energy`s Hanford site. Taylor`s model is primarily based on additions of modifying cations to a Na{sub 2}O-B{sub 2}O{sub 3}-SiO{sub 2} (NBS) submixture of the multicomponent glass. The position of the submixture relative to the miscibility dome defines the development probability of amorphous phase separation. Although prediction of amorphous phase separation in Hanford glasses (via experimental SEM/TEM analysis) is the primary thrust of this work; reported durability data is also provides limited insight into the composition/durability relationship. Using a modified model similar to Taylor`s, the results indicate that immiscibility may be predicted for multicomponent waste glasses by the addition of Li{sub 2}O to the ``alkali`` corner of the NBS submixture.

  4. AN APPROACH TO THERMOCHEMICAL MODELING OF NUCLEAR WASTE GLASS

    EPA Science Inventory

    This initial work is aimed at developing a basic understanding of the phase equilibria and solid solution behavior of the constituents of waste glass. Current, experimentally determined values are less than desirable since they depend on measurement of the leach rate under non-r...

  5. Deformation mechanisms during nanoindentation of sodium borosilicate glasses of nuclear interest

    SciTech Connect

    Kilymis, D. A.; Delaye, J.-M.

    2014-07-07

    In this paper we analyze results of Molecular Dynamics simulations of Vickers nanoindentation, performed for sodium borosilicate glasses of interest in the nuclear industry. Three glasses have been studied in their pristine form, as well as a disordered one that is analogous to the real irradiated glass. We focused in the behavior of the glass during the nanoindentation in order to reveal the mechanisms of deformation and how they are affected by microstructural characteristics. Results have shown a strong dependence on the SiO{sub 2} content of the glass, which promotes densification due to the open structure of SiO{sub 4} tetrahedra and also due to the strength of Si-O bonds. Densification for the glasses is primarily expressed by the relative decrease of the Si-O-Si and Si-O-B angles, indicating rotation of the structural units and decrease of free volume. The increase of alkali content on the other hand results to higher plasticity of the matrix and increased shear flow. The most important effect on the deformation mechanism of the disordered glasses is that of the highly depolymerized network that will also induce shear flow and, in combination with the increased free volume, will result in the decreased hardness of these glasses, as has been previously observed.

  6. Reaction sintered glass: A durable matrix for spinel-forming nuclear waste compositions

    NASA Astrophysics Data System (ADS)

    Gong, W. L.; Lutze, W.; Ewing, R. C.

    2000-01-01

    Glass formation by reaction sintering under isostatic pressure is an innovative process to vitrify refractory-rich high-level radioactive waste. We used a typical defense waste composition, containing spinel-forming components such as ˜4 wt% of Cr 2O 3, ˜23 wt% Al 2O 3, ˜13 wt% Fe 2O 3, and ˜9 wt% UO 2, with CeO 2 simulating UO 2. Reaction sintered silicate glasses with waste loading up to 45 wt% were prepared within three hours, by hot pressing at 800°C. The glass former was amorphous silica. Simulated waste was added as calcined oxides. The reaction sintered glass samples were characterized using scanning and analytical electron microscopy. The results show that extensive reaction sintering took place and a continuous glass phase formed. Waste components such as Na 2O, CaO, MnO 2, and Fe 2O 3, dissolved completely in the continuous glass phase. Cr 2O 3, Al 2O 3, and CeO 2 were only partially dissolved due to incomplete dissolution (Al 2O 3) or super-saturation and reprecipitation (Cr 2O 3 and CeO 2). The precipitation mechanism is related to a time dependent alkali content in the developing glass phase. Short-term corrosion tests in water showed that the glasses are chemically more durable than melted nuclear waste glasses. Based on hydration energies calculations, the long-term chemical durability of our reaction sintered glasses is expected to be comparable to that of rhyolitic and tektite glasses.

  7. The role of natural glasses as analogues in projecting the long-term alteration of high-level nuclear waste glasses: Part 1

    SciTech Connect

    Mazer, J.J.

    1993-12-31

    The common observation of glasses persisting in natural environments for long periods of time (up to tens of millions of years) provides compelling evidence that these materials can be kinetically stable in a variety of subsurface environments. This paper reviews how natural and historical synthesized glasses can be employed as natural analogues for understanding and projecting the long-term alteration of high-level nuclear waste glasses. The corrosion of basaltic glass results in many of the same alteration features found in laboratory testing of the corrosion of high-level radioactive waste glasses. Evidence has also been found indicating similarities in the rate controlling processes, such as the effects of silica concentration on corrosion in groundwater and in laboratory leachates. Naturally altered rhyolitic glasses and tektites provide additional evidence that can be used to constrain estimates of long-term waste glass alteration. When reacted under conditions where water is plentiful, the corrosion for these glasses is dominated by network hydrolysis, while the corrosion is dominated by molecular water diffusion and secondary mineral formation under conditions where water contact is intermittent or where water is relatively scarce. Synthesized glasses that have been naturally altered result in alkali-depleted alteration features that are similar to those found for natural glasses and for nuclear waste glasses. The characteristics of these alteration features appear to be dependent on the alteration conditions which affect the dominant reaction processes during weathering. In all cases, care must be taken to ensure that the information being provided by natural analogues is related to nuclear waste glass corrosion in a clear and meaningful way.

  8. An approach to thermochemical modeling of nuclear waste glass

    SciTech Connect

    Besmann, T.M.; Beahm, E.C.; Spear, K.E.

    1998-11-01

    This initial work is aimed at developing a basic understanding of the phase equilibria and solid solution behavior of the constituents of waste glass. Current, experimentally determined values are less than desirable since they depend on measurement of the leach rate under non-realistic conditions designed to accelerate processes that occur on a geologic time scale. The often-used assumption that the activity of a species is either unity or equal to the overall concentration of the metal can also yield misleading results. The associate species model, a recent development in thermochemical modeling, will be applied to these systems to more accurately predict chemical activities in such complex systems as waste glasses.

  9. AN ALTERNATIVE HOST MATRIX BASED ON IRON PHOSPHATE GLASSES FOR THE VITRIFICATION OF SPECIALIZED NUCLEAR WASTE FORMS

    EPA Science Inventory

    Borosilicate glass is the only material currently approved and being used to vitrify high level nuclear waste. Unfortunately, many high level nuclear waste feeds in the U.S. contain components which are chemically incompatible with borosilicate glasses. Current plans call for vit...

  10. Lead-iron phosphate glass as a containment medium for the disposal of high-level nuclear wastes

    DOEpatents

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

    1984-04-11

    Disclosed are lead-iron phosphate glasses containing a high level of Fe/sub 2/O/sub 3/ for use as a storage medium for high-level radioactive nuclear waste. By combining lead-iron phosphate glass with various types of simulated high-level nuclear waste

  11. Multicomponent leach tests in Standard Canadian Shield Saline Solution on glasses containing simulated nuclear waste

    SciTech Connect

    Heimann, R.B.; Wood, D.D.; Hamon, R.F.

    1984-01-01

    Leaching experiments on borosilicate glass frit and simulated nuclear waste glasses were performed as a preliminary to leaching experiments on glasses incorporating radioactive waste. The experimental design included (1) simulated waste glass, (2) ASTM Grade-2 titanium container material, (3) clay buffer material, (4) Standard Canadian Shield Saline Solution, and (5) granitic rock. Cumulative fractions of release for boron were determined, as well as the solution concentrations of silicon, iron, strontium and cesium. The leach rates for boron after 28 d were approximately 5 x 10/sup -6/ kg x m/sup -2/ x s/sup -1/ in Hastelloy vessels. There is an apparently strong relationship between the clay/groundwater ratio, the concentration of iron in the solution, and the concentrations of silicon, strontium, and cesium.

  12. Rhenium solubility in borosilicate nuclear waste glass: implications for the processing and immobilization of technetium-99.

    PubMed

    McCloy, John S; Riley, Brian J; Goel, Ashutosh; Liezers, Martin; Schweiger, Michael J; Rodriguez, Carmen P; Hrma, Pavel; Kim, Dong-Sang; Lukens, Wayne W; Kruger, Albert A

    2012-11-20

    The immobilization of technetium-99 ((99)Tc) in a suitable host matrix has proven to be a challenging task for researchers in the nuclear waste community around the world. In this context, the present work reports on the solubility and retention of rhenium, a nonradioactive surrogate for (99)Tc, in a sodium borosilicate glass. Glasses containing target Re concentrations from 0 to 10,000 ppm [by mass, added as KReO(4) (Re(7+))] were synthesized in vacuum-sealed quartz ampules to minimize the loss of Re from volatilization during melting at 1000 °C. The rhenium was found as Re(7+) in all of the glasses as observed by X-ray absorption near-edge structure. The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) using inductively coupled plasma optical emission spectroscopy. At higher rhenium concentrations, additional rhenium was retained in the glasses as crystalline inclusions of alkali perrhenates detected with X-ray diffraction. Since (99)Tc concentrations in a glass waste form are predicted to be <10 ppm (by mass), these Re results implied that the solubility should not be a limiting factor in processing radioactive wastes, assuming Tc as Tc(7+) and similarities between Re(7+) and Tc(7+) behavior in this glass system. PMID:23101883

  13. Current Understanding and Remaining Challenges in Modeling Long-Term Degradation of Borosilicate Nuclear Waste Glasses

    SciTech Connect

    Vienna, John D.; Ryan, Joseph V.; Gin, Stephane; Inagaki, Yaohiro

    2013-12-01

    Chemical durability is not a single material property that can be uniquely measured. Instead it is the response to a host of coupled material and environmental processes whose rates are estimated by a combination of theory, experiment, and modeling. High-level nuclear waste (HLW) glass is perhaps the most studied of any material yet there remain significant technical gaps regarding their chemical durability. The phenomena affecting the long-term performance of HLW glasses in their disposal environment include surface reactions, transport properties to and from the reacting glass surface, and ion exchange between the solid glass and the surrounding solution and alteration products. The rates of these processes are strongly influenced and are coupled through the solution chemistry, which is in turn influenced by the reacting glass and also by reaction with the near-field materials and precipitation of alteration products. Therefore, those processes must be understood sufficiently well to estimate or bound the performance of HLW glass in its disposal environment over geologic time-scales. This article summarizes the current state of understanding of surface reactions, transport properties, and ion exchange along with the near-field materials and alteration products influences on solution chemistry and glass reaction rates. Also summarized are the remaining technical gaps along with recommended approaches to fill those technical gaps.

  14. Low-temperature lithium diffusion in simulated high-level boroaluminosilicate nuclear waste glasses

    SciTech Connect

    Neeway, James J.; Kerisit, Sebastien N.; Gin, Stephane; Wang, Zhaoying; Zhu, Zihua; Ryan, Joseph V.

    2014-12-01

    Ion exchange is recognized as an integral, if underrepresented, mechanism influencing glass corrosion. However, due to the formation of various alteration layers in the presence of water, it is difficult to conclusively deconvolute the mechanisms of ion exchange from other processes occurring simultaneously during corrosion. In this work, an operationally inert non-aqueous solution was used as an alkali source material to isolate ion exchange and study the solid-state diffusion of lithium. Specifically, the experiments involved contacting glass coupons relevant to the immobilization of high-level nuclear waste, SON68 and CJ-6, which contained Li in natural isotope abundance, with a non-aqueous solution of 6LiCl dissolved in dimethyl sulfoxide at 90 °C for various time periods. The depth profiles of major elements in the glass coupons were measured using time-of-flight secondary ion mass spectrometry (ToF-SIMS). Lithium interdiffusion coefficients, DLi, were then calculated based on the measured depth profiles. The results indicate that the penetration of 6Li is rapid in both glasses with the simplified CJ-6 glass (D6Li ≈ 4.0-8.0 × 10-21 m2/s) exhibiting faster exchange than the more complex SON68 glass (DLi ≈ 2.0-4.0 × 10-21 m2/s). Additionally, sodium ions present in the glass were observed to participate in ion exchange reactions; however, different diffusion coefficients were necessary to fit the diffusion profiles of the two alkali ions. Implications of the diffusion coefficients obtained in the absence of alteration layers to the long-term performance of nuclear waste glasses in a geological repository system are also discussed.

  15. Comprehensive data base of high-level nuclear waste glasses: September 1987 status report: Volume 1, Discussion and glass durability data

    SciTech Connect

    Kindle, C.H.; Kreiter, M.R.

    1987-12-01

    The Materials Characterization Center (MCC) at Pacific Northwest Laboratory is assembling a comprehensive data base (CDB) of experimental data collected for high-level nuclear waste package components. Data collected throughout the world are included in the data base; current emphasis is on waste glasses and their properties. The goal is to provide a data base of properties and compositions and an analysis of dominant property trends as a function of composition. This data base is a resource that nuclear waste producers, disposers, and regulators can use to compare properties of a particular high-level nuclear waste glass product with the properties of other glasses of similar compositions. Researchers may use the data base to guide experimental tests to fill gaps in the available knowledge or to refine empirical models. The data are incorporated into a computerized data base that will allow the data to be extracted based on, for example, glass composition or test duration. 3 figs.

  16. ANNUAL PROGRESS REPORT. IRON PHOSPHATE GLASSES: AN ALTERNATIVE FOR VITRIFYING CERTAIN NUCLEAR WASTES

    EPA Science Inventory

    A high priority has been given to investigating the vitrification of three specific nuclear wastes in iron phosphate glasses (IPG). These wastes, which were recommended by the Tank Focus Area (TFA) group of Hanford, are poorly suited for vitrification in the currently DOE-approve...

  17. Glass Property Models, Constraints, and Formulation Approaches for Vitrification of High-Level Nuclear Wastes at the US Hanford Site

    SciTech Connect

    Kim, Dong-Sang

    2015-03-02

    The legacy nuclear wastes stored in underground tanks at the US Department of Energy’s Hanford site is planned to be separated into high-level waste and low-activity waste fractions and vitrified separately. Formulating optimized glass compositions that maximize the waste loading in glass is critical for successful and economical treatment and immobilization of nuclear wastes. Glass property-composition models have been developed and applied to formulate glass compositions for various objectives for the past several decades. The property models with associated uncertainties and combined with composition and property constraints have been used to develop preliminary glass formulation algorithms designed for vitrification process control and waste form qualification at the planned waste vitrification plant. This paper provides an overview of current status of glass property-composition models, constraints applicable to Hanford waste vitrification, and glass formulation approaches that have been developed for vitrification of hazardous and highly radioactive wastes stored at the Hanford site.

  18. Oxidation state of multivalent elements in high-level nuclear waste glass

    SciTech Connect

    Reynolds, J.G.

    2007-07-01

    Nuclear waste contains many different elements that have more than one oxidation state. When the nuclear waste is treated by vitrification, the behavior of the element in the melter and resulting glass product depends on the stable oxidation state. The stable oxidation state in any medium can be calculated from the standard potential in that medium. Consequently, the standard potential of multi-valent elements has been measured in many silicate-melts, including ones relevant to nuclear waste treatment. In this study, the relationship between the standard potential in molten nuclear waste glass and the standard potential in water will be quantified so that the standard potential of elements that have not been measured in glass can be estimated. The regression equation was found to have an R{sup 2} statistic of 0.96 or 0.83 depending on the number of electrons transferred in the reaction. The Nernst equation was then used to calculate the oxidation state of other relevant multi-valent elements in nuclear waste glass from these standard potentials and the measured ferrous to ferric iron ratio. The calculated oxidation states were consistent with all oxidation state measurements available. The calculated oxidation states were used to rationalize the behavior of many of the multi-valent elements. For instance, chromium increases glass crystallization because it is in the trivalent-state, iodine volatilises from the melter because it is in the volatile zero-valent state, and the leaching behavior of arsenic is driven by its oxidation state. Thus, these thermodynamic calculations explain the behavior of many trace elements during the vitrification process. (authors)

  19. Nuclear waste glass product consistency test (PCT): Version 7.0. Revision 3

    SciTech Connect

    Jantzen, C.M.; Bibler, N.E.; Beam, D.C.; Ramsey, W.G.

    1994-06-01

    Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass. The glass will be produced in the Defense Waste Processing Facility (DWPF), poured into stainless steel canisters, and eventually disposed of in a geologic repository. In order to comply with the Waste Acceptance Product Specifications (WAPS), the durability of the glass needs to be measured during production to assure its long term stability and radionuclide release properties. A durability test, designated the Product Consistency Test (PCT), was developed for DWPF glass in order to meet the WAPS requirements. The response of the PCT procedure was based on extensive testing with glasses of widely different compositions. The PCT was determined to be very reproducible, to yield reliable results rapidly, and to be easily performed in shielded cell facilities with radioactive samples. Version 7.0 of the PCT procedure is attached. This draft version has been submitted to ASTM for full committee (C26, Nuclear Fuel Cycle) ballot after being balloted successfully through subcommittee C26.13 on Repository Waste Package Materials Testing.

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

    NASA Astrophysics Data System (ADS)

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

    2006-08-01

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

  1. FTIR spectra and properties of iron borophosphate glasses containing simulated nuclear wastes

    NASA Astrophysics Data System (ADS)

    Liao, Qilong; Wang, Fu; Chen, Kuiru; Pan, Sheqi; Zhu, Hanzhen; Lu, Mingwei; Qin, Jianfa

    2015-07-01

    30 wt.% simulated nuclear wastes were successfully immobilized by B2O3-doped iron phosphate base glasses. The structure and thermal stability of the prepared wasteforms were characterized by Fourier transform infrared spectroscopy and differential thermal analysis, respectively. The subtle structural variations attributed to different B2O3 doping modes have been discussed in detail. The results show that the thermal stability and glass forming tendency of the iron borophosphate glass wasteforms are faintly affected by different B2O3 doping modes. The main structural networks of iron borophosphate glass wasteforms are PO43-, P2O74-, [BO4] groups. Furthermore, for the wasteform prepared by using 10B2O3-36Fe2O3-54P2O5 as base glass, the distributions of Fe-O-P bonds, [BO4], PO43- and P2O74- groups are optimal. In general, the dissolution rate (DR) values of the studied iron borophosphate wasteforms are about 10-8 g cm-2 min-1. The obtained conclusions can offer some useful information for the disposal of high-level radioactive wastes using boron contained phosphate glasses.

  2. Characteristics of colloids generated during the corrosion of nuclear waste glasses in groundwater

    SciTech Connect

    Feng, X.; Buck, E.C.; Mertz, C.; Bates, J.K.; Cunnane, J.C.; Chaiko, D.

    1993-10-01

    Aqueous colloidal suspensions were generated by reacting nuclear waste glasses with groundwater at 90{degrees}C at different ratios of the glass surface area to solution volume (S/V). The colloids have been characterized in terms of size, charge, identity, and stability with respect to salt concentration, pH, and time, by examination using dynamic light scattering, electrophoretic mobility, and transmission electron microscopy. The colloids are predominately produced by precipitation from solution, possibly with contribution from reacted layers that have spallated from the glass. These colloids are silicon-rich minerals. The colloidal suspensions agglomerate when the salinity of the solutions increase. The following implications for modeling the colloidal transport of contaminants have been derived from this study: (1) The sources of the colloids are not only solubility-limited real colloids and the pseudo colloids formed by adsorption of radionuclides onto a groundwater colloid, but also from the spalled surface layers of reacted waste glasses. (2) In a repository, the local environment is likely to be glass-reaction dominated and the salt concentration is likely to be high, leading to rapid colloid agglomeration and settling; thus, colloid transport may be insignificant. (3) If large volumes of groundwater contact the glass reaction site, the precipitated colloids may become resuspended, and colloid transport may become important. (4) Under most conditions, the colloids are negatively charged and will deposit readily on positively charged surfaces. Negatively charged surfaces will, in general, facilitate colloid stability and transport.

  3. Mineralogy and thermodynamic properties of magnesium phyllosilicates formed during the alteration of a simplified nuclear glass

    NASA Astrophysics Data System (ADS)

    Debure, Mathieu; De Windt, Laurent; Frugier, Pierre; Gin, Stéphane; Vieillard, Philippe

    2016-07-01

    The precipitation of crystallized magnesium phyllosilicates generally sustains the alteration rate of nuclear waste containment glass. However, glass alteration slows down to a residual rate as soon as Mg disappears from the solution. The identification of the phyllosilicates formed is therefore crucial for modeling the long-term behavior of nuclear glass. This study deals with batch alteration of the simplified nuclear glass ISG in presence of magnesium, and the characterization of the secondary phases. Morphological, chemical and structural analyses (MET, EDX, XRD) were performed to determine the nature and structure of the precipitated phases identified as trioctahedral smectites. Analyses conducted on the secondary phases proved the presence of Al, Na and Ca in the Mg-phyllosilicate phases. Such elements had been suspected but never quantitatively measured. The experimental results were then used to determine the thermodynamic solubility constants for each precipitated secondary phase at various temperatures. The calculated values were consistent with those available for sodium and magnesium saponites in the existing thermodynamic databases.

  4. Interaction study between nuclear waste-glass melt and ceramic melter bellow liner materials

    NASA Astrophysics Data System (ADS)

    Sengupta, Pranesh

    2011-04-01

    Identification of proper materials for plant scale vitrification furnaces, engaged in immobilization of high level nuclear waste has always been a great challenge. Fast degradation of pour spout materials very often cause problem towards smooth pouring of waste-glass melt in canister and damages bellow kept in between. The present experimental study describes the various reaction products that form due to interaction between waste-glass melt and potential bellow liner materials such as copper, stainless steel and nickel based Superalloys (Alloy 690, 625). The results indicate that copper based material has lesser tendency to form adherent glassy layer.

  5. High-level nuclear waste borosilicate glass: A compendium of characteristics

    SciTech Connect

    Cunnane, J.C.; Bates, J.K.; Ebert, W.L.; Feng, X.; Mazer, J.J.; Wronkiewicz, D.J.; Sproull, J.; Bourcier, W.L.; McGrail, B.P.

    1992-12-01

    With the imminent startup, in the United States, of facilities for vitrification of high-level nuclear waste, a document has been prepared that compiles the scientific basis for understanding the alteration of the waste glass products under the range of service conditions to which they may be exposed during storage, transportation, and eventual geologic disposal. A summary of selected parts of the content of this document is provided. Waste glass alterations in a geologic repository may include corrosion of the glass network due to groundwater and/or water vapor contact. Experimental testing results are described and interpreted in terms of the underlying chemical reactions and physical processes involved. The status of mechanistic modeling, which can be used for long-term predictions, is described and the remaining uncertainties associated with long-term simulations are summarized.

  6. High-level nuclear waste borosilicate glass: A compendium of characteristics

    SciTech Connect

    Cunnane, J.C.; Bates, J.K.; Ebert, W.L.; Feng, X.; Mazer, J.J.; Wronkiewicz, D.J. ); Sproull, J. ); Bourcier, W.L. ); McGrail, B.P. )

    1992-01-01

    With the imminent startup, in the United States, of facilities for vitrification of high-level nuclear waste, a document has been prepared that compiles the scientific basis for understanding the alteration of the waste glass products under the range of service conditions to which they may be exposed during storage, transportation, and eventual geologic disposal. A summary of selected parts of the content of this document is provided. Waste glass alterations in a geologic repository may include corrosion of the glass network due to groundwater and/or water vapor contact. Experimental testing results are described and interpreted in terms of the underlying chemical reactions and physical processes involved. The status of mechanistic modeling, which can be used for long-term predictions, is described and the remaining uncertainties associated with long-term simulations are summarized.

  7. Rhenium Solubility in Borosilicate Nuclear Waste Glass: Implications for the Processing and Immobilization of Technetium-99

    SciTech Connect

    McCloy, John S.; Riley, Brian J.; Goel, Ashutosh; Liezers, Martin; Schweiger, Michael J.; Rodriguez, Carmen P.; Hrma, Pavel R.; Kim, Dong-Sang; Lukens, Wayne W.; Kruger, Albert A.

    2012-10-26

    The immobilization of 99Tc in a suitable host matrix has proved to be an arduous task for the researchers in nuclear waste community around the world. At the Hanford site in Washington State, the total amount of 99Tc in low-activity waste (LAW) is ~1300 kg and the current strategy is to immobilize the 99Tc in borosilicate glass with vitrification. In this context, the present article reports on the solubility/retention of rhenium, a nonradioactive surrogate for 99Tc, in a LAW borosilicate glass. Due to the radioactive nature of technetium, rhenium was chosen as a simulant because of the similarity between their ionic radii and other chemical aspects. The glasses containing Re (0 – 10,000 ppm by mass) were synthesized in vacuum-sealed quartz ampoules in order to minimize the loss of Re by volatilization during melting at 1000 °C. The rhenium was found to predominantly exist as Re (VII) in all the glasses as observed by X-ray absorption near-edge structure (XANES). The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) with inductively coupled plasma-optical emission spectroscopy (ICP-OES). At higher rhenium concentrations, some additional material was retained in the glasses in the form of crystalline inclusions that were detected by X-ray diffraction (XRD) and laser ablation-ICP mass spectrometry (LA-ICP-MS). The implications of these results on the immobilization of 99Tc from radioactive wastes in borosilicate glasses have been discussed.

  8. Platinum group metal particles aggregation in nuclear glass melts under the effect of temperature

    NASA Astrophysics Data System (ADS)

    Hanotin, Caroline; Puig, Jean; Neyret, Muriel; Marchal, Philippe

    2016-08-01

    The viscosity of simulated high level radioactive waste glasses containing platinum group metal particles is studied over a wide range of shear stress, as a function of the particles content and the temperature, thanks to a stress imposed rheometer, coupled to a high-temperature furnace. The system shows a very shear thinning behavior. At high shear rate, the system behaves as a suspension of small clusters and individual particles and is entirely controlled by the viscosity of the glass matrix as classical suspensions. At low shear rate, above a certain fraction in platinum group metal particles, the apparition of macroscopic aggregates made up of chains of RuO2 particles separated by thin layers of glass matrix strongly influences the viscosity of the nuclear glass and leads, in particular, to the apparition of yield stress and thixotropic effects. The maximum size of these clusters as well as their effective volume fraction have been estimated by a balance between Van der Waals attractive forces and hydrodynamic forces due to shear flow. We showed experimentally and theoretically that this aggregation phenomenon is favored by an increase of the temperature, owing to the viscosity decrease of the glass matrix, leading to an unusual increase of the suspension viscosity.

  9. Development of a leach model for a commercial nuclear waste glass

    SciTech Connect

    Kuhn, W.L.; Peters, R.D.; Simonson, S.A.

    1983-10-01

    A leach model is presented for a commonly studied commercial nuclear waste glass, PNL 76-68. Boron release is taken to be a monitor of the reaction rate of the glass, while the actual releases of many other glass constituents into solution during static tests are evidently controlled by solubilities. The reaction rate determined in this way passes from linear to parabolic kinetics over the duration of the experiments analyzed, and boron concentrations in solution are found to be a function of the product of time and surface areato-solution volume ratio. This behavior is found to be explained well by assuming the reaction is impeded by resorption of reaction products onto the reacting surface. Two model parameters are found as functions of temperature by fitting the model to published data. It is concluded that the accumulation of silica near the glass surface in a waste package in a repository could limit the rate of reaction of the glass, but not that the reaction would cease as silica reaches its solubility limit in solution.

  10. Development of a leach model for a commercial nuclear waste glass

    SciTech Connect

    Kuhn, W.L.; Peters, K.D.; Simonson, S.A.

    1983-10-01

    A leach model is presented for a commonly studied commercial nuclear waste glass, PNL 76-68. Boron release is taken to be a monitor of the reaction rate of the glass, while the actual releases of many other glass constituents into solution during static tests are evidently controlled by solubilities. The reaction rate determined in this way passes from linear to parabolic kinetics over the duration of the experiments analyzed, and boron concentrations in solution are found to be a function of the product of time and surface area-to-solution volume ratio. This behavior is found to be explained well by assuming the reaction is impeded by resorption of reaction products onto the reacting surface. Two model parameters are found as functions of temperature by fitting the model to published data. It is conluded that the accumulation of silica near the glass surface in a waste package in a repository could limit the rate of reaction of the glass, but not that the reaction would cease as silica reaches its solubility limit in solution.

  11. Properties of nuclear waste melts and glasses: Contact-refractory corrosion and vapor phase hydration

    NASA Astrophysics Data System (ADS)

    Lu, Xiaodong

    Control of refractory corrosion in waste glass melts and meeting vapor phase hydration test (VHT) requirement for Hanford low-activity waste (LAW) glass product are two critical issues among many technical challenges of nuclear waste vitrification. In this study, refractory corrosion was treated as a complex non-equilibrium, multi-component and multi-phase reactive transport process and studied both thermodynamically and kinetically. Dissolution tests of granular refractory materials into under-saturated melts coupled with crystallization tests from supersaturated melts were used to determine the possible equilibrium points. The test results show that spinet phase is the most stable phase of K-3 refractory. Solubility of glass-refractory interface material controls the long term refractory corrosion rate and protects refractory from further corrosion. Therefore, refractory corrosion rate can be possibly adjusted by controlling the underlying solubility of the interface material. A set of monolithic refractory corrosion and dissolution tests was carried out to study the kinetic effects of refractory porosity and glass melt viscosity, the two major kinetic factors associated with reactive transport process. The test results show that temperature and glass melt viscosity have intensive effects on refractory material dissolution rate. Fast closure of channels near the glass-refractory interface during corrosion reaction by fast transformation of solid solution to spinel and spinel re-crystallization helps stop further corrosion reaction. Glass composition can be "passivated" by engineering the formulation to maximizing the beneficial alteration process. For the study of VHT kinetics, data from simulated LAW glasses studied previously at Pacific Northwest National Laboratory and Vitreous State Laboratory was modeled based on Avrami equation and its variant, the so-called generalized Avrami equation for better modeling of the VHT data. The results show that the kinetics

  12. Reuse of nuclear byproducts, NaF and HF in metal glass industries

    SciTech Connect

    Park, J.W.; Lee, H.W.; Yoo, S.H.; Moon, H.S.; Cho, N.C.

    1997-02-01

    A study has been performed to evaluate the radiological safety and feasibility associated with reuse of NaF(Sodium Fluoride) and HF(Hydrofluoric Acid) which are generated as byproducts from the nuclear fuel fabrication process. The investigation of oversea`s experience reveals that the byproduct materials are most often used in the metal and glass industries. For the radiological safety evaluation, the uranium radioactivities in the byproduct materials were examined and shown to be less than radioactivities in natural materials. The radiation doses to plant personnel and the general public were assessed to be very small and could be ignored. The Korea nuclear regulatory body permits the reuse of NaF in the metal industry on the basis of associated radioactivity being {open_quote}below regulatory concern{close_quote}. HF is now under review for reuse acceptability in the steel and glass industries.

  13. Nepheline Crystallization in Nuclear Waste Glasses: Progress toward acceptance of high-alumina formulations

    SciTech Connect

    McCloy, John S.; Schweiger, Michael J.; Rodriguez, Carmen P.; Vienna, John D.

    2011-09-01

    We have critically compiled and analyzed historical data for investigating the quantity of nepheline (NaAlSiO4) precipitation as a function of composition in simulated nuclear waste glasses. To understand composition we used two primary methods: 1) investigating the Al2O3-SiO2-Na2O ternary with filtering for different B2O3 levels and 2) creating a quadrant system consisting of compositions reduced to two metric numbers. These metrics are 1) the nepheline discriminator (ND) which depends only on the SiO2 content by weight normalized to the total weight of the Al2O3-SiO2-Na2O sub-mixture and 2) the optical basicity (OB) which contains contributions from all constituents in the glass. Nepheline precipitation is expected to be suppressed at high SiO2 levels (ND >0.62) or at low basicities (OB <0.55 to 0.57). Changes in sodium aluminosilicate glass OB due to additions of CaO and B2O3 correlate with observed effects on nepheline formation. We propose that additional composition space is available for formulating high-waste-loading, high-Al¬2O3 nuclear waste glasses when Na2O levels are less than ~0.125 (normalized by weight on the Al2O3-SiO2-Na2O sub-mixture). However, this compositional space is considerably extended to higher Na2O levels when adding >5 wt% B2O3. The OB concept can help further refine regions of nepheline-free glass formation.

  14. Conversion of Nuclear Waste into Nuclear Waste Glass: Experimental Investigation and Mathematical Modeling

    SciTech Connect

    Hrma, Pavel

    2014-12-18

    The melter feed, slurry, or calcine charged on the top of a pool of molten glass forms a floating layer of reacting material called the cold cap. Between the cold-cap top, which is covered with boiling slurry, and its bottom, where bubbles separate it from molten glass, the temperature changes by up to 1000 K. The processes that occur over this temperature interval within the cold cap include liberation of gases, conduction and consumption of heat, dissolution of quartz particles, formation and dissolution of intermediate crystalline phases, and generation of foam and gas cavities. These processes have been investigated using thermal analyses, optical and electronic microscopies, x-ray diffraction, as well as other techniques. Properties of the reacting feed, such as heat conductivity and density, were measured as functions of temperature. Investigating the structure of quenched cold caps produced in a laboratory-scale melter complemented the crucible studies. The cold cap consists of two main layers. The top layer contains solid particles dissolving in the glass-forming melt and open pores through which gases are escaping. The bottom layer contains bubbly melt or foam where bubbles coalesce into larger cavities that move sideways and release the gas to the atmosphere. The feed-to-glass conversion became sufficiently understood for representing the cold-cap processes via mathematical models. These models, which comprise heat transfer, mass transfer, and reaction kinetics models, have been developed with the final goal to relate feed parameters to the rate of glass melting.

  15. Leaching of actinide-doped nuclear waste glass in a tuff-dominated system

    SciTech Connect

    Bazan, F.; Rego, J.; Aines, R.D.

    1987-01-01

    A laboratory leaching test has been performed as part of a project to evaluate the suitability of tuff rocks at Yucca Mountain, Nevada, as a site for a high-level nuclear waste repository. Glass samples were placed in water inside tuff vessels, and then the tuff vessels were placed in water inside Teflon containers. Glass-component leach rates and migration through the tuff were measured for samples of the ATM-8 actinide glass, which is a PNL 76-68 based glass doped with low levels of {sup 99}Tc, {sup 237}Np, {sup 238}U, and {sup 239}Pu to simulate wastes. Disc samples of this glass were leached at 90{sup 0}C for 30, 90, and 183 days inside tuff vessels using a natural groundwater (J-13 well-water) as the leachant. At the end of each leaching interval, the J-13 water present inside and outside the rock vessel was analyzed for glass components in solutions. Boron, molybdenum, and technetium appear to migrate through the rock at rates that depend on the porosity of each vessel and the time. The actinide elements were found only in the inner leachate. Normalized elemental mass loss values for boron, molybdenum, and technetium were calculated using concentrations of the inner and outer leachates and assuming a negligible retention on the rock. The maximum normalized release was 2.3 g/m{sup 2} for technetium. Boron, molybdenum, technetium, and neptunium were released linearly with respect to each other, with boron and molybdenum released at about 85% of the technetium rate, and neptunium at 5 to 10% of the technetium rate. Plutonium was found at low levels in the inner leachate but was strongly sorbed on the steel and Teflon supports. Neptunium was sorbed to a lesser extent. 8 refs., 6 figs., 6 tabs.

  16. Obsidians and tektites: Natural analogues for water diffusion in nuclear waste glasses

    SciTech Connect

    Mazer, J.J.; Bates, J.K.; Bradley, C.R.; Stevenson, C.M.

    1991-11-01

    Projected scenarios for the proposed Yucca Mountain repository include significant periods of time when high relative humidity atmospheres will be present, thus the reaction processes of interest will include those known to occur under these conditions. The ideal natural analog for the proposed Yucca Mountain repository would consist of natural borosilicate glasses exposed to expected repository conditions for thousands of years; however, the prospects for identifying such an analog are remote, but an important caveat for using natural analog studies is to relate the reaction processes in the analog to those in the system of interest, rather than a strict comparison of the glass compositions. In lieu of this, identifying natural glasses that have reacted via reaction processes expected in the repository is the most attractive option. The goal of this study is to quantify molecular water diffusion in the natural analogs obsidian and tektites. Results from this study can be used in assessing the importance of factors affecting molecular water diffusion in nuclear waste glasses, relative to other identified reaction processes. In this way, a better understanding of the long-term reaction mechanism can be developed and incorporated into performance assessment models. 17 refs., 4 figs.

  17. Fibrous-glass aerosols: a literature review. Special report. [On nuclear submarines

    SciTech Connect

    Laverty, B.R.

    1987-10-02

    The submarine atmospheric is a topic of interest, considering that once submerged, the craft relies on its own electrostatic precipitators (ESP's), scrubbers, and filters to create, ideally, an environment with minimal aerosolized toxic materials and other by-products. Historically, atmosphere sampling aboard nuclear submarines has shown contaminants. Other contaminants include: ozone, (major source: by-product of the ESP's); freon, (major source: ship's refrigeration system and air-conditioning plants); hydrogen, (major source: ship's batteries); carbon dioxide, (major source: human respiration); and carbon monoxide, (major source: cigarette smoking). Contaminants tested for but not found were elemental mercury and asbestos. Considering that asbestos is no longer recommended for use, secondary to its carcinogenic and co-carcinogenic qualities, fibrous glass has become a common substitute. One use of fibrous glass aboard the Ohio class submarine is acoustic and thermal insulation around perforated ducting, which runs through many exposed, high traffic spaces, i.e. crew's berthing spaces. Although the raw fibrous glass is protected from the environment it is possible, through natural wear and tear of the housing material, that at some time the insulating material may become exposed and mechanically aerosolized. Obvious questions then are: a) do submarine aerosols contain fiber glass, and b) are there health hazards related to the inhalation of these fibers. This paper reviews the current knowledge as to the health hazard of exposure.

  18. Conversion of Nuclear Waste into Nuclear Waste Glass: Experimental Investigation and Mathematical Modeling

    DOE PAGESBeta

    Hrma, Pavel

    2014-12-18

    The melter feed, slurry, or calcine charged on the top of a pool of molten glass forms a floating layer of reacting material called the cold cap. Between the cold-cap top, which is covered with boiling slurry, and its bottom, where bubbles separate it from molten glass, the temperature changes by up to 1000 K. The processes that occur over this temperature interval within the cold cap include liberation of gases, conduction and consumption of heat, dissolution of quartz particles, formation and dissolution of intermediate crystalline phases, and generation of foam and gas cavities. These processes have been investigated usingmore » thermal analyses, optical and electronic microscopies, x-ray diffraction, as well as other techniques. Properties of the reacting feed, such as heat conductivity and density, were measured as functions of temperature. Investigating the structure of quenched cold caps produced in a laboratory-scale melter complemented the crucible studies. The cold cap consists of two main layers. The top layer contains solid particles dissolving in the glass-forming melt and open pores through which gases are escaping. The bottom layer contains bubbly melt or foam where bubbles coalesce into larger cavities that move sideways and release the gas to the atmosphere. The feed-to-glass conversion became sufficiently understood for representing the cold-cap processes via mathematical models. These models, which comprise heat transfer, mass transfer, and reaction kinetics models, have been developed with the final goal to relate feed parameters to the rate of glass melting.« less

  19. Raman Spectra, Structural Units and Durability of Nuclear Waste Glasses With Variations in Composition and Crystallization: Implications for Intermediate Order in the Glass Network

    SciTech Connect

    Raman, Swaminathan Venkat

    2002-11-01

    The Raman spectra of nuclear waste glasses are composed of large variations in half-width and intensity for the commonly observed bridging (Q0) and nonbridging (Q1 to Q4) bands in silicate structures. With increase in waste concentration in a boroaluminosilicate melt, the bands of quenched glasses are distinctly localized with half-width and intensity indicative of increase in atomic order. Since the nuclear waste glasses contain disparate components, and since the bands depart from the typical random network, a systematic study for the origin of these bands as a function of composition and crystallization was undertaken. From a comparative study of Raman spectra of boroaluminosilicate glasses containing Na2O-ZrO2, Na2O-MgO, MgO-Na2O-ZrO2, Na2O-CaO-ZrO2, Na2O-CaO, and Na2O-MgO-CaF2 component sets and orthosilicate crystals of zircon and forsterite, intermediate order is inferred. An edge-sharing polyhedral structural unit is proposed to account for narrow bandwidth and high intensity for Q2 antisymmetric modes, and decreased leaching of sodium with ZrO2 concentration in glass. The intense Q4 band in nuclear waste glass is similar to the intertetrahedral antisymmetric modes in forsterite. The Raman spectra of zircon contains intratetrahedral quartz-like peaks and intertetrahedral non-bridging silicate peaks. The quartz-like peaks nearly vanish in the background of forsterite spectrum. This difference between the Raman spectra of the two orthosilicate crystals presumably results from their biaxial and uniaxial effects on polarizability ellipsoids. The results also reveal formation of 604, 956 and 961 cm-1 defect bands with composition and crystallization.

  20. Model for the conversion of nuclear waste melter feed to glass

    SciTech Connect

    Pokorny, Richard; Hrma, Pavel R.

    2014-02-01

    The rate of batch-to-glass conversion is a primary concern for the vitrification of nuclear waste, as it directly influences the life cycle of the cleanup process. This study describes the development of an advanced model of the cold cap, which augments the previous model by further developments on the structure and the dynamics of the foam layer. The foam layer on the bottom of the cold cap consists of the primary foam, cavities, and the secondary foam, and forms an interface through which the heat is transferred to the cold cap. Other model enhancements include the behavior of intermediate crystalline phases and the dissolution of quartz particles. The model relates the melting rate to feed properties and melter conditions, such as the molten glass temperature, foaminess of the feed, or the heat fraction supplied to the cold cap from the plenum space. The model correctly predicts a 25% increase in melting rate when changing the alumina source in the melter feed from Al(OH)3 to AlO(OH). It is expected that this model will be incorporated in the full glass melter model as its integral component.

  1. Model for the conversion of nuclear waste melter feed to glass

    NASA Astrophysics Data System (ADS)

    Pokorny, Richard; Hrma, Pavel

    2014-02-01

    The rate of batch-to-glass conversion is a primary concern for the vitrification of nuclear waste, as it directly influences the life cycle of the cleanup process. This study describes the development of an advanced model of the cold cap, which augments the previous model by further developments on the structure and the dynamics of the foam layer. The foam layer on the bottom of the cold cap consists of the primary foam, cavities, and the secondary foam, and forms an interface through which the heat is transferred to the cold cap. Other model enhancements include the behavior of intermediate crystalline phases and the dissolution of quartz particles. The model relates the melting rate to feed properties and melter conditions, such as the molten glass temperature, foaminess of the melt, or the heat fraction supplied to the cold cap from the plenum space. The model correctly predicts a 25% increase in melting rate when changing the alumina source in the melter feed from Al(OH)3 to AlO(OH). It is expected that this model will be incorporated in the full glass melter model as its integral component.

  2. Study on the colloids generated from testing of high-level nuclear waste glasses

    SciTech Connect

    Feng, X.; Buck, E.C.; Mertz, C.; Bates, J.K.; Cunnane, J.C.; Chaiko, D.J.

    1993-03-01

    The generation of colloids in the interaction of high-level nuclear waste glasses with groundwater at 90{degrees}C has been investigated. The stability of the colloidal suspensions has been characterized with respect to salt concentration, pH time, particle size, and zeta potential. The compositions and the morphology of the colloids have also been determined with transmission electron microscopy (TEM). From ourtest results combined with earlier ones, we conclude that the waste glass may contribute to the colloid formation by increasing ion concentration in groundwater, which causes nucleation of colloids; by releasing radionuclides that adsorb onto existing groundwater colloids; and by spalling colloidal-size fragments from the surface layer of the reacted glass. The colloids are silicon-rich particles, such as smectites and uranium silicates. When the salt concentration in the solution is high the colloidal suspensions agglomerate. However, the agglomerated particles can be resuspended if the salt concentration is lowered by dilution with groundwater. The colloids agglomerate quickly after the leachate is cooled to room temperature. Most of the colloids settle out of the solution within a few days at ambient temperature. The isoelectric point is at a pH of approximately 1.0. Between pH 1 and 10.5, the colloids are negatively charged, which suggests that they will deposit readily on, positively charged surfaces. The average particle size islargest at the isoelectric point and is smallest around pH 6.

  3. Study on the colloids generated from testing of high-level nuclear waste glasses

    SciTech Connect

    Feng, X.; Buck, E.C.; Mertz, C.; Bates, J.K.; Cunnane, J.C.; Chaiko, D.J.

    1993-01-01

    The generation of colloids in the interaction of high-level nuclear waste glasses with groundwater at 90[degrees]C has been investigated. The stability of the colloidal suspensions has been characterized with respect to salt concentration, pH time, particle size, and zeta potential. The compositions and the morphology of the colloids have also been determined with transmission electron microscopy (TEM). From ourtest results combined with earlier ones, we conclude that the waste glass may contribute to the colloid formation by increasing ion concentration in groundwater, which causes nucleation of colloids; by releasing radionuclides that adsorb onto existing groundwater colloids; and by spalling colloidal-size fragments from the surface layer of the reacted glass. The colloids are silicon-rich particles, such as smectites and uranium silicates. When the salt concentration in the solution is high the colloidal suspensions agglomerate. However, the agglomerated particles can be resuspended if the salt concentration is lowered by dilution with groundwater. The colloids agglomerate quickly after the leachate is cooled to room temperature. Most of the colloids settle out of the solution within a few days at ambient temperature. The isoelectric point is at a pH of approximately 1.0. Between pH 1 and 10.5, the colloids are negatively charged, which suggests that they will deposit readily on, positively charged surfaces. The average particle size islargest at the isoelectric point and is smallest around pH 6.

  4. DIADDHEM set-up: New IBA facility for studying the helium behavior in nuclear glasses

    NASA Astrophysics Data System (ADS)

    Chamssedine, F.; Sauvage, T.; Peuget, S.

    2010-06-01

    The immobilization of fission products and minor actinides by vitrification is the reference process for industrial management of high-level radioactive wastes generated from spent fuel reprocessing. The glassy matrix is subjected to radiation damage and radiogenic helium generation due to the alpha decays of minor actinides. A specific experimental study has been conducted to better understand the behavior of helium and its diffusion mechanisms in the borosilicate glass. Helium production is simulated by external irradiation with 3He + ions at a concentration (2 × 10 15 He cm -2) equivalent to the one obtained after 1000 years of glass storage. He diffusion coefficients as function of temperature are extracted from the evolution of the depth profiles after annealing. The 3He(d, α) 1H Nuclear Reaction Analysis (NRA) technique is successfully used for in situ low-temperature measurements of depth profiles. Its high depth resolution allows detecting helium mobility at a temperature as low as 250 K and the presence of a trapped helium fraction. The good agreement of our first values of diffusion coefficients with the literature data highlights the relevance of the implantation technique in the study of helium diffusion mechanisms in borosilicate glasses.

  5. GdBr3: CE in a glass wafer as a nuclear radiation monitor.

    PubMed

    Kang, Zhitao; Rosson, Robert; Barta, M Brooke; Nadler, Jason; Wagner, Brent; Kahn, Bernd

    2013-05-01

    A glass wafer that contains cerium-activated gadolinium-based scintillator has been tested as a nuclear radiation monitor. The detector is prepared by mixing powdered gadolinium and cerium (3+) bromides with alumina, silica, and lithium fluoride, melting the mixture at 1,400°C, and then quenching and annealing the glass. The resulting clear glass matrix emits stimulated blue light that can be collected by a conventional photomultiplier tube. Spectral analysis of radionuclides with this detector shows the energy peaks for alpha particles, the energy continuum for beta particles, the Compton continuum and full-energy peaks for gamma rays, and an energy continuum with specific reaction-product peaks for neutrons. Energy resolution for the 5.5-MeV alpha particle and 0.662-MeV gamma-ray peaks is about 20%. This resolution, although threefold poorer than for single-crystal NaI(Tl) scintillators, contributes to radionuclide identification and quantification. Application of this detector to radiation monitoring is proposed, as well as approaches for improving light collection and energy resolution that will facilitate radionuclide identification and monitoring, especially for alpha particles, beta particles, and low-energy gamma rays. PMID:23532079

  6. (6)Li, (7)Li Nuclear Magnetic Resonance Investigation of Lithium Coordination in Binary Phosphate Glasses

    SciTech Connect

    Alam, T.M.; Boyle, T.J.; Brow, R.K.; Conzone, S.

    1999-02-08

    {sup 6}Li and {sup 7}Li solid state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy has been used to investigate the local coordination environment of lithium in a series of xLi{sub 2}O {center_dot} (1-x)P{sub 2}O{sub 5} glasses, where 0.05 {le} x {le} 0.55. Both the {sup 6}Li and {sup 7}Li show chemical shift variations with changes in the Li{sub 2}O concentration, but the observed {sup 6}Li NMR chemical shifts closely approximate the true isotropic chemical shift and can provide a measure of the lithium bonding environment. The {sup 6}Li NMR results indicate that in this series of lithium phosphate glasses the Li atoms have an average coordination between four and five. The results for the metaphosphate glass agree with the coordination number and range of chemical shifts observed for crystalline LiPO{sub 3}. An increase in the {sup 6}Li NMR chemical shift with increasing Li{sub 2}O content was observed for the entire concentration range investigated, correlating with increased cross-linking of the phosphate tetrahedral network by O-Li-O bridges. The {sup 6}Li chemical shifts were also observed to vary monotonically through the anomalous glass transition temperature (T{sub g}) minimum. This continuous chemical shift variation shows that abrupt changes in the Li coordination environment do not occur as the Li{sub 2}O concentration is increased, and such abrupt changes can not be used to explain the T{sub g} minimum.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  8. Characterization of borate glasses by W-band pulse electron-nuclear double resonance spectroscopy

    SciTech Connect

    Kordas, George; Goldfarb, Daniella

    2008-10-21

    (100-x) mol % B{sub 2}O{sub 3} x mol %Me{sub 2}O (Me=Li,Na,K) glasses, exposed to {gamma}-{sup 60}Co irradiation to produce paramagnetic states, were characterized by W-band (95 GHz) pulse electron-nuclear double resonance (ENDOR) spectroscopy in order to characterize local structures occurring in the range of compositions between x=16 and x=25 at which the 'boron oxide' anomaly occurs. The high resolution of nuclear frequencies allowed resolving the {sup 7}Li and {sup 11}B ENDOR lines. In the samples with x=16 and x=20 glasses, {sup 11}B hyperfine couplings of 16, 24, and 36 MHz were observed and attributed to the tetraborate, triborate, and boron oxygen hole center (BOHC) structures, respectively. The x=25 samples showed hyperfine couplings of 15 MHz for the tetraborate and 36 MHz for BOHC. Density functional theory (DFT) calculations predicted for these structures negative hyperfine couplings, which were confirmed by W-band ENDOR. This suggests that a spin polarization mechanism accounts for the negative hyperfine structure splitting.

  9. Characterization of borate glasses by W-band pulse electron-nuclear double resonance spectroscopy.

    PubMed

    Kordas, George; Goldfarb, Daniella

    2008-10-21

    (100-x) mol % B(2)O(3) x mol % Me(2)O (Me = Li,Na,K) glasses, exposed to gamma-(60)Co irradiation to produce paramagnetic states, were characterized by W-band (95 GHz) pulse electron-nuclear double resonance (ENDOR) spectroscopy in order to characterize local structures occurring in the range of compositions between x=16 and x=25 at which the "boron oxide" anomaly occurs. The high resolution of nuclear frequencies allowed resolving the (7)Li and (11)B ENDOR lines. In the samples with x=16 and x=20 glasses, (11)B hyperfine couplings of 16, 24, and 36 MHz were observed and attributed to the tetraborate, triborate, and boron oxygen hole center (BOHC) structures, respectively. The x=25 samples showed hyperfine couplings of 15 MHz for the tetraborate and 36 MHz for BOHC. Density functional theory (DFT) calculations predicted for these structures negative hyperfine couplings, which were confirmed by W-band ENDOR. This suggests that a spin polarization mechanism accounts for the negative hyperfine structure splitting. PMID:19045204

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

    PubMed

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

    2016-07-01

    We have examined variations in the (29)Si nuclear shielding tensor parameters of SiO4 tetrahedra in a series of seven alkali and alkaline earth silicate glass compositions, Cs2O·4.81 SiO2, Rb2O·3.96 SiO2, Rb2O·2.25 SiO2, K2O·4.48 SiO2, Na2O·4.74 SiO2, BaO·2.64 SiO2, and SrO·2.36 SiO2, using natural abundance (29)Si two-dimensional magic-angle flipping (MAF) experiments. Our analyses of these 2D spectra reveal a linear dependence of the (29)Si nuclear shielding anisotropy of Q((3)) sites on the Si-non-bridging oxygen bond length, which in turn depends on the cation potential and coordination of modifier cations to the non-bridging oxygen. We also demonstrate how a combination of Cu(2+) as a paramagnetic dopant combined with echo train acquisition can reduce the total experiment time of (29)Si 2D NMR measurements by two orders of magnitude, enabling higher throughput 2D NMR studies of glass structure. PMID:27187210

  11. Radiation effects in moist-air systems and the influence of radiolytic product formation on nuclear waste glass corrosion

    SciTech Connect

    Wronkiewicz, D.J.; Bates, J.K.; Buck, E.C.; Hoh, J.C.; Emery, J.W.; Wang, L.M.

    1997-07-01

    Ionizing radiation may affect the performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water to produce a variety of radiolytic products. Tests were conducted to examine the effects of radiolysis under high gas/liquid ratios. Results indicate that nitrate is the predominant radiolytic product produced following both gamma and alpha radiation exposure, with lesser amounts of nitrite and carboxylic acids. The formation of nitrogen acids during exposure to long-lived, alpha-particle-emitting transuranic elements indicates that these acids may play a role in influencing nuclear waste form reactions in a long-term unsaturated disposal scenario. Experiments were also conducted with samples that simulate the composition of Savannah River Plant nuclear waste glasses. Radiolytic product formation in batch tests (340 m{sup {minus}1}, 90 C) resulted in a small increase in the release rates of many glass components, such as alkali and alkaline earth elements, although silicon and uranium release rates were slightly reduced indicating an overall beneficial effect of radiation on waste form stability. The radiolytic acids increased the rate of ion exchange between the glass and the thin film of condensate, resulting in accelerated corrosion rates for the glass. The paragenetic sequence of alteration phases formed on both the irradiated and nonirradiated glass samples reacted in the vapor hydration tests matches closely with those developed during volcanic glass alteration in naturally occurring saline-alkaline lake systems. This correspondence suggests that the high temperatures used in these tests have not changed the underlying glass reaction mechanism relate to that which controls glass reactions under ambient surficial conditions.

  12. Heat Transfer in Waste Glass Melts - Measurement and Implications for Nuclear Waste Vitrification

    NASA Astrophysics Data System (ADS)

    Wang, Chuan

    Thermal properties of waste glass melts, such as high temperature density and thermal conductivity, are relevant to heat transfer processes in nuclear waste vitrification. Experimental measurement techniques were developed and applied to four nuclear waste glasses representative of those currently projected for treatment of Hanford HLW and LAW streams to study heat flow mechanisms in nuclear waste vitrification. Density measurement results by Archimedes' method indicated that densities of the melts investigated varied considerably with composition and temperature. Thermal diffusivities of waste melts were determined at nominal melter operating temperatures using a temperature-wave technique. Thermal conductivities were obtained by combining diffusivity data with the experimentally-acquired densities of the melts and their known heat capacities. The experimental results display quite large positive dependences of conductivities on temperature for some samples and much weaker positive temperature dependences for others. More importantly, there is observed a big change in the slopes of the conductivities versus temperature as temperature is increased for two of the melts, but not for the other two. This behavior was interpreted in terms of the changing contributions of radiation and conduction with temperature and composition dependence of the absorption coefficient. Based on the obtained thermal conductivities, a simple model for a waste glass melter was set up, which was used to analyze the relative contributions of conduction and radiation individually and collectively to the overall heat flow and to investigate factors and conditions that influence the radiation contribution to heat flow. The modeling results showed that unlike the case at lower temperatures, the radiant energy flow through waste melts could be predominant compared with conduction at temperature of about 900 °C or higher. However, heat flow due to radiation was roughly equal to that from

  13. Dynamics of asymmetric binary glass formers. I. A dielectric and nuclear magnetic resonance spectroscopy study

    NASA Astrophysics Data System (ADS)

    Kahlau, R.; Bock, D.; Schmidtke, B.; Rössler, E. A.

    2014-01-01

    Dielectric spectroscopy as well as 2H and 31P nuclear magnetic resonance spectroscopy (NMR) are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene (PS/PS-d3) in the full concentration (cTPP) range. In addition, depolarized light scattering and differential scanning calorimetry experiments are performed. Two glass transition temperatures are found: Tg1(cTPP) reflects PS dynamics and shows a monotonic plasticizer effect, while the lower Tg2(cTPP) exhibits a maximum and is attributed to (faster) TPP dynamics, occurring in a slowly moving or immobilized PS matrix. Dielectric spectroscopy probing solely TPP identifies two different time scales, which are attributed to two sub-ensembles. One of them, again, shows fast TPP dynamics (α2-process), the other (α1-process) displays time constants identical with those of the slow PS matrix. Upon heating the α1-fraction of TPP decreases until above some temperature Tc only a single α2-population exists. Inversely, below Tc a fraction of the TPP molecules is trapped by the PS matrix. At low cTPP the α2-relaxation does not follow frequency-temperature superposition (FTS), instead it is governed by a temperature independent distribution of activation energies leading to correlation times which follow Arrhenius laws, i.e., the α2-relaxation resembles a secondary process. Yet, 31P NMR demonstrates that it involves isotropic reorientations of TPP molecules within a slowly moving or rigid matrix of PS. At high cTPP the super-Arrhenius temperature dependence of τ2(T), as well as FTS are recovered, known as typical of the glass transition in neat systems.

  14. Dynamics of asymmetric binary glass formers. I. A dielectric and nuclear magnetic resonance spectroscopy study

    SciTech Connect

    Kahlau, R.; Bock, D.; Schmidtke, B.; Rössler, E. A.

    2014-01-28

    Dielectric spectroscopy as well as {sup 2}H and {sup 31}P nuclear magnetic resonance spectroscopy (NMR) are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene (PS/PS-d{sub 3}) in the full concentration (c{sub TPP}) range. In addition, depolarized light scattering and differential scanning calorimetry experiments are performed. Two glass transition temperatures are found: T{sub g1}(c{sub TPP}) reflects PS dynamics and shows a monotonic plasticizer effect, while the lower T{sub g2}(c{sub TPP}) exhibits a maximum and is attributed to (faster) TPP dynamics, occurring in a slowly moving or immobilized PS matrix. Dielectric spectroscopy probing solely TPP identifies two different time scales, which are attributed to two sub-ensembles. One of them, again, shows fast TPP dynamics (α{sub 2}-process), the other (α{sub 1}-process) displays time constants identical with those of the slow PS matrix. Upon heating the α{sub 1}-fraction of TPP decreases until above some temperature T{sub c} only a single α{sub 2}-population exists. Inversely, below T{sub c} a fraction of the TPP molecules is trapped by the PS matrix. At low c{sub TPP} the α{sub 2}-relaxation does not follow frequency-temperature superposition (FTS), instead it is governed by a temperature independent distribution of activation energies leading to correlation times which follow Arrhenius laws, i.e., the α{sub 2}-relaxation resembles a secondary process. Yet, {sup 31}P NMR demonstrates that it involves isotropic reorientations of TPP molecules within a slowly moving or rigid matrix of PS. At high c{sub TPP} the super-Arrhenius temperature dependence of τ{sub 2}(T), as well as FTS are recovered, known as typical of the glass transition in neat systems.

  15. Dynamics of asymmetric binary glass formers. II. Results from nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Bock, D.; Kahlau, R.; Pötzschner, B.; Körber, T.; Wagner, E.; Rössler, E. A.

    2014-03-01

    Various 2H and 31P nuclear magnetic resonance (NMR) spectroscopy techniques are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene-d3 (PS) over the full concentration range. The results are quantitatively compared to those of a dielectric spectroscopy (DS) study on the same system previously published [R. Kahlau, D. Bock, B. Schmidtke, and E. A. Rössler, J. Chem. Phys. 140, 044509 (2014)]. While the PS dynamics does not significantly change in the mixtures compared to that of neat PS, two fractions of TPP molecules are identified, one joining the glass transition of PS in the mixture (α1-process), the second reorienting isotropically (α2-process) even in the rigid matrix of PS, although at low concentration resembling a secondary process regarding its manifestation in the DS spectra. Pronounced dynamical heterogeneities are found for the TPP α2-process, showing up in extremely stretched, quasi-logarithmic stimulated echo decays. While the time window of NMR is insufficient for recording the full correlation functions, DS results, covering a larger dynamical range, provide a satisfactory interpolation of the NMR data. Two-dimensional 31P NMR spectra prove exchange within the broadly distributed α2-process. As demonstrated by 2H NMR, the PS matrix reflects the faster α2-process of TPP by performing a spatially highly hindered motion on the same timescale.

  16. Dynamics of asymmetric binary glass formers. II. Results from nuclear magnetic resonance spectroscopy

    SciTech Connect

    Bock, D.; Kahlau, R.; Pötzschner, B.; Körber, T.; Wagner, E.; Rössler, E. A.

    2014-03-07

    Various {sup 2}H and {sup 31}P nuclear magnetic resonance (NMR) spectroscopy techniques are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene-d{sub 3} (PS) over the full concentration range. The results are quantitatively compared to those of a dielectric spectroscopy (DS) study on the same system previously published [R. Kahlau, D. Bock, B. Schmidtke, and E. A. Rössler, J. Chem. Phys. 140, 044509 (2014)]. While the PS dynamics does not significantly change in the mixtures compared to that of neat PS, two fractions of TPP molecules are identified, one joining the glass transition of PS in the mixture (α{sub 1}-process), the second reorienting isotropically (α{sub 2}-process) even in the rigid matrix of PS, although at low concentration resembling a secondary process regarding its manifestation in the DS spectra. Pronounced dynamical heterogeneities are found for the TPP α{sub 2}-process, showing up in extremely stretched, quasi-logarithmic stimulated echo decays. While the time window of NMR is insufficient for recording the full correlation functions, DS results, covering a larger dynamical range, provide a satisfactory interpolation of the NMR data. Two-dimensional {sup 31}P NMR spectra prove exchange within the broadly distributed α{sub 2}-process. As demonstrated by {sup 2}H NMR, the PS matrix reflects the faster α{sub 2}-process of TPP by performing a spatially highly hindered motion on the same timescale.

  17. Difference between nuclear spin relaxation and ionic conductivity relaxation in superionic glasses

    NASA Astrophysics Data System (ADS)

    Ngai, K. L.

    1993-04-01

    Tatsumisago, Angell, and Martin [J. Chem. Phys. 97, 6968 (1992)] have compared conductivity relaxation data and 7Li nuclear spin lattice relaxation (SLR) data measured on a lithium chloroborate glass and found pronounced differences in the most probable relaxation times. The electrical conductivity relaxation (ECR) time, τ*σ, at some temperature occurs on a time scale shorter by some two orders of magnitude than the 7Li spin lattice relaxation correlation time, τ*s, and has a significantly lower activation energy. SLR and ECR monitor the motions of ions through different dynamic variables and correlation functions. Using this fact and the coupling model, I am able to explain quantitatively all aspects of the difference between SLR and ECR, and to establish relations between their different relaxation characteristics. The large difference between the observed activation energies of SLR and ECR alone should have implications on the validity of any proposed theory of the dynamics of ionic transport.

  18. Comprehensive data base of high-level nuclear waste glasses: September 1987 status report: Volume 2, Additional appendices

    SciTech Connect

    Kindle, C.H.; Kreiter, M.R.

    1987-12-01

    The Materials Characterization Center (MCC) is assembling a comprehensive data base (CDB) of experimental data collected for high-level nuclear waste package components. The status of the CDB is summarized in Volume I of this report. Volume II contains appendices that present data from the data base and an evaluation of glass durability models applied to the data base.

  19. MASBAL: A computer program for predicting the composition of nuclear waste glass produced by a slurry-fed ceramic melter

    SciTech Connect

    Reimus, P.W.

    1987-07-01

    This report is a user's manual for the MASBAL computer program. MASBAL's objectives are to predict the composition of nuclear waste glass produced by a slurry-fed ceramic melter based on a knowledge of process conditions; to generate simulated data that can be used to estimate the uncertainty in the predicted glass composition as a function of process uncertainties; and to generate simulated data that can be used to provide a measure of the inherent variability in the glass composition as a function of the inherent variability in the feed composition. These three capabilities are important to nuclear waste glass producers because there are constraints on the range of compositions that can be processed in a ceramic melter and on the range of compositions that will be acceptable for disposal in a geologic repository. MASBAL was developed specifically to simulate the operation of the West Valley Component Test system, a commercial-scale ceramic melter system that will process high-level nuclear wastes currently stored in underground tanks at the site of the Western New York Nuclear Services Center (near West Valley, New York). The program is flexible enough, however, to simulate any slurry-fed ceramic melter system. 4 refs., 16 figs., 5 tabs.

  20. The determination of the Fe sup 2+ /Fe sup 3+ ratio in simulated nuclear waste glass by ion chromatography

    SciTech Connect

    Jantzen, C.M.

    1990-10-01

    Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass in the Defense Waste Processing Facility (DWPF). In this facility, control of the oxidation/reduction (redox) equilibrium in the glass melter is critical for processing of the nuclear waste. Therefore, the development of a rapid and reliable analytical method for the determination of the redox equilibrium is of considerable interest. Redox has been determined by measuring the ratio of ferrous to ferric ions in the glass melt. Two analytical techniques for glass redox measurement have been investigated for the DWPF: Mossbauer Spectroscopy which may be subject to interferences from the radiation in actual waste, and a rapid and simple chemical dissolution/spectrophotometric technique. Comparisons of these techniques have been made at several laboratories including Clemson University. In the study attached, the determination of the redox ratio by Ion Chromatography (IC) was investigated as a potential new technology. Clemson University performed IC analyses on the same glasses as previously examined by wet chemical and Mossbauer techniques. Results from all three techniques were highly correlated and IC was reported to be a promising new technology for redox measurement. 19 refs., 19 figs., 5 tabs.

  1. Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: Application to a nuclear glass specimen altered 25 years in a granitic environment

    SciTech Connect

    Gin, Stephane; Ryan, Joseph V.; Schreiber, Daniel K.; Neeway, James J.; Cabie, M.

    2013-04-08

    Here, we report and discuss results of atom probe tomography (APT) and energy-filtered transmission electron microscopy (EFTEM) applied to a borosilicate glass sample of nuclear interest altered for nearly 26 years at 90°C in a confined granitic medium in order to better understand the rate-limiting mechanisms under conditions representative of a deep geological repository for vitrified radioactive waste. The APT technique allows the 3D reconstruction of the elemental distribution at the reactive interphase with sub-nanometer precision. Profiles of the B distribution at pristine glass/hydrated glass interface obtained by different techniques are compared to show the challenge of accurate measurements of diffusion profiles at this buried interface on the nanometer length scale. Our results show that 1) Alkali from the glass and hydrogen from the solution exhibit anti-correlated 15 ± 3 nm wide gradients located between the pristine glass and the hydrated glass layer, 2) boron exhibits an unexpectedly sharp profile located just at the outside of the alkali/H interdiffusion layer; this sharp profile is more consistent with a dissolution front than a diffusion-controlled release of boron. The resulting apparent diffusion coefficients derived from the Li and H profiles are DLi = 1.5 × 10-22 m2.s-1 and DH = 6.8 × 10-23 m2.s-1. These values are around two orders of magnitude lower than those observed at the very beginning of the alteration process, which suggests that interdiffusion is slowed at high reaction progress by local conditions that could be related to the porous structure of the interphase. As a result, the accessibility of water to the pristine glass could be the rate-limiting step in these conditions. More generally, these findings strongly support the importance of interdiffusion coupled with hydrolysis reactions of the silicate network on the long-term dissolution

  2. Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: Application to a nuclear glass specimen altered 25 years in a granitic environment

    DOE PAGESBeta

    Gin, Stephane; Ryan, Joseph V.; Schreiber, Daniel K.; Neeway, James J.; Cabie, M.

    2013-04-08

    Here, we report and discuss results of atom probe tomography (APT) and energy-filtered transmission electron microscopy (EFTEM) applied to a borosilicate glass sample of nuclear interest altered for nearly 26 years at 90°C in a confined granitic medium in order to better understand the rate-limiting mechanisms under conditions representative of a deep geological repository for vitrified radioactive waste. The APT technique allows the 3D reconstruction of the elemental distribution at the reactive interphase with sub-nanometer precision. Profiles of the B distribution at pristine glass/hydrated glass interface obtained by different techniques are compared to show the challenge of accurate measurements ofmore » diffusion profiles at this buried interface on the nanometer length scale. Our results show that 1) Alkali from the glass and hydrogen from the solution exhibit anti-correlated 15 ± 3 nm wide gradients located between the pristine glass and the hydrated glass layer, 2) boron exhibits an unexpectedly sharp profile located just at the outside of the alkali/H interdiffusion layer; this sharp profile is more consistent with a dissolution front than a diffusion-controlled release of boron. The resulting apparent diffusion coefficients derived from the Li and H profiles are DLi = 1.5 × 10-22 m2.s-1 and DH = 6.8 × 10-23 m2.s-1. These values are around two orders of magnitude lower than those observed at the very beginning of the alteration process, which suggests that interdiffusion is slowed at high reaction progress by local conditions that could be related to the porous structure of the interphase. As a result, the accessibility of water to the pristine glass could be the rate-limiting step in these conditions. More generally, these findings strongly support the importance of interdiffusion coupled with hydrolysis reactions of the silicate network on the long-term dissolution rate, contrary to what has been suggested by recent interfacial dissolution

  3. Study of fluorine in silicate glass with 19F nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Duncan, T. M.; Douglass, D. C.; Csencsits, R.; Walker, K. L.

    1986-07-01

    We report an application of nuclear magnetic resonance (NMR) spectroscopy to the study of fluorine-doped silicate glass prepared by the modified chemical vapor deposition process, prior to drawing the rod into fibers. The silica contains 1.03-wt. % fluorine, as determined by the calibrated intensity of the 19F NMR spectrum. The isotropic chemical shift of the 19F spectrum shows that fluorine bonds only to silicon; there is no evidence of oxyfluorides. Analysis of the distribution of nuclear dipolar couplings between fluorine nuclei reveals that the relative populations of silicon monofluoride sites [Si(O-)3F] and species having near-neighbor fluorines, such as silicon difluoride sites [Si(O-)2F2], are nearly statistically random. That is, to a good approximation, the fluorine substitutes randomly into the oxygen sites of the silica network. There is no evidence of local clusters of fluorine sites, silicon trifluoride sites [Si(O-)F3], or silicon tetrafluoride (SiF4).

  4. Measurement of the nuclear electromagnetic cascade development in glass at energies above 200 GeV

    NASA Technical Reports Server (NTRS)

    Gillespie, C. R.; Huggett, R. W.; Humphreys, D. R.; Jones, W. V.; Levit, L. B.

    1971-01-01

    The longitudinal development of nuclear-electromagnetic cascades with energies greater than 200 GeV was measured in a low-Z (glass) absorber. This was done in the course of operating an ionization spectrometer at mountain altitude in an experiment to study the properties of gamma rays emitted from individual interactions at energies around 10,000 GeV. The ionization produced by a cascade is sampled by 20 sheets of plastic scintillator spaced uniformly in depth every 2.2 radiation lengths. Adjacent pairs of scintillators are viewed by photomultipliers which measure the mean ionization produced by an individual cascade in 10 layers each 1.1 interaction length (4.4 radiation lengths) thick. The longitudinal development of the cascades was measured for about 250 cascades having energies ranging from 200 GeV to 2500 GeV. The observations are compared with the predictions of calculations made for this specific spectrometer using a three-dimensional Monte Carlo model of the nuclear-electromagnetic cascade.

  5. The relationship between glass viscosity and composition: A first principles model for vitrification of nuclear waste

    SciTech Connect

    Jantzen, C.M.

    1990-12-31

    The Defense Waste Processing Facility will incorporate high-level liquid waste into borosilicate glass for stabilization and permanent disposal in a geologic repository. The viscosity of the melt determines the rate of melting of the raw feed, the rate of gas bubble release due to foaming and fining, the rate of homogenization, and thus, the quality of the glass produced. The viscosity of the glass is in turn, a function of both glass composition and temperature. A model describing the viscosity dependence on composition, temperature, and glass structure (bonding) has been derived for glasses ranging from pure frits to frit plus 35 wt % simulated waste. 17 refs., 37 figs.

  6. The relationship between glass viscosity and composition: A first principles model for vitrification of nuclear waste

    SciTech Connect

    Jantzen, C.M.

    1990-01-01

    540The Defense Waste Processing Facility will incorporate high-level liquid waste into borosilicate glass for stabilization and permanent disposal in a geologic repository. The viscosity of the melt determines the rate of melting of the raw feed, the rate of gas bubble release due to foaming and fining, the rate of homogenization, and thus, the quality of the glass produced. The viscosity of the glass is in turn, a function of both glass composition and temperature. A model describing the viscosity dependence on composition, temperature, and glass structure (bonding) has been derived for glasses ranging from pure frits to frit plus 35 wt % simulated waste. 17 refs., 37 figs.

  7. Effects of {alpha}-decay on mechanical properties of simulated nuclear waste glass

    SciTech Connect

    Inagaki, Y.; Furuya, H.; Ono, Y.; Idemitsu, K.; Banba, T.; Matsumoto, S.; Muraoka, S.

    1993-12-31

    A simulated nuclear waste glass was self-irradiated by doping with short-lived actinides of {sup 238}Pu and {sup 244}Cm. Changes in the hardness, the Young`s modulus and the fracture toughness, as a function of irradiation dose, were measured by use of identation techniques. The irradiated glass was annealed at temperatures from 573K to 723K for periods of up to 48 hours, and the recovery of these changes were measured as a function of annealing and time. It was observed that the hardness and the Young`s modulus decreased, while the fracture toughness increased exponentially with the cumulative dose. The maximum values of the relative changes in the hardness, the Young`s modulus and the fracture toughness were about -25%, -30% and +45%, respectively. The results of the annealing show that the hardness and the Young`s modulus were almost recovered to the original values at temperatures above 673 K within 10 hours, while the recovery of the fracture toughness was minimal in this region of temperature and time. The changes in the hardness and the Young`s modulus can be well explained by the model, in which the changes is proportional to the volume fraction of damaged zones, F, and the recovery of F is first order. On the other hand, the changes in the fracture toughness cannot be explained by the model, which suggests that the mechanism of the change in the fracture toughness is different from that in the hardness and the Young`s modulus.

  8. Cerium, uranium, and plutonium behavior in glass-bonded sodalite, a ceramic nuclear waste form.

    SciTech Connect

    Lewis, M. A.; Lexa, D.; Morss, L. R.; Richmann, M. K.

    1999-09-03

    Glass-bonded sodalite is being developed as a ceramic waste form (CWF) to immobilize radioactive fission products, actinides, and salt residues from electrometallurgical treatment of spent nuclear reactor fuel. The CWF consists of about 75 mass % sodalite, 25 mass % glass, and small amounts of other phases. This paper presents some results and interpretation of physical measurements to characterize the CWF structure, and dissolution tests to measure the release of matrix components and radionuclides from the waste form. Tests have been carried out with specimens of the CWF that contain rare earths at concentrations similar to those expected in the waste form. Parallel tests have been carried out on specimens that have uranium or plutonium as well as the rare earths at concentrations similar to those expected in the waste forms; in these specimens UCl{sub 3} forms UO{sub 2} and PuCl{sub 3} forms PuO{sub 2}. The normalized releases of rare earths in dissolution tests were found to be much lower than those of matrix elements (B, Si, Al, Na). When there is no uranium in the CWF, the release of cerium is two to ten times lower than the release of the other rare earths. The low release of cerium may be due to its tetravalent state in uranium-free CWF. However, when there is uranium in the CWF, the release of cerium is similar to that of the other rare earths. This trivalent behavior of cerium is attributed to charge transfer or covalent interactions among cerium, uranium, and oxygen in (U,Ce)O{sub 2}.

  9. Photoelectron, nuclear gamma-ray and infrared absorption spectroscopic studies of neptunium in sodium silicate glass

    SciTech Connect

    Veal, B.W.; Carnall, W.T.; Dunlap, B.D.; Mitchell, A.W.; Lam, D.J.

    1986-04-01

    The valence state of neptunium ions in sodium silicate glasses prepared under reducing and oxidizing conditions has been investigated by the x-ray photoelectron, Moessbauer and optical absorption spectroscopic techniques. Results indicate that the Np ions are tetravalent in glasses prepared under reducing conditions and pentavalent in glasses prepared under oxidizing conditions.

  10. Optimization of glass composition for the vitrification of nuclear waste at the Savannah River Plant

    SciTech Connect

    Soper, P D; Roberts, G J; Lightner, L F; Walker, D D; Plodinec, M J

    1982-01-01

    Waste glasses of different compositions were compared in terms of leachability, viscosity, liquidus temperature, and coefficient of expansion. The compositions of the glasses were determined by statistical optimization. Waste glass of the optimized composition is more durable than the current reference composition but can still be processed at low temperature.

  11. Examining the role of canister cooling conditions on the formation of nepheline from nuclear waste glasses

    SciTech Connect

    Christian, J. H.

    2015-09-01

    Nepheline (NaAlSiO₄) crystals can form during slow cooling of high-level waste (HLW) glass after it has been poured into a waste canister. Formation of these crystals can adversely affect the chemical durability of the glass. The tendency for nepheline crystallization to form in a HLW glass increases with increasing concentrations of Al₂O₃ and Na₂O.

  12. INCORPORATION OF MONO SODIUM TITANATE AND CRYSTALLINE SILICOTITANATE FEEDS IN HIGH LEVEL NUCLEAR WASTE GLASS

    SciTech Connect

    Fox, K.; Johnson, F.; Edwards, T.

    2010-11-23

    Four series of glass compositions were selected, fabricated, and characterized as part of a study to determine the impacts of the addition of Crystalline Silicotitanate (CST) and Monosodium Titanate (MST) from the Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) glass waste form and the applicability of the DWPF process control models. All of the glasses studied were considerably more durable than the benchmark Environmental Assessment (EA) glass. The measured Product Consistency Test (PCT) responses were compared with the predicted values from the current DWPF durability model. One of the KT01-series and two of the KT03-series glasses had measured PCT responses that were outside the lower bound of the durability model. All of the KT04 glasses had durabilities that were predictable regardless of heat treatment or compositional view. In general, the measured viscosity values of the KT01, KT03, and KT04-series glasses are well predicted by the current DWPF viscosity model. The results of liquidus temperature (T{sub L}) measurements for the KT01-series glasses were mixed with regard to the predictability of the T{sub L} for each glass. All of the measured T{sub L} values were higher than the model predicted values, although most fell within the 95% confidence intervals. Overall, the results of this study show a reasonable ability to incorporate the anticipated SCIX streams into DWPF-type glass compositions with TiO{sub 2} concentrations of 4-5 wt % in glass.

  13. Specific outcomes of the research on the radiation stability of the French nuclear glass towards alpha decay accumulation

    NASA Astrophysics Data System (ADS)

    Peuget, S.; Delaye, J.-M.; Jégou, C.

    2014-01-01

    This paper presents an overview of the main results of the French research on the long-term behavior of SON68 nuclear glass towards alpha decay accumulation. The effect of the radiation damage induced by alpha decay and also helium build-up were investigated by examining glass specimens, doped with a short-lived actinide 244Cm, irradiated by light and heavy ions. Additionally, atomistic simulations by molecular dynamics have provided further information on the atomic-scale effects of the macroscopic phenomena observed. These studies have shown that some macroscopic properties vary with the accumulation of alpha decay, but then stabilize after integrated doses of the order of 4 × 1018 α g-1. For example, the glass density diminishes by about 0.6%, its Young's modulus by about 15%, and its hardness by about 30%, while its fracture toughness increases by around 50%. The SEM and TEM characterization showed that the glass is still homogeneous. No phase separation, crystallization or bubbles formation was noticed up to an alpha decay dose corresponding to several thousand years of disposal of nuclear glass canister. Moreover the initial alteration rate of the glass is not significantly affected by the glass damage induced by alpha decays or heavy ions irradiations. The comparison of the macroscopic evolutions of the Cm doped glass with those obtained for glasses irradiated with light or heavy ions (from either experimental and molecular dynamic studies) suggests that the macroscopic evolutions are induced by the nuclear interactions induced by the recoil nuclei of alpha decay. The analysis of the behavior of the glass structure subjected to ballistic effects with various spectroscopic studies, together with the results of atomistic modeling by molecular dynamics, have identified some slight changes in the local order around some cations. Moreover a modification of the medium-range order has also been demonstrated through changes in the bond angles between network

  14. Influence of gamma irradiation effects on the residual alteration rate of the French SON68 nuclear glass

    NASA Astrophysics Data System (ADS)

    Rolland, S.; Tribet, M.; Jollivet, P.; Jégou, C.; Broudic, V.; Marques, C.; Ooms, H.; Toulhoat, P.

    2013-02-01

    The residual rate regime of SON68 nuclear glass has been investigated here by static experiments under external irradiation. The experiments were carried out in a gamma irradiator with 60Co sources. Four dose rates were studied: two high dose rates (5 and 10 kGy h-1) to exacerbate electronic radiation effects, and two lower dose rates (0.8 and 0.05 kGy h-1). The objective of this work is not to assess potential LET effects but to assess more widely electronic effects on the residual rate regime which controls the long term stability of the glass under geological disposal. Fresh glasses were leached in argon atmosphere at 90 °C and at a high surface-area-to-volume ratio (SA/V = 10 000 m-1). Under these conditions the system quickly reaches the residual alteration rate regime. The alteration rate was monitored by solution analyses: the release of glass alteration tracer elements—in particular boron, sodium and lithium—was measured by ICP-AES. The hydrogen peroxide produced by water radiolysis was quantified by chemiluminescence. Radiation effects on the glass and its gel network were characterized by scanning electron microscopy (SEM) and Transmission Electron Microscopy (TEM). Higher H2O2 concentrations were measured on irradiated samples in the presence of glass, suggesting an irradiation effect on the glass and its alteration layer. However, the data obtained on glass alteration show that potential defects or changes induced by gamma irradiation do not modify the kinetics of alteration up to a gamma dose rate of 10 kGy h-1: the residual rates measured for the different dose rates studied are similar and comparable to experiments performed without irradiation. Moreover, these observations are consistent with SEM and TEM characterizations which show that the alteration layer formed under gamma irradiation is similar to the alteration layer formed without irradiation. This study demonstrates that species produced by pure water radiolysis and defects induced by

  15. Resarch investigation on dense scintillation glass for use in total absorption nuclear cascade detectors

    NASA Technical Reports Server (NTRS)

    Hensler, J. R.

    1973-01-01

    Three approaches to the development of a high density scintillation glass were investigated: They include the increase of density of glass systems containing cerium - the only systems which were known to show scintillation, the testing of a novel silicate glass system containing significant concentrations of silver produced by ion exchange and never tested previously, and the hot pressing of a diphasic compact of low density scintillation glass with high density passive glass. In first two cases, while ultraviolet excited fluorescence was maintained in the glasses showing high density, scintillation response to high energy particles was not retained in the case of the cerium containing glasses or developed in the case of the silver containing glasses. In the case of the compacts, the extremely long path length caused by the multiple internal reflections which occur in such a body resulted in attenuation even with glasses of high specific transmission. It is not clear why the scintillation efficiency is not maintained in the higher density cerium containing glasses.

  16. IMPACT OF URANIUM AND THORIUM ON HIGH TIO2 CONCENTRATION NUCLEAR WASTE GLASSES

    SciTech Connect

    Fox, K.; Edwards, T.

    2012-01-11

    This study focused on the potential impacts of the addition of Crystalline Silicotitanate (CST) and Monosodium Titanate (MST) from the Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) glass waste form and the applicability of the DWPF process control models. MST from the Salt Waste Processing Facility (SWPF) is also considered in the study. The KT08-series of glasses was designed to evaluate any impacts of the inclusion of uranium and thorium in glasses containing the SCIX components. All but one of the study glasses were found to be amorphous by X-ray diffraction (XRD). One of the slowly cooled glasses contained a small amount of trevorite, which is typically found in DWPF-type glasses and had no practical impact on the durability of the glass. The measured Product Consistency Test (PCT) responses for the study glasses and the viscosities of the glasses were well predicted by the current DWPF models. No unexpected issues were encountered when uranium and thorium were added to the glasses with SCIX components.

  17. INTRINSIC DOSIMETRY OF GLASS CONTAINERS USED TO TRANSPORT NUCLEAR MATERIALS: Potential Implications to the Field of Nuclear Forensics

    SciTech Connect

    Schwantes, Jon M.; Miller, Steven D.; Piper, Roman K.; Murphy, Mark K.; Amonette, James E.; Bonde, Steven E.; Duckworth, Douglas C.

    2008-09-15

    Thermoluminescence (TL) and Electron Paramagnetic Resonance (EPR) dosimetry were used to measure dose effects in borosilicate glass with time, from 10 minutes to ~60 days following exposure to a dose of up to 10,000 Rad. TL and EPR results were consistent and performed similarly, with both techniques capable of achieving an estimated limit of detection of between 50-100 Rad. Three peaks were identified in the TL glow curve at roughly 110oC, 205oC, and 225oC. The intensity of the 205oC peak was the dominant peak over the time period of this study. The stability of all of the peaks with time since irradiation increased with their corresponding temperature and little or no variation was observed in the glow curve response to a specified total dose attained at different dose rates. The intensity of the 205oC peak decreased logarithmically with time regardless of total dose. Based upon a conservative limit of detection of 330 Rad, a 10,000 Rad dose would still be detected 2.7E3 years after exposure. This paper introduces the concept of intrinsic dosimetry, the consideration of a measured dose received to container walls in concert with the physical characteristics of the radioactive material contained inside those walls, as a method for gathering rather unique pathway information about the history of that sample. Three hypothetical scenarios are presented to introduce this method and to illustrate how intrinsic dosimetry might benefit the fields of nuclear forensics and waste management.

  18. Chemical decomposition of high-level nuclear waste storage/disposal glasses under irradiation. 1998 annual progress report

    SciTech Connect

    Griscom, D.L.; Merzbacher, C.I.

    1998-06-01

    'The objective of this project is to employ the technique of electron spin resonance (ESR), in conjunction with other experimental methods, to study radiation-induced decomposition of vitreous compositions proposed for immobilization/disposal of high-level nuclear wastes (HLW) or excess weapons plutonium. ESR is capable of identifying, even at the parts-per-million level, displaced atoms, ruptured bonds, and free radicals created by radiation in such glassy forms. For example, one of the scientific goals is to determine whether ESR-detectable superoxide (O{sub 2}{sup -}) and ozonide (O{sub 3}{sup -}) ions are precursors of radiation-induced oxygen gas bubbles reported by other investigators. The fundamental understandings obtained in this study will enable reliable predictions of the long-term effects of and decays of the immobilized radionuclides on HLW glasses. This report represents the results of an 18-month effort performed under a 3-year research award. Four categories of materials were studied: (1) several actual and proposed HLW glass compositions fabricated at Savannah River Technology Center (SRTC), samples of which had been irradiated to a dose of 30 MGy (1 Gy = 100 rad) to simulate decay effects, (2) several high-iron phosphate glasses fabricated at the University of Missouri-Rolla (UMR), (3) one other model HLW glass and several simulated natural glasses which had been implanted with 160-keV He{sup +} ions to simulate-decay damage, and (4) an actual geological glass damaged by decays of trace amounts of contained {sup 238}U and {sup 232}Th over a period of 65 Myears. Among the category-1 materials were two samples of Defense Waste Processing Facility (DWPF) borosilicate glasses modeling compositions currently being used to vitrify HLW at SRTC. The ESR spectra recorded for the unirradiated DWPF-glass simulants were attributable to Fe 3{sup +} ions. The 30-MGy irradiation was found to change the Fe{sup 3+} concentration of these glasses by a

  19. The reaction of synthetic nuclear waste glass in steam and hydrothermal solution

    SciTech Connect

    Ebert, W.L.; Bates, J.K.

    1989-12-31

    Glass monoliths of the WVCM 44, WVCM 50, SRL 165, and SRL 202 compositions were reacted in steam and in hydrothermal liquid at 200{degree}C. The glass reaction resulted in the formation of leached surface layers in both environments. The reaction in steam proceeds at a very low rate until precipitates form, after which the glass reaction proceeds at a greater rate. Precipitates were formed on all glass types reacted in steam. The assemblage of phases formed was unique to each glass type, but several precipitates were common to all glasses, including analcime, gyrolite, and weeksite. Reaction in steam occurs in a thin layer of condensed water which becomes saturated with respect to the observed phases after only a few days of reaction. The reaction in steam is accelerated relative to reaction in hydrothermal liquid in the sense that secondary phases from after a shorter reaction time, that is, after less glass has reacted, because of the smaller effective leachant volume present in the steam environment. A knowledge of the secondary phases which form and their influence on the glass reaction rate is crucial to the modeling effort of the repository program. 9 refs., 3 figs., 2 tabs.

  20. Towards optimization of nuclear waste glass: Constraints, property models, and waste loading

    SciTech Connect

    Hrma, P.

    1994-04-01

    Vitrification of both low- and high-level wastes from 177 tanks at Hanford poses a great challenge to glass makers, whose task is to formulate a system of glasses that are acceptable to the federal repository for disposal. The enormous quantity of the waste requires a glass product of the lowest possible volume. The incomplete knowledge of waste composition, its variability, and lack of an appropriate vitrification technology further complicates this difficult task. A simple relationship between the waste loading and the waste glass volume is presented and applied to the predominantly refractory (usually high-activity) and predominantly alkaline (usually low-activity) waste types. Three factors that limit waste loading are discussed, namely product acceptability, melter processing, and model validity. Glass formulation and optimization problems are identified and a broader approach to uncertainties is suggested.

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

    NASA Astrophysics Data System (ADS)

    Neeway, James J.; Abdelouas, Abdesselam; Ribet, Solange; El Mendili, Yassine; Schumacher, Stéphan; Grambow, Bernd

    2015-04-01

    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 32Si-doped SON68 also suggest that the movement of Si through the claystone is controlled by a chemically coupled transport with a Si retention factor, Kd, of 900 mL/g.

  2. First principles process-product models for vitrification of nuclear waste: Relationship of glass composition to glass viscosity, resistivity, liquidus temperature, and durability

    SciTech Connect

    Jantzen, C.M.

    1991-01-01

    Borosilicate glasses will be used in the USA and in Europe to immobilize radioactive high level liquid wastes (HLLW) for ultimate geologic disposal. Process and product quality models based on glass composition simplify the fabrication of the borosilicate glass while ensuring glass processability and quality. The process model for glass viscosity is based on a relationship between the glass composition and its structural polymerization. The relationship between glass viscosity and electrical resistivity is also shown to relate to glass polymerization. The process model for glass liquidus temperature calculates the solubility of the liquidus phases based on the free energies of formation of the precipitating species. The durability product quality model is based on the calculation of the thermodynamic hydration free energy from the glass composition.

  3. First principles process-product models for vitrification of nuclear waste: Relationship of glass composition to glass viscosity, resistivity, liquidus temperature, and durability

    SciTech Connect

    Jantzen, C.M.

    1991-12-31

    Borosilicate glasses will be used in the USA and in Europe to immobilize radioactive high level liquid wastes (HLLW) for ultimate geologic disposal. Process and product quality models based on glass composition simplify the fabrication of the borosilicate glass while ensuring glass processability and quality. The process model for glass viscosity is based on a relationship between the glass composition and its structural polymerization. The relationship between glass viscosity and electrical resistivity is also shown to relate to glass polymerization. The process model for glass liquidus temperature calculates the solubility of the liquidus phases based on the free energies of formation of the precipitating species. The durability product quality model is based on the calculation of the thermodynamic hydration free energy from the glass composition.

  4. Leaching Savannah River Plant nuclear waste glass in a saturated tuff environment

    SciTech Connect

    Bibler, N.E.; Wicks, G.G.; Oversby, V.M.

    1984-11-01

    Samples of SRP glass containing either simulated or actual radioactive waste were leached at 90{sup 0}C under conditions simulating a saturated tuff repository environment. The leach vessels were fabricated of tuff and actual tuff groundwater was used. Thus, the glass was leached only in the presence of those materials (including the Type 304L stainless steel canister material) that would be in the actual repository. Tests were performed for time periods up t 6 months at a SA/V ratio of 100 m{sup -1}. Results with glass containing simulated waste indicated that stainless steel canister material around the glass did not significantly affect the leaching. Based on Li and B (elements not in significant concentrations in the tuff or tuff groundwater), glass containing simulated waste leached identically to glass containing actual radioactive waste. The tuff buffered the pH so that only a slight increase was observed as a result of leaching. Results with glass containing actual radioactive waste indicated that tuff reduced the concentrations of Cs-137, Sr-90, and Pu-238 in the free groundwater in the simulated repository by 10 to 100X. Also, radiolysis of the groundwater by the glass (approximately 1000 rad/h) did not significantly affect the pH in the presence of tuff. Measured normalized mass losses in the presence of tuff for the glass based on Cs-137, Sr-90, and Pu-238 in the free groundwater were extremely low, nominally 0.02, 0.02, and 0.005 g/m{sup 2}, respectively, indicating that the glass-tuff system retained radionuclides well. 9 references, 2 figures, 3 tables.

  5. Understanding of the mechanical and structural changes induced by alpha particles and heavy ions in the French simulated nuclear waste glass

    NASA Astrophysics Data System (ADS)

    Karakurt, G.; Abdelouas, A.; Guin, J.-P.; Nivard, M.; Sauvage, T.; Paris, M.; Bardeau, J.-F.

    2016-07-01

    Borosilicate glasses are considered for the long-term confinement of high-level nuclear wastes. External irradiations with 1 MeV He+ ions and 7 MeV Au5+ ions were performed to simulate effects produced by alpha particles and by recoil nuclei in the simulated SON68 nuclear waste glass. To better understand the structural modifications, irradiations were also carried out on a 6-oxides borosilicate glass, a simplified version of the SON68 glass (ISG glass). The mechanical and macroscopic properties of the glasses were studied as function of the deposited electronic and nuclear energies. Alpha particles and gold ions induced a volume change up to -0.7% and -2.7%, respectively, depending on the glass composition. Nano-indentations tests were used to determine the mechanical properties of the irradiated glasses. A decrease of about -22% to -38% of the hardness and a decrease of the reduced Young's modulus by -8% were measured after irradiations. The evolution of the glass structure was studied by Raman spectroscopy, and also 11B and 27Al Nuclear Magnetic Resonance (MAS-NMR) on a 20 MeV Kr irradiated ISG glass powder. A decrease of the silica network connectivity after irradiation with alpha particles and gold ions is deduced from the structural changes observations. NMR spectra revealed a partial conversion of BO4 to BO3 units but also a formation of AlO5 and AlO6 species after irradiation with Kr ions. The relationships between the mechanical and structural changes are also discussed.

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

    SciTech Connect

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

    2015-02-01

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

  7. CRYSTALLIZATION IN MULTICOMPONENT GLASSES

    SciTech Connect

    KRUGER AA; HRMA PR

    2009-10-08

    In glass processing situations involving glass crystallization, various crystalline forms nucleate, grow, and dissolve, typically in a nonuniform temperature field of molten glass subjected to convection. Nuclear waste glasses are remarkable examples of multicomponent vitrified mixtures involving partial crystallization. In the glass melter, crystals form and dissolve during batch-to-glass conversion, melter processing, and product cooling. Crystals often agglomerate and sink, and they may settle at the melter bottom. Within the body of cooling glass, multiple phases crystallize in a non-uniform time-dependent temperature field. Self-organizing periodic distribution (the Liesegnang effect) is common. Various crystallization phenomena that occur in glass making are reviewed.

  8. A review of literature pertaining to the leaching and sorption of radionuclides associated with nuclear explosive melt glasses

    SciTech Connect

    Smith, D.K.

    1993-05-01

    For the purposes of groundwater characterization, environmental remediation and health risk assessment, the mechanism and rate by which radionuclides bound within nuclear device melt glass are manifest in Nevada Test Site groundwaters must be known. Exchange between radionuclides and groundwater is dominated by the kinetics of leaching and the resultant sorption of derivative nuclides by minerals along the flow-path. In this context, a survey of the report literature has been conducted to review work related to these subjects. This report provides a representative, although not exhaustive, summary of the literature; because of the specialized nature of nuclear melt glass, emphasis was given to the report literature available from Lawrence Livermore and Los Alamos National Laboratories, the Department of Energy and its predecessor agencies and pertinent contractors. Where data is corroborated in journal literature, those references are also included. Before the risk to ground waters is estimated with any accuracy, recommendations for continued future work integrate systematic characterization of melt glass with leaching studies of these heterogeneous matrices.

  9. The liquidus temperature of nuclear waste glasses: an international Round-Robin Study

    SciTech Connect

    Riley, Brian J.; Hrma, Pavel R.; Vienna, John D.; Schweiger, Michael J.; Rodriguez, Carmen P.; Crum, Jarrod V.; Lang, Jesse B.; Marra, James C.; Johnson, Fabienne; Peeler, David K.; Leonelli, Cristina; Ferrari, Anna M.; Lancellotti, Isabella; Dussossoy, Jean-Lue A.; Hand, Russell J.; Schofield, James M.; Connelly, Andrew J.; Short, Rick; Harrison, Mike T.

    2012-12-01

    Ten institutions from five countries participated in a Round Robin study to contribute to the Precision and Bias section of an American Society for Testing and Materials standard procedure that Pacific Northwest National Laboratory (PNNL) is developing for measuring the liquidus temperature (TL) of radioactive and simulated waste glasses. In this study, three separate TL measurement methods were a gradient temperature (GT) method, a uniform temperature (UT) method, and a crystal fraction extrapolation (CF) method. Three different glasses were measured with a combination of these three methods. The TL values reported by different institutions are generally consistent and vary within a narrow range. The precision of a TL measurement was evaluated as ±10°C regardless of the method used for making the measurement. The Round Robin glasses were all previously studied at PNNL and included ARG-1 (Glass A), Zr-9 (Glass B), and AmCm2-19 (Glass C), with measured TL values spanning the temperature range ~960-1240°C. The three methods discussed here in more detail are the GT, UT, and CF methods. A best-case precision for TL has been obtained from the data, even though the data were not acquired for all three glasses using all three methods from each participating organization.

  10. Helium diffusion coefficient measurements in R7T7 nuclear glass by 3He(d,α) 1H nuclear reaction analysis

    NASA Astrophysics Data System (ADS)

    Chamssedine, F.; Sauvage, T.; Peuget, S.; Fares, T.; Martin, G.

    2010-05-01

    The immobilization of fission products and minor actinides by vitrification is the reference process for industrial management of high-level radioactive wastes generated by spent fuel reprocessing. Radiation damage and radiogenic helium accumulation must be specifically studied to evaluate the effects of minor actinide alpha decay on the glass long-term behavior under repository conditions. A specific experimental study was conducted for a comprehensive evaluation of the behavior of helium and its diffusion mechanisms in borosilicate nuclear waste glass. Helium production was simulated by external implantation with 3He ions at a concentration (≈1 at.%) 30 times higher than obtained after 10,000 years of storage. Helium diffusion coefficients as a function of temperature were extracted from the depth profiles after annealing. The 3He(d,α) 1H nuclear reaction analysis (NRA) technique was successfully adopted for low-temperature in situ measurements of depth profiles. Its high depth resolution revealed helium mobility at temperatures as low as 253 K and the presence of a trapped helium fraction. The diffusion coefficients of un-trapped helium atoms follow an Arrhenius law between 253 K and 323 K. An activation energy of 0.55 ± 0.03 eV was determined, which is consistent with a process controlled by diffusion in the glass free volume.

  11. An International Initiative on Long-Term Behavior of High-Level Nuclear Waste Glass

    SciTech Connect

    Gin, Stephane; Abdelouas, Abdesselam; Criscenti, Louise J; Ebert, William L; Ferrand, K; Geisler, T; Harrison, Michael T; Inagaki, Y; Mitsui, S; Mueller, K T; Marra, James C; Pantano, Carlo G; Pierce, Eric M; Ryan, Joseph V; Schofield, J M; Steefel, Carl I; Vienna, John D.

    2013-01-01

    Nations using borosilicate glass as an immobilization material for radioactive waste have reinforced the importance of scientific collaboration to obtain a consensus on the mechanisms controlling the longterm dissolution rate of glass. This goal is deemed to be crucial for the development of reliable performance assessment models for geological disposal. The collaborating laboratories all conduct fundamental and/or applied research using modern materials science techniques. This paper briefly reviews the radioactive waste vitrification programs of the six participant nations and summarizes the current state of glass corrosion science, emphasizing the common scientific needs and justifications for on-going initiatives.

  12. Development of Vitrification Process and Glass Formulation for Nuclear Waste Conditioning

    SciTech Connect

    Petitjean, V.; Fillet, C.; Boen, R.; Veyer, C.; Flament, T.

    2002-02-26

    The vitrification of high-level waste is the internationally recognized standard to minimize the impact to the environment resulting from waste disposal as well as to minimize the volume of conditioned waste to be disposed of. COGEMA has been vitrifying high-level waste industrially for over 20 years and is currently operating three commercial vitrification facilities based on a hot metal crucible technology, with outstanding records of safety, reliability and product quality. To further increase the performance of vitrification facilities, CEA and COGEMA have been developing the cold crucible melter technology since the beginning of the 1980s. This type of melter is characterized by a virtually unlimited equipment service life and a great flexibility in dealing with various types of waste and allowing development of high temperature matrices. In complement of and in parallel with the vitrification process, a glass formulation methodology has been developed by the CEA in order to tailor matrices for the wastes to be conditioned while providing the best adaptation to the processing technology. The development of a glass formulation is a trade-off between material properties and qualities, technical feasibility, and disposal safety criteria. It involves non-radioactive and radioactive laboratories in order to achieve a comprehensive matrix qualification. Several glasses and glass ceramics have thus been studied by the CEA to be compliant with industrial needs and waste characteristics: glasses or other matrices for a large spectrum of fission products, or for high contents of specifics elements such as sodium, phosphate, iron, molybdenum, or actinides. New glasses or glass-ceramics designed to minimize the final wasteform volume for solutions produced during the reprocessing of high burnup fuels or to treat legacy wastes are now under development and take benefit from the latest CEA hot-laboratories and technology development. The paper presents the CEA state

  13. Characterization of high level nuclear waste glass samples following extended melter idling

    SciTech Connect

    Fox, K.

    2015-06-16

    The Savannah River Site Defense Waste Processing Facility (DWPF) melter was recently idled with glass remaining in the melt pool and riser for approximately three months. This situation presented a unique opportunity to collect and analyze glass samples since outages of this duration are uncommon. The objective of this study was to obtain insight into the potential for crystal formation in the glass resulting from an extended idling period. The results will be used to support development of a crystal-tolerant approach for operation of the high level waste melter at the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Two glass pour stream samples were collected from DWPF when the melter was restarted after idling for three months. The samples did not contain crystallization that was detectible by X-ray diffraction. Electron microscopy identified occasional spinel and noble metal crystals of no practical significance. Occasional platinum particles were observed by microscopy as an artifact of the sample collection method. Reduction/oxidation measurements showed that the pour stream glasses were fully oxidized, which was expected after the extended idling period. Chemical analysis of the pour stream glasses revealed slight differences in the concentrations of some oxides relative to analyses of the melter feed composition prior to the idling period. While these differences may be within the analytical error of the laboratories, the trends indicate that there may have been some amount of volatility associated with some of the glass components, and that there may have been interaction of the glass with the refractory components of the melter. These changes in composition, although small, can be attributed to the idling of the melter for an extended period. The changes in glass composition resulted in a 70-100 °C increase in the predicted spinel liquidus temperature (TL) for the pour stream glass samples relative to the analysis of the melter feed prior to

  14. Minor component study for simulated high-level nuclear waste glasses (Draft)

    SciTech Connect

    Li, H.; Langowskim, M.H.; Hrma, P.R.; Schweiger, M.J.; Vienna, J.D.; Smith, D.E.

    1996-02-01

    Hanford Site single-shell tank (SSI) and double-shell tank (DSI) wastes are planned to be separated into low activity (or low-level waste, LLW) and high activity (or high-level waste, HLW) fractions, and to be vitrified for disposal. Formulation of HLW glass must comply with glass processibility and durability requirements, including constraints on melt viscosity, electrical conductivity, liquidus temperature, tendency for phase segregation on the molten glass surface, and chemical durability of the final waste form. A wide variety of HLW compositions are expected to be vitrified. In addition these wastes will likely vary in composition from current estimates. High concentrations of certain troublesome components, such as sulfate, phosphate, and chrome, raise concerns about their potential hinderance to the waste vitrification process. For example, phosphate segregation in the cold cap (the layer of feed on top of the glass melt) in a Joule-heated melter may inhibit the melting process (Bunnell, 1988). This has been reported during a pilot-scale ceramic melter run, PSCM-19, (Perez, 1985). Molten salt segregation of either sulfate or chromate is also hazardous to the waste vitrification process. Excessive (Cr, Fe, Mn, Ni) spinel crystal formation in molten glass can also be detrimental to melter operation.

  15. Deuteron NMR (Nuclear Magnetic Resonance) in relation to the glass transition in polymers

    NASA Technical Reports Server (NTRS)

    Roessler, E.; Sillescu, H.; Spiess, H. W.; Wallwitz, R.

    1983-01-01

    H-2NMR is introduced as a tool for investigating slow molecular motion in the glass transition region of amorphous polymers. In particular, we compare H-2 spin alignment echo spectra of chain deuterated polystyrene with model calculations for restricted rotational Brownian motion. Molecular motion in the polyztyrene-toluene system has been investigated by analyzing H-2NMR of partially deuterated polystyrene and toluene, respectively. The diluent mobility in the mixed glass has been decomposed into solid and liquid components where the respective average correlation times differ by more than 5 decades.

  16. Plutonium leaching from a reference nuclear waste glass in synthetic interstitial claywater

    SciTech Connect

    Wang, Lian; Van Iseghem, P.

    1993-12-31

    The steady-state concentration of Pu was measured upon leaching Pu doped glass in synthetic interstitial claywater (SIC) and humic acid free interstitial solution (IS). The solubility of PuO{sub 2}{center_dot}xH{sub 2}O (am) was determined in the same chemical condition. The results then were compared with the Pu solubility calculated by using a published solubility product and complex stability constants. The humic acid (HA) influence on the Pu leaching from the glass and the colloid formation were investigated.

  17. Kinetics of Cold-Cap Reactions for Vitrification of Nuclear Waste Glass Based on Simultaneous Differential Scanning Calorimetry - Thermogravimetry (DSC-TGA) and Evolved Gas Analysis (EGA)

    SciTech Connect

    Rodriguez, Carmen P.; Pierce, David A.; Schweiger, Michael J.; Kruger, Albert A.; Chun, Jaehun; Hrma, Pavel R.

    2013-12-03

    For vitrifying nuclear waste glass, the feed, a mixture of waste with glass-forming and modifying additives, is charged onto the cold cap that covers 90-100% of the melt surface. The cold cap consists of a layer of reacting molten glass floating on the surface of the melt in an all-electric, continuous glass melter. As the feed moves through the cold cap, it undergoes chemical reactions and phase transitions through which it is converted to molten glass that moves from the cold cap into the melt pool. The process involves a series of reactions that generate multiple gases and subsequent mass loss and foaming significantly influence the mass and heat transfers. The rate of glass melting, which is greatly influenced by mass and heat transfers, affects the vitrification process and the efficiency of the immobilization of nuclear waste. We studied the cold-cap reactions of a representative waste glass feed using both the simultaneous differential scanning calorimetry thermogravimetry (DSC-TGA) and the thermogravimetry coupled with gas chromatography-mass spectrometer (TGA-GC-MS) as complementary tools to perform evolved gas analysis (EGA). Analyses from DSC-TGA and EGA on the cold-cap reactions provide a key element for the development of an advanced cold-cap model. It also helps to formulate melter feeds for higher production rate.

  18. Hydrothermal Alteration of Glass from Underground Nuclear Tests: Formation and Transport of Pu-clay Colloids at the Nevada National Security Site

    SciTech Connect

    Zavarin, M.; Zhao, P.; Joseph, C.; Begg, J.; Boggs, M.; Dai, Z.; Kersting, A. B.

    2015-05-27

    The testing of nuclear weapons at the Nevada National Security Site (NNSS), formerly the Nevada Test Site (NTS), has led to the deposition of substantial quantities of plutonium into the environment. Approximately 2.8 metric tons (3.1×104 TBq) of Pu were deposited in the NNSS subsurface as a result of underground nuclear testing. While 3H is the most abundant anthropogenic radionuclide deposited in the NNSS subsurface (4.7×106 TBq), plutonium is the most abundant from a molar standpoint. The only radioactive elements in greater molar abundance are the naturally occurring K, Th, and U isotopes. 239Pu and 240Pu represent the majority of alpha-emitting Pu isotopes. The extreme temperatures associated with underground nuclear tests and the refractory nature of Pu results in most of the Pu (98%) being sequestered in melted rock, referred to as nuclear melt glass (Iaea, 1998). As a result, Pu release to groundwater is controlled, in large part, by the leaching (or dissolution) of nuclear melt glass over time. The factors affecting glass dissolution rates have been studied extensively. The dissolution of Pu-containing borosilicate nuclear waste glasses at 90ºC has been shown to lead to the formation of dioctahedral smectite colloids. Colloid-facilitated transport of Pu at the NNSS has been observed. Recent groundwater samples collected from a number of contaminated wells have yielded a wide range of Pu concentrations from 0.00022 to 2.0 Bq/L. While Pu concentrations tend to fall below the Maximum Contaminant Level (MCL) established by the Environmental Protection Agency (EPA) for drinking water (0.56 Bq/L), we do not yet understand what factors limit the Pu concentration or its transport behavior. To quantify the upper limit of Pu concentrations produced as a result of melt glass dissolution and determine the nature of colloids and Pu associations, we performed a 3 year nuclear melt glass dissolution experiment

  19. Europium Structural Effect on a Borosilicate Glass of Nuclear Interest: Combining Experimental Techniques with Reverse Monte Carlo Modelling to Investigate Short to Medium Range Order

    NASA Astrophysics Data System (ADS)

    Bouty, O.; Delaye, J. M.; Peuget, S.; Charpentier, T.

    In-depth understanding of the effects of actinides in borosilicate glass matrices used for nuclear waste disposal is of great importance for nuclear spent fuel reprocessing cycle and fission products immobilization. This work carried out on ternary simplified glasses (Si, B, Na) doped respectively with 1 mol. % and 3.85 mol. % europium, presents a comprehensive study on the behaviour of trivalent europium taken as a surrogate of trivalent actinides. Neutron scattering, Wide Angle X- ray Scattering, Nuclear Magnetic Resonance, Raman Spectroscopy and Reverse Monte Carlo simulations were performed. For both glasses, it was found that europium coordination number was around 6 ± 0.2, revealing an octahedral spatial configuration. Europium species accommodates in both silicate and borate site distributions but preferentially in the silicate network. Europium induces a IVB/IIIB ratio decrease and a silicate network polymerization according to NMR 29Si chemical shift and Raman spectra evolution.

  20. ANNUAL REPORT. IRON PHOSPHATE GLASSES: AN ALTERNATIVE FOR VITRIFYING CERTAIN NUCLEAR WASTES

    EPA Science Inventory

    The two multifaceted objectives of this research project are to (1) investigate the feasibility of vitrifying 2 or 3 high priority wastes, as identified by the Tank Focus Area group, using iron phosphate glasses (i.e., determine chemical durability as a function of waste loading,...

  1. Crystallization in simulated glasses from Hanford high-level nuclear waste composition range

    SciTech Connect

    Kim, Dong-Sang; Hrma, P.; Smith, D.E.; Schweiger, M.J.

    1993-04-01

    Glass crystallization was investigated as part of a property-composition relationship study of Hanford waste glasses. Non-radioactive glass samples were heated in a gradient furnace over a wide range of temperatures. The liquidus temperature was measured, and primary crystalline phases were determined using optical microscopy and Scanning Electron Microscopy with Energy Dispersive Spectrometry (SEM/EDS). Samples have also been heat treated according to a simulated canister centerline cooling curve. The crystalline phases in these samples have been identified by optical microscopy, SEM/EDS, and X-ray diffraction (XRD). Major components of the borosilicate glasses that were melted at approximately 1150{degrees}C were SiO{sub 2}, B{sub 2}O{sub 3}, Na{sub 2}O, Li{sub 2}O, CaO, MgO, Fe{sub 2}O{sub 3}, Al{sub 2}O{sub 3}, ZrO{sub 2}, and ``Others`` (sum of minor components). The major crystalline phases identified in this study were zircon, nepheline, calcium silicate, lithium silicate, and a range of solid solutions from clinopyroxenes, orthopyroxenes, olivines, and spiners.

  2. New functionality of chalcogenide glasses for radiation sensing of nuclear wastes.

    PubMed

    Ailavajhala, M S; Gonzalez-Velo, Y; Poweleit, C D; Barnaby, H J; Kozicki, M N; Butt, D P; Mitkova, M

    2014-03-30

    Data about gamma radiation induced effects in Ge40Se60 chalcogenide thin films and radiation induced silver diffusion within these are presented. Blanket films and devices were created to study the structural changes, diffusion products, and device performance. Raman spectroscopy, X-ray diffraction, current vs. voltage (I-V) and impedance measurements expound the behavior of Ge40Se60 glass and silver diffusion within this glass under radiation. Raman study shows that there is a decrease in the area ratio between edge shared and corner shared structural units revealing structural reorganization occurring in the glasses as a result of gamma radiation. X-ray diffraction studies revealed that with sufficiently radiation dose it is also possible to create Ag2Se in selenium-depleted systems. Oxidation of the Ge enriched chalcogenide backbone is confirmed through the electrical performance of the sensing elements based on these films. Combination of these structural and diffusion products influences the device performance. The I-V behavior is characterized by increase in current and then stabilization as a function of radiation dose. Additionally, device modeling is also presented using Silvaco software and analytical methods to shed light on the device behavior. This type of sensor design and material characterizations facilitate in improving the radiation sensing capabilities of silver containing chalcogenide glass thin films. PMID:24332317

  3. Cold-cap reactions in vitrification of nuclear waste glass: experiments and modeling

    SciTech Connect

    Chun, Jaehun; Pierce, David A.; Pokorny, Richard; Hrma, Pavel R.

    2013-05-01

    Cold-cap reactions are multiple overlapping reactions that occur in the waste-glass melter during the vitrification process when the melter feed is being converted to molten glass. In this study, we used differential scanning calorimetry (DSC) to investigate cold-cap reactions in a high-alumina high-level waste melter feed. To separate the reaction heat from both sensible heat and experimental instability, we employed the run/rerun method, which enabled us to define the degree of conversion based on the reaction heat and to estimate the heat capacity of the reacting feed. Assuming that the reactions are nearly independent and can be approximated by the nth order kinetics, we obtained the kinetic parameters using the Kissinger method combined with least squares analysis. The resulting mathematical simulation of the cold-cap reactions provides a key element for the development of an advanced cold-cap model.

  4. Development and testing of matrices for the encapsulation of glass and ceramic nuclear waste forms.

    SciTech Connect

    Wald, J.W.; Brite, D.W.; Gurwell, W.E.; Buckwalter, C.Q.; Bunnell, L.R.; Gray, W.J.; Blair, H.T.; Rusin, J.M.

    1982-02-01

    This report details the results of research on the matrix encapsulation of high level wastes at PML over the past few years. The demonstrations and tests described were designed to illustrate how the waste materials are effected when encapsulated in an inert matrix. Candidate materials evaluated for potential use as matrices for encapslation of pelletized ceramics or glass marbles were categorized into four groups: metals, glasses, ceramics, and graphite. Two processing techniques, casting and hot pressing, were investigated as the most promising methods of formation or densification of the matrices. The major results reported deal with the development aspects. However, chemical durability tests (leach tests) of the matrix materials themselves and matrix-waste form composites are also reported. Matrix waste forms can provide a low porosity, waste-free barrier resulting in increased leach protection, higher impact strength and improved thermal conductivity compared to unencapsulated glass or ceramic waste materials. Glass marbles encapsulated in a lead matrix offer the most significant improvement in waste form stability of all combinations evaluated. This form represents a readily demonstrable process that provides high thermal conductivity, mechanical shock resistance, radiation shielding and increased chemical durability through both a chemical passivation mechanism and as a physical barrier. Other durable matrix waste forms evaluated, applicable primarily to ceramic pellets, involved hot-pressed titanium or TiO/sub 2/ materials. In the processing of these forms, near 100% dense matrices were obtained. The matrix materials had excellent compatibility with the waste materials and superior potential chemical durability. Cracking of the hot-pressed ceramic matrix forms, in general, prevented the realization of their optimum properties.

  5. Chemical decomposition of high-level nuclear waste storage/disposal glasses under irradiation. 1997 annual progress report

    SciTech Connect

    Griscom, D.L.; Merzbacher, C.I.

    1997-01-01

    'The objective of this research is to use the sensitive technique of electron spin resonance (ESR) to look for evidence of radiation-induced chemical decomposition of vitreous forms contemplated for immobilization of plutonium and/or high-level nuclear wastes, to interpret this evidence in terms of existing knowledge of glass structure, and to recommend certain materials for further study by other techniques, particularly electron microscopy and measurements of gas evolution by high-vacuum mass spectroscopy. Previous ESR studies had demonstrated that an effect of y rays on a simple binary potassium silicate glass was to induce superoxide (O{sub 2}{sup -}) and ozonide (O{sub 3}{sup -}) as relatively stable product of long-term irradiation Accordingly, some of the first experiments performed as a part of the present effort involved repeating this work. A glass of composition 44 K{sub 2}O: 56 SiO{sub 2} was prepared from reagent grade K{sub 2}CO3 and SiO{sub 2} powders melted in a Pt crucible in air at 1,200 C for 1.5 hr. A sample irradiated to a dose of 1 MGy (1 MGy = 10{sup 8} rad) indeed yielded the same ESR results as before. To test the notion that the complex oxygen ions detected may be harbingers of radiation-induced phase separation or bubble formation, a small-angle neutron scattering (SANS) experiment was performed. SANS is theoretically capable of detecting voids or bubbles as small as 10 \\305 in diameter. A preliminary experiment was carried out with the collaboration of Dr. John Barker (NIST). The SANS spectra for the irradiated and unirradiated samples were indistiguishable. A relatively high incoherent background (probably due to the presence of protons) may obscure scattering from small gas bubbles and therefore decrease the effective resolution of this technique. No further SANS experiments are planned at this time.'

  6. Direct conversion of surplus fissile materials, spent nuclear fuel, and other materials to high-level-waste glass

    SciTech Connect

    Forsberg, C.W.; Elam, K.R.

    1995-01-31

    With the end of the cold war the United States, Russia, and other countries have excess plutonium and other materials from the reductions in inventories of nuclear weapons. The United States Academy of Sciences (NAS) has recommended that these surplus fissile materials (SFMs) be processed so they are no more accessible than plutonium in spent nuclear fuel (SNF). This spent fuel standard, if adopted worldwide, would prevent rapid recovery of SFMs for the manufacture of nuclear weapons. The NAS recommended investigation of three sets of options for disposition of SFMs while meeting the spent fuel standard: (1) incorporate SFMs with highly radioactive materials and dispose of as waste, (2) partly burn the SFMs in reactors with conversion of the SFMs to SNF for disposal, and (3) dispose of the SFMs in deep boreholes. The US Government is investigating these options for SFM disposition. A new method for the disposition of SFMs is described herein: the simultaneous conversion of SFMs, SNF, and other highly radioactive materials into high-level-waste (HLW) glass. The SFMs include plutonium, neptinium, americium, and {sup 233}U. The primary SFM is plutonium. The preferred SNF is degraded SNF, which may require processing before it can be accepted by a geological repository for disposal.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  9. Application of the NNWSI [Nevada Nuclear Waste Storage Investigations] unsaturated test method to actinide doped SRL [Savannah River Laboratory] 165 type glass

    SciTech Connect

    Bates, J.K.; Gerding, T.J.

    1990-08-01

    The results of tests done using the Unsaturated Test Method are presented. These tests, done to determine the suitability of glass in a potential high-level waste repository as developed by the Nevada Nuclear Waste Storage Investigations Project, simulate conditions anticipated for the post-containment phase of the repository when only limited contact between the waste form and water is expected. The reaction of glass occurs via processes that are initiated due to glass/water vapor and glass/liquid water contact. Vapor interaction results in the initiation of an exchange process between water and the more mobile species (alkalis and boron) in the glass. The liquid reaction produces interactions similar to those seen in standard leaching tests, except due to the limited amount of water present and the presence of partially sensitized 304L stainless steel, the formation of reaction products greatly exceeds that found in MCC-1 type leach tests. The effect of sensitized stainless steel on the reaction is to enhance breakdown of the glass matrix thereby increasing the release of the transuranic elements from the glass. However, most of the Pu and Am released is entrained by either the metal components of the test or by the reaction phases, and is not released to solution. 16 refs., 20 figs., 17 tabs.

  10. Characterisation of heterogeneous molybdate and chromate phase assemblages in model nuclear waste glasses by multinuclear magnetic resonance spectroscopy.

    PubMed

    Greer, Brandon J; Kroeker, Scott

    2012-05-28

    A series of sodium borosilicate glasses containing cesium, molybdenum, and chromium was prepared to investigate the partitioning of chromium amongst the glass and phase-separated crystalline molybdates. The precipitates were examined by (133)Cs, (23)Na, and (95)Mo MAS NMR, revealing a phase assemblage consisting of Na(2)MoO(4), Na(2)MoO(4)·2H(2)O, Cs(2)MoO(4), Cs(2)CrO(4), CsNaMoO(4)·2H(2)O, and Cs(3)Na(MoO(4))(2). (133)Cs MAS NMR indicates random substitution of Cr into the Mo sites of Cs(3)Na(MoO(4))(2) and provides a quantitative assessment of Cr incorporation. The sample compositions were verified by various analytical techniques and highlight the centrality of NMR in the identification and quantification of heterogeneous crystalline composites, including sensitivity to cationic substitution. The observation and facile interconversion of hydrated phases invites careful consideration of these materials for nuclear waste disposal. PMID:22532058

  11. Glass-transition temperature gradient in nanocomposites: evidence from nuclear magnetic resonance and differential scanning calorimetry.

    PubMed

    Papon, Aurélie; Montes, Hélène; Hanafi, Mohamed; Lequeux, François; Guy, Laurent; Saalwächter, Kay

    2012-02-10

    The slowing-down of the dynamics of a polymer chain near a surface has been observed for many years now. Here we show that the behavior of model nanocomposites can be quantitatively described with a gradient of glass-transition temperature. We describe with a single parameter-the range of this gradient-the temperature and solvent effect on the spin relaxation dynamics. Moreover, this parameter allows a quantitative description of the nanocomposite calorimetric response from the one of the bulk polymer. PMID:22401088

  12. Biological effect of Acidithiobacillus thiooxidans on some potentially toxic elements during alteration of SON 68 nuclear glass

    NASA Astrophysics Data System (ADS)

    Bachelet, M.; Crovisier, J. L.; Stille, P.; Vuilleumier, S.; Geoffroy, V.

    2009-04-01

    Although underground nuclear waste repositories are not expected to be favourable places for microbial activity, one should not exclude localized action of extremophilic bacteria on some materials involved in the storage concept. Among endogenous or accidentally introduced acidophiles, some are susceptible to lead to a locally drastic decreased in pH, with potential consequences on materials corrosion. Experiments were performed with Acidithiobacillus thiooxidans on 100-125 m french reference nuclear glass SON68 grains in a mineral medium under static conditions during 60 days at 25degC. Growth medium was periodically renewed and analyzed by ICP-AES and ICP-MS spectrometry for both major, trace and ultra-trace elements. Biofilm formation was evidenced by confocal laser microscopy, staining DNA with ethidium bromide and exopolysaccharides with calcofluor white. Biofilm thickness around material grains exceeded 20 m under the chosen experimental conditions. It can be noticed that while numerous studies on biofilm formation upon interaction between Acidithiobacillus ferrooxidans and materials are found in the literature, evidence for biofilm formation is still scarce for the case of the acidophilic bacterium A. thiooxidans. Presence of biofilm is a key parameter for material alteration at the solid/solution interface in biotic systems. Indeed, various constitutive elements of materials trapped in the polyanionic polymer of biofilm may also influence the alteration process. In particular, biofilm may reduce the alteration rate of materials by forming a protective barrier at their surface (Aouad et al., 2008). In this study, glass alteration rates, determined using strontium as tracer, showed that the progressive formation of a biofilm on the surface of glass has a protective effect against its alteration. Uranium and rare earth elements (REE) are efficiently trapped in the biogenic compartment of the system (exopolysaccharides + bacterial cells). Besides, the ratio

  13. Hydrotalcite formed by alteration of R7T7 nuclear waste glass and basaltic glass in salt brine at 190{degrees}C

    SciTech Connect

    Abdelouas, A.; Crovisier, J.L.; Lutze, W.; Mueller, R.; Bernotat, W.

    1994-12-31

    The R7T7 and synthetic basaltic glasses were submitted to corrosion in a saline MgCl{sub 2} dominated solution at 190{degrees}C. For both glasses, the early alteration product is a hydrotalcite-like compound in which HPO{sub 4}{sup 2{minus}}, SO{sub 4}{sup 2{minus}} and Cl{sup {minus}} substitutes to CO{sub 3}{sup 2{minus}}. The measured d{sub 003} spacing is 7.68 {angstrom} for the hydrotalcite formed from R7T7 glass and 7.62 {angstrom} for the hydrotalcite formed from basaltic glass which reflect the high aluminium content. Chemical microanalyses show that the hydrotalcite is subsequently covered by a silica-rich gel which evolves into saponite after few months.

  14. Nuclear magnetic resonance investigation of metallic sodium nanoparticles in porous glass

    NASA Astrophysics Data System (ADS)

    Uskov, A. V.; Nefedov, D. Yu.; Charnaya, E. V.; Shevchenko, E. V.; Haase, J.; Michel, D.; Kumzerov, Yu. A.; Fokin, A. V.; Bugaev, A. S.

    2016-06-01

    Sodium nanoparticles embedded in porous glass have been studied by NMR. The measurements have been carried out on pulse spectrometers in magnetic fields of 9.4 and 17.6 T in a wide temperature range. Changes in the magnitude and temperature dependence of the 23Na Knight shift with respect to those in bulk sodium have been discovered. An additional component of the NMR line shifted to high frequencies has been observed in the temperature range from 240 to 100 K. Investigation of the specific heat has revealed a considerable decrease in the melting and crystallization temperatures of sodium under nanoconfinement, which were not accompanied by abrupt changes in the Knight shift.

  15. An alternative host matrix based on iron phosphate glasses for the vitrification of specialized nuclear waste forms. Annual progress report, September 15, 1996--September 14, 1997

    SciTech Connect

    Day, D.E.; Ray, C.S.; Marasinghe, K.

    1997-09-23

    'Objectives of this project are to: (1) investigate the glass composition and processing conditions that yield optimum properties for iron phosphate glasses for vitrifying radioactive waste, (2) determine the atomic structure of iron phosphate glasses and the structure-property relationships, (3) determine how the physical and structural properties of iron phosphate glasses are affected by the addition of simulated high level nuclear waste components, and (4) investigate the process and products of devitrification of iron phosphate waste forms. The glass forming ability of about 125 iron phosphate melts has been investigated in different oxidizing to reducing atmospheres using various iron oxide raw materials such as Fe{sub 2}O{sub 3}, FeO, Fe{sub 3}O{sub 4}, and FeC{sub 2}O{sub 4} 2H{sub 2}O. The chemical durability, redox equilibria between Fe(II) and Fe(III), crystallization behavior and structural features for these glasses and their crystalline forms have been investigated using a variety of techniques including Mossbauer spectroscopy, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), Extended x-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) analysis, differential thermal and thermogravimetric analysis (DTA/TGA), and X-ray and neutron diffraction.'

  16. CHEMICAL DECOMPOSITION OF HIGH-LEVEL NUCLEAR WASTE STORAGE/DISPOSAL GLASSES UNDER IRRADIATION

    EPA Science Inventory

    The Offices of Energy Research and Environmental Management are immediately concerned with the development of storage/immobilization media for high-level nuclear wastes and excess weapons plutonium. These media must be stable and free of risk to the public or to the environment f...

  17. RHENIUM SOLUBILITY IN BOROSILICATE NUCLEAR WASTE GLASS IMPLICATIONS FOR THE PROCESSING AND IMMOBILIZATION OF TECHNETIUM-99 (AND SUPPORTING INFORMATION WITH GRAPHICAL ABSTRACT)

    SciTech Connect

    AA KRUGER; A GOEL; CP RODRIGUEZ; JS MCCLOY; MJ SCHWEIGER; WW LUKENS; JR, BJ RILEY; D KIM; M LIEZERS; P HRMA

    2012-08-13

    The immobilization of 99Tc in a suitable host matrix has proved a challenging task for researchers in the nuclear waste community around the world. At the Hanford site in Washington State in the U.S., the total amount of 99Tc in low-activity waste (LAW) is {approx} 1,300 kg and the current strategy is to immobilize the 99Tc in borosilicate glass with vitrification. In this context, the present article reports on the solubility and retention of rhenium, a nonradioactive surrogate for 99Tc, in a LAW sodium borosilicate glass. Due to the radioactive nature of technetium, rhenium was chosen as a simulant because of previously established similarities in ionic radii and other chemical aspects. The glasses containing target Re concentrations varying from 0 to10,000 ppm by mass were synthesized in vacuum-sealed quartz ampoules to minimize the loss of Re by volatilization during melting at 1000 DC. The rhenium was found to be present predominantly as Re7 + in all the glasses as observed by X-ray absorption near-edge structure (XANES). The solubility of Re in borosilicate glasses was determined to be {approx}3,000 ppm (by mass) using inductively coupled plasma-optical emission spectroscopy (ICP-OES). At higher rhenium concentrations, some additional material was retained in the glasses in the form of alkali perrhenate crystalline inclusions detected by X-ray diffraction (XRD) and laser ablation-ICP mass spectrometry (LA-ICP-MS). Assuming justifiably substantial similarities between Re7 + and Tc 7+ behavior in this glass system, these results implied that the processing and immobilization of 99Tc from radioactive wastes should not be limited by the solubility of 99Tc in borosilicate LAW glasses.

  18. Quasicrystalline Approach to Prediting the Spinel-Nepheline Liquidus: Application to Nuclear Waste Glass Processing

    SciTech Connect

    Jantzen, Carol

    2005-10-10

    The crystal-melt equilibria in complex fifteen component melts are modeled based on quasicrystalline concepts. A pseudobinary phase diagram between acmite (which melts incongruently to a transition metal ferrite spinel) and nepheline is defined. The pseudobinary lies within the Al{sub 2}O{sub 3}-Fe{sub 2}O{sub 3}-Na{sub 2}O-SiO{sub 2} quaternary system that defines the crystallization of basalt glass melts. The pseudobinary provides the partitioning of species between the melt and the primary liquidus phases. The medium range order of the melt and the melt-crystal exchange equilibria are defined based on a constrained mathematical treatment that considers the crystallochemical coordination of the elemental species in acmite and nepheline. The liquidus phases that form are shown to be governed by the melt polymerization and the octahedral site preference energies. This quasicrystalline liquidus model has been used to prevent unwanted crystallization in the world's largest high level waste (HLW) melter for the past three years while allowing >10 wt% higher waste loadings to be processed.

  19. Nuclear Spin Lattice Relaxation and Conductivity Studies of the Non-Arrhenius Conductivity Behavior in Lithium Fast Ion Conducting Sulfide Glasses

    SciTech Connect

    Benjamin Michael Meyer

    2003-05-31

    As time progresses, the world is using up more of the planet's natural resources. Without technological advances, the day will eventually arrive when these natural resources will no longer be sufficient to supply all of the energy needs. As a result, society is seeing a push for the development of alternative fuel sources such as wind power, solar power, fuel cells, and etc. These pursuits are even occurring in the state of Iowa with increasing social pressure to incorporate larger percentages of ethanol in gasoline. Consumers are increasingly demanding that energy sources be more powerful, more durable, and, ultimately, more cost efficient. Fast Ionic Conducting (FIC) glasses are a material that offers great potential for the development of new batteries and/or fuel cells to help inspire the energy density of battery power supplies. This dissertation probes the mechanisms by which ions conduct in these glasses. A variety of different experimental techniques give a better understanding of the interesting materials science taking place within these systems. This dissertation discusses Nuclear Magnetic Resonance (NMR) techniques performed on FIC glasses over the past few years. These NMR results have been complimented with other measurement techniques, primarily impedance spectroscopy, to develop models that describe the mechanisms by which ionic conduction takes place and the dependence of the ion dynamics on the local structure of the glass. The aim of these measurements was to probe the cause of a non-Arrhenius behavior of the conductivity which has been seen at high temperatures in the silver thio-borosilicate glasses. One aspect that will be addressed is if this behavior is unique to silver containing fast ion conducting glasses. more specifically, this study will determine if a non-Arrhenius correlation time, {tau}, can be observed in the Nuclear Spin Lattice Relaxation (NSLR) measurements. If so, then can this behavior be modeled with a new single distribution

  20. Initial comparison of leach behavior between fully radioactive and simulated nuclear waste glass through long-term testing: Part 2, Reacted layer analysis

    SciTech Connect

    Bates, J.K.; Feng, X.; Bradley, C.R.; Buck, E.C.

    1992-04-01

    An initial comparison of glass behavior of simulated nuclear waste glasses has been made through long-term testing of general glass types SRL165, SRL131 and SRL200. The data demonstrate that up to 560 days at S/V of 2000/m, the reacted layers consist of one outer clay layer, which is undetermined by discontinuous etch pits. The regions between the etch pits are alkali depleted. The surface layer becomes thicker as test duration progresses and the reacted layer after the same test time is thinner at higher S/V than at lower S/V. The relative glass durability measured by the thickness of the reacted layer is 165/42S > 131/11S > 200S, which is consistent with solution analyses. In general, the reacted layers on all glass compositions are poorly crystallized which makes the clay identification difficult. The diffraction spacings and EDS compositions for 131/11S and 200S, although not unique to, are consistent with Na (or Ca-) montmorillonite or nontronite. Both of these are dioctahedral smectite.

  1. Initial comparison of leach behavior between fully radioactive and simulated nuclear waste glass through long-term testing: Part 2, Reacted layer analysis

    SciTech Connect

    Bates, J.K.; Feng, X.; Bradley, C.R.; Buck, E.C.

    1992-01-01

    An initial comparison of glass behavior of simulated nuclear waste glasses has been made through long-term testing of general glass types SRL165, SRL131 and SRL200. The data demonstrate that up to 560 days at S/V of 2000/m, the reacted layers consist of one outer clay layer, which is undetermined by discontinuous etch pits. The regions between the etch pits are alkali depleted. The surface layer becomes thicker as test duration progresses and the reacted layer after the same test time is thinner at higher S/V than at lower S/V. The relative glass durability measured by the thickness of the reacted layer is 165/42S > 131/11S > 200S, which is consistent with solution analyses. In general, the reacted layers on all glass compositions are poorly crystallized which makes the clay identification difficult. The diffraction spacings and EDS compositions for 131/11S and 200S, although not unique to, are consistent with Na (or Ca-) montmorillonite or nontronite. Both of these are dioctahedral smectite.

  2. Micro-fluidics and integrated optics glass sensor for in-line micro-probing of nuclear samples

    SciTech Connect

    Schimpf, A.; Bucci, D.; Broquin, J.E.; Canto, F.; Magnaldo, A.; Couston, L.

    2012-08-15

    We study the miniaturization of Thermal Lens Spectrometry (TLS) towards Lab-on-chip integration in order to reduce the volume of fluid assays in nuclear process control. TLS is of great interest in this context since it combines the advantages of optical detection methods with an inherent suitability for small-scale samples. After validating the experimental principle in a classical thermal lens crossed-beam setup, we show the integration of a Young-interferometer with a microcapillary on a glass substrate, reducing the necessary sample size to 400 nl. The interferometer translates the photo-thermally induced refractive index change in the fluid to a phase shift of the fringe pattern, which can then be detected by a camera. Measurements of Co(II) in ethanol yield a detection limit of c = 5 x 10{sup -4} M for the crossed-beam setup and c = 6 x 10{sup -3} M for the integrated sensor. At an interaction length of 10 m, it detects a minimum absorbance of K = 1.2 x 10{sup -4} in a probed volume of 14 pl. (authors)

  3. INTERNATIONAL STUDIES OF ENHANCED WASTE LOADING AND IMPROVED MELT RATE FOR HIGH ALUMINA CONCENTRATION NUCLEAR WASTE GLASSES

    SciTech Connect

    Fox, K; David Peeler, D; James Marra, J

    2008-09-11

    The goal of this study was to determine the impacts of glass compositions with high aluminum concentrations on melter performance, crystallization and chemical durability for Savannah River Site (SRS) and Hanford waste streams. Glass compositions for Hanford targeted both high aluminum concentrations in waste sludge and a high waste loading in the glass. Compositions for SRS targeted Sludge Batch 5, the next sludge batch to be processed in the Defense Waste Processing Facility (DWPF), which also has a relatively high aluminum concentration. Three frits were selected for combination with the SRS waste to evaluate their impact on melt rate. The glasses were melted in two small-scale test melters at the V. G. Khlopin Radium Institute. The results showed varying degrees of spinel formation in each of the glasses. Some improvements in melt rate were made by tailoring the frit composition for the SRS feeds. All of the Hanford and SRS compositions had acceptable chemical durability.

  4. Intrinsic dosimetry of glass containers used to transport nuclear materials: Potential implications to the fields of waste management and nuclear forensics

    SciTech Connect

    Schwantes, Jon M.; Miller, Steve D.; Piper, Roman K.; Murphy, Mark K.; Amonette, James E.; Bonde, Steven E.; Duckworth, Douglas C.

    2009-04-12

    Thermoluminescence (TL) and Electron Paramagnetic Resonance (EPR) dosimetry were used to measure dose effects in borosilicate glass with time, from 10 min to w60 days following exposure to a dose of up to 100 Gy. TL and EPR results were consistent and performed similarly, with both techniques capable of achieving an estimated limit of detection of between 0.5 and 1 Gy. Three peaks were identified in the TL glow curve at roughly 110 C, 205 C, and 225 C. The intensity of the 205 C peak was the dominant peak over the time period of this study. The stability of all of the peaks with time since irradiation increased with their corresponding temperature and no significant variation was observed in the glow curve response to a specified total dose attained at different dose rates. The intensity of the 205 C peak decreased logarithmically with time regardless of total dose. Based upon a conservative limit of detection of 3.3 Gy, a 100 Gy dose would still be detected 2.7E3 years after exposure. Here, we introduce the concept of intrinsic dosimetry, the measurement of the total absorbed dose received by the walls of a container containing radioactive material. The foreseen advantage of intrinsic dosimetry comes from considering the measured absorbed dose received by containers in concert with the characteristics (amount, type) of the source of that dose, the radioactive material contained within the walls of the container, in order to provide enhanced information about the history of an unknown sample in question. Three hypothetical scenarios are presented to introduce this method and to illustrate how intrinsic dosimetry might benefit the fields of nuclear forensics and waste management.

  5. Glass science tutorial: Lecture No. 7, Waste glass technology for Hanford

    SciTech Connect

    Kruger, A.A.

    1995-07-01

    This paper presents the details of the waste glass tutorial session that was held to promote knowledge of waste glass technology and how this can be used at the Hanford Reservation. Topics discussed include: glass properties; statistical approach to glass development; processing properties of nuclear waste glass; glass composition and the effects of composition on durability; model comparisons of free energy of hydration; LLW glass structure; glass crystallization; amorphous phase separation; corrosion of refractories and electrodes in waste glass melters; and glass formulation for maximum waste loading.

  6. Effects of neutron irradiation on glass ceramics as pressure-less joining materials for SiC based components for nuclear applications

    NASA Astrophysics Data System (ADS)

    Ferraris, M.; Casalegno, V.; Rizzo, S.; Salvo, M.; Van Staveren, T. O.; Matejicek, J.

    2012-10-01

    This paper reports on the microstructure and properties of two glass-ceramics based on SiO2-Al2O3-MgO (SAMg) and SiO2-Al2O3-Y2O3 (SAY), which have been designed to be used as pressure-less low activation joining materials for SiC/SiC and SiC based components for nuclear applications. Glass-ceramic pellets (SAY and SAMg) were irradiated for approximately 1 year in the reactor core of the LVR-15 research reactor at Nuclear Research Institute Rez, Czech Republic, at about 50 °C, 6.92 × 1024 n/m2 (E > 1 MeV, about 1 dpa in steel); SiC/SiC composites joined by SAY were irradiated about 1 year at High Flux Reactor (HFR), Petten, The Netherlands, 550 °C, 9-11 × 1024 n/m2 (E > 1 MeV, about 1.4-1.8 dpa in C), 600 °C, 16-22 × 1024 n/m2 (E > 1 MeV, about 2.6-3.3 dpa in C) and 820 °C 31-32 × 1024 n/m2(E > 1 MeV, about 5 dpa in C). Optical microscopy with image analysis and scanning electron microscopy (SEM) with X-ray microanalysis (EDS) were used to investigate the glass-ceramics morphology and composition, showing a remarkable similarity before and after neutron irradiation for both glass-ceramics. Comparison of bending strength for irradiated and non-irradiated SAY joined SiC/SiC indicate that the mechanical strength is unaffected by irradiation at these conditions.

  7. IR and Raman Spectroscopy of Sodium-Aluminophosphate Glasses for Immobilizing High-Level Wastes from Spent Nuclear Fuel Reprocessing

    NASA Astrophysics Data System (ADS)

    Stefanovsky, S. V.; Myasoedov, B. F.; Remizov, M. B.; Belanova, E. A.

    2014-09-01

    The structure of sodium-aluminophosphate glasses containing constituents of high-level wastes (cesium, magnesium, copper, and molybdenum oxides) from uranium-graphite reactors was studied by IR and Raman spectroscopy coupled with x-ray diffraction. The structural network was shown to be composed of short P-O chains with embedded AlO4 tetrahedra. Cross-linking by Mg2+ was possible in the Mg-bearing samples. The effect of the other oxides (Cs2O, MoO3, CuO) on the glass structure was negligible for the occurring amounts. The glasses devitrified partially upon quenching and more strongly upon annealing. This was reflected in splitting of the vibrational bands for bonds in the glass anionic structural motif.

  8. Secondary phase formation and the microstructural evolution of surface layers during vapor phase alteration of the French SON 68 nuclear waste glass at 200{degrees}C

    SciTech Connect

    Gong, W.L.; Ewing, R.C.; Wang, L.M.

    1995-12-31

    The SON 68 inactive {open_quotes}R7T7{close_quotes} composition is the French reference glass for the LWR nuclear waste glass. Vapor phase alteration was used to accelerate the reaction progress of glass corrosion and to develop the characteristic suite of secondary, alteration phases. Extensive solid-state characterization (AEM/SEM/HRTEM) was completed on six inactive R7T7 waste glasses which were altered in the presence of saturated water vapor (200{degrees}C) for 91, 241, 908, 1000, 1013, and 1021 days. The AEM samples were examined in cross-section (lattice-fringe imaging, micro-diffraction, and quantitative thin-film EDS analysis). The glass monoliths were invariably covered with a thin altered rind. The layer became thicker with time: 0.5 {mu}m for 22 days; 4 {mu}m for 91 days; 6 {mu}m for 241 days; 10 {mu}m for 908 days; 26 {mu}m for 1013 days; and <35 {mu}m for 1021 days. The composite alteration layer of the SON 68 samples is at least four time less thick than that of the SRL 131 glass composition. Six distinctive zones, based on phase chemistry and microstructure, were distinguished within the well-developed surface layers. Numerous crystalline phases such as analcime, tobermorite, apatite, and weeksite were identified on the surfaces of the reacted glasses as precipitates. Two crystalline phases, Ag{sub 2}TeO{sub 3} and (Ca,Sr)Mo{sub 3}O{sub 9}(OH){sub 2}, were found within the inner zones of surface layers, and they must have nucleated in situ, indicating that Ag, Te, Sr, and Mo can be retained within the surface layer. The majority of the surface layer volume is composed of two morphologically and chemically different structures: one consists of well-crystallized fibrous smectite aggregates occurring along with cavities, the A-domain; and the other consists of poorly-crystallized regions containing needle-like smectite (montmorillonite) crystallites, a silica-rich amorphous matrix, and possibly ZrO{sub 2} particles, the B-domain.

  9. Dynamics of asymmetric non-polymeric binary glass formers—A nuclear magnetic resonance and dielectric spectroscopy study

    SciTech Connect

    Pötzschner, B.; Mohamed, F.; Lichtinger, A.; Bock, D.; Rössler, E. A.

    2015-10-21

    We study a dynamically asymmetric binary glass former with the low-T{sub g} component m-tri-cresyl phosphate (m-TCP: T{sub g} = 206 K) and a spirobichroman derivative as a non-polymeric high-T{sub g} component (T{sub g} = 382 K) by means of {sup 1}H nuclear magnetic resonance (NMR), {sup 31}P NMR, and dielectric spectroscopy which allow component-selectively probing the dynamics. The entire concentration range is covered, and two main relaxation processes with two T{sub g} are identified, T{sub g1} and T{sub g2}. The slower one is attributed to the high-T{sub g} component (α{sub 1}-process), and the faster one is related to the m-TCP molecules (α{sub 2}-process). Yet, there are indications that a small fraction of m-TCP is associated also with the α{sub 1}-process. While the α{sub 1}-relaxation only weakly broadens upon adding m-TCP, the α{sub 2}-relaxation becomes extremely stretched leading to quasi-logarithmic correlation functions at low m-TCP concentrations—as probed by {sup 31}P NMR stimulated echo experiments. Frequency-temperature superposition does not apply for the α{sub 2}-process and it reflects an isotropic, liquid-like motion which is observed even below T{sub g1}, i.e., in the matrix of the arrested high-T{sub g} molecules. As proven by 2D {sup 31}P NMR, the corresponding dynamic heterogeneities are of transient nature, i.e., exchange occurs within the distribution G(lnτ{sub α2}). At T{sub g1} a crossover is found for the temperature dependence of (mean) τ{sub α2}(T) from non-Arrhenius above to Arrhenius below T{sub g1} which is attributed to intrinsic confinement effects. This “fragile-to-strong” transition also leads to a re-decrease of T{sub g2}(c{sub m−TCP}) at low concentration c{sub m−TCP}, i.e., a maximum is observed in T{sub g2}(c{sub m−TCP}) while T{sub g1}(c{sub m−TCP}) displays the well-known plasticizer effect. Although only non-polymeric components are involved, we re-discover essentially all features previously

  10. Dynamics of asymmetric non-polymeric binary glass formers—A nuclear magnetic resonance and dielectric spectroscopy study

    NASA Astrophysics Data System (ADS)

    Pötzschner, B.; Mohamed, F.; Lichtinger, A.; Bock, D.; Rössler, E. A.

    2015-10-01

    We study a dynamically asymmetric binary glass former with the low-Tg component m-tri-cresyl phosphate (m-TCP: Tg = 206 K) and a spirobichroman derivative as a non-polymeric high-Tg component (Tg = 382 K) by means of 1H nuclear magnetic resonance (NMR), 31P NMR, and dielectric spectroscopy which allow component-selectively probing the dynamics. The entire concentration range is covered, and two main relaxation processes with two Tg are identified, Tg1 and Tg2. The slower one is attributed to the high-Tg component (α1-process), and the faster one is related to the m-TCP molecules (α2-process). Yet, there are indications that a small fraction of m-TCP is associated also with the α1-process. While the α1-relaxation only weakly broadens upon adding m-TCP, the α2-relaxation becomes extremely stretched leading to quasi-logarithmic correlation functions at low m-TCP concentrations—as probed by 31P NMR stimulated echo experiments. Frequency-temperature superposition does not apply for the α2-process and it reflects an isotropic, liquid-like motion which is observed even below Tg1, i.e., in the matrix of the arrested high-Tg molecules. As proven by 2D 31P NMR, the corresponding dynamic heterogeneities are of transient nature, i.e., exchange occurs within the distribution G(lnτα2). At Tg1 a crossover is found for the temperature dependence of (mean) τα2(T) from non-Arrhenius above to Arrhenius below Tg1 which is attributed to intrinsic confinement effects. This "fragile-to-strong" transition also leads to a re-decrease of Tg2(cm-TCP) at low concentration cm-TCP, i.e., a maximum is observed in Tg2(cm-TCP) while Tg1(cm-TCP) displays the well-known plasticizer effect. Although only non-polymeric components are involved, we re-discover essentially all features previously reported for polymer-plasticizer systems.

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

    SciTech Connect

    Marra, J.; Billings, A.

    2009-06-24

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

  12. High level nuclear waste glass corrosion in synthetic clay pore solution and retention of actinides in secondary phases

    NASA Astrophysics Data System (ADS)

    Bosbach, D.; Luckscheiter, B.; Brendebach, B.; Denecke, M. A.; Finck, N.

    2009-03-01

    The corrosion of the simulated high level waste glass GP WAK1 in synthetic clay pore solution was studied in batch-type experiments at 323 and 363 K with special focus on the effect of high carbonate concentration in solution. The corrosion rate after 130 days was <10-4g m-2 d-1 - no significant effect of the carbonate was identified. During glass corrosion, crystalline secondary phases (powellite, barite, calcite, anhydrite and clay-like Mg(Ca,Fe)-silicates) were formed. To obtain a molecular level picture of radionuclide speciation within the alteration layer, spectroscopic methods have been applied including grazing incidence X-ray absorption spectroscopy (XAS) to study the structural changes in the coordination of uranyl upon alteration layer formation. The number of equatorial oxygen atoms increases from 4 in the bulk glass to 5 in the alteration layer. Furthermore, reduced coordination symmetry was found. Hectorite, a frequently observed secondary clay mineral within the glass alteration layer, was synthesized in the presence of trivalent f-elements (e.g. Eu) and structurally characterized using time-resolved laser fluorescence spectroscopy. Structural incorporation into the octahedral layer is indicated.

  13. Glass sealing

    SciTech Connect

    Brow, R.K.; Kovacic, L.; Chambers, R.S.

    1996-04-01

    Hernetic glass sealing technologies developed for weapons component applications can be utilized for the design and manufacture of fuel cells. Design and processing of of a seal are optimized through an integrated approach based on glass composition research, finite element analysis, and sealing process definition. Glass sealing procedures are selected to accommodate the limits imposed by glass composition and predicted calculations.

  14. The behavior of silicon and boron in the surface of corroded nuclear waste glasses : an EFTEM study.

    SciTech Connect

    Buck, E. C.; Smith, K. L.; Blackford, M. G.

    1999-11-23

    Using electron energy-loss filtered transmission electron microscopy (EFTEM), we have observed the formation of silicon-rich zones on the corroded surface of a West Valley (WV6) glass. This layer is approximately 100-200 nm thick and is directly underneath a precipitated smectite clay layer. Under conventional (C)TEM illumination, this layer is invisible; indeed, more commonly used analytical techniques, such as x-ray energy dispersive spectroscopy (EDS), have failed to describe fully the localized changes in the boron and silicon contents across this region. Similar silicon-rich and boron-depleted zones were not found on corroded Savannah River Laboratory (SRL) borosilicate glasses, including SRL-EA and SRL-51, although they possessed similar-looking clay layers. This study demonstrates a new tool for examining the corroded surfaces of materials.

  15. Mapping of rare earth elements in nuclear waste glass-ceramic using micro laser-induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, X.; Motto-Ros, V.; Panczer, G.; De Ligny, D.; Yu, J.; Benoit, J. M.; Dussossoy, J. L.; Peuget, S.

    2013-09-01

    A micro-LIBS system was set up based on a quadruple Nd:YAG laser at 266 nm coupled with a microscope. Elemental mapping was performed on a Mo-rich glass-ceramic sample containing CaMoO4 crystallites hundreds of microns in length and about 25 μm in section diameter. The topography of single-shot laser-induced craters was characterized using an atomic force microscope (AFM), which revealed a crater size less than 7 μm. Mappings of Mo, Ca, Sr, Al, Fe, Zr and rare earth elements such as Eu, Nd, Pr and La were undertaken. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was conducted to validate the micro-LIBS analysis. Principal components analysis calculation was used to investigate the correlation of elements in the two phases of glass-ceramic. Correlation between Ca, Sr, rare earth elements and Mo indicates their preferential incorporation into the calcium molybdate crystalline phase. Anti-correlation between Fe, Zr, Al and Mo revealed their affinity to the glass phase.

  16. A Two-Stage Layered Mixture Experiment Design for a Nuclear Waste Glass Application-Part 1

    SciTech Connect

    Cooley, Scott K.; Piepel, Gregory F.; Gan, Hao; Kot, Wing; Pegg, Ian L.

    2003-12-01

    A layered experimental design involving mixture variables was generated to support developing property-composition models for high-level waste (HLW) glasses. The design was generated in two stages, each having unique characteristics. Each stage used a layered design having an outer layer, an inner layer, a center point, and some replicates. The layers were defined by single- and multi-variable constraints. The first stage involved 15 glass components treated as mixture variables. For each layer, vertices were generated and optimal design software was used to select alternative subsets of vertices and calculate design optimality measures. Two partial quadratic mixture models, containing 25 terms for the outer layer and 30 terms for the inner layer, were the basis for the optimal design calculations. Distributions of predicted glass property values were plotted and evaluated for the alternative subsets of vertices. Based on the optimality measures and the predicted property distributions, a ''best'' subset of vertices was selected for each layer to form a layered design for the first stage. The design for the second stage was selected to augment the first-stage design. The discussion of the second-stage design begins in this Part 1 and is continued in Part 2 (Cooley and Piepel, 2003b).

  17. (77)Se nuclear spin-lattice relaxation in binary Ge-Se glasses: insights into floppy versus rigid behavior of structural units.

    PubMed

    Sen, Sabyasachi; Kaseman, Derrick C; Hung, Ivan; Gan, Zhehong

    2015-04-30

    The mechanism of (77)Se nuclear spin-lattice relaxation is investigated in binary Ge-Se glasses. The (77)Se nuclides in Se-Se-Se chain sites relax faster via dipolar coupling fluctuation compared to those in Ge-Se-Ge sites shared by GeSe4 tetrahedra that relax slower via the fluctuation of the chemical shift anisotropy. The relaxation rate for the Se-Se-Se sites decreases markedly with increasing magnetic field, whereas that for the Ge-Se-Ge sites displays no appreciable dependence on the magnetic field such that the extent of differential relaxation between the two Se environments becomes small at high fields on the order of 19.6 T. The corresponding dynamical correlation time is three orders of magnitude shorter (∼10(-9) s) for the Se-Se-Se sites, compared to that for the Ge-Se-Ge sites (∼10(-6) s). The large decoupling in the time scale between these Se environments provides direct experimental support to the commonly made assumption that the selenium chains are mechanically floppy, and the interconnected GeSe4 tetrahedra form the rigid elements in the selenide glass structure. PMID:25848959

  18. Biodegradation of the french reference nuclear glass SON 68 by Acidithiobacillus thiooxidans : protective effect of the biofilm,U and REE retention

    NASA Astrophysics Data System (ADS)

    Bachelet, M.; Crovisier, J.; Stille, P.; Boutin, R.; Vuilleumier, S.; Geoffroy, V.

    2008-12-01

    Although underground nuclear waste repositories are not expected to be favourable places for microbial activity, one should not exclude localized action of extremophilic bacteria on some materials involved in the storage concept. Among endogenous or accidentally introduced acidophiles, some are susceptible to lead to a locally drastic decreased in pH with potential consequences on materials corrosion. Experiments were performed with Acidithiobacillus thiooxidans on 100-125 μm french reference nuclear glass SON68 grains in a mineral medium under static conditions during 60 days at 25°C. Growth medium was periodically renewed and analyzed by ICP-AES and ICP-MS spectrometry for both major, traces and ultra-traces elements. Biofilm formation was evidenced by confocal laser microscopy, staining DNA with ethidium bromide and exopolysaccharides with calcofluor white. Biofilm thickness around material grains exceeded 20 μm under the chosen experimental conditions. It can be noticed that while numerous studies on biofilm formation upon interaction between Acidithiobacillus ferrooxidans and materials can be found in the literature, evidence for biofilm formation is still scarce for the case of the acidophilic bacterium A. thiooxidans. Presence of biofilm is a key parameter for material alteration at the solid/solution interface in biotic systems. Indeed, various constitutive elements of materials trapped in the polyanionic polymer of biofilm may also influence the alteration process. In particular, biofilm may reduce the alteration rate of materials by forming a protective barrier at their surface (Aouad et al., 2008). In this study, glass alteration rates, determined using strontium, molybdenum and caesium as tracers, showed that the biofilm has a protective effect against glass alteration. U and REE are efficiently trapped in the biogenic compartment of the system (exopolysaccharides (EPS) + bacterial cells). Biofilm analysis are in progress to determine whether these

  19. Chalcogenide glasses

    SciTech Connect

    Taylor, P.C.

    1987-08-15

    Although there are some significant exceptions, most important glass-forming systems contain elements from the sixth, or chalcogenide, column of the periodic table (oxygen, sulfur, selenium, or tellurium). The glasses that contain oxygen are typically insulators, while those that contain the heavier chalcogen elements are usually semiconductors. Even though oxygen is technically a chalcogen element, the term chalcogenide glass is commonly used to denote those largely covalent, semiconducting glasses contain sulfur, selenium, or tellurium as one of the constituents.

  20. Waste glass weathering

    SciTech Connect

    Bates, J.K.; Buck, E.C.

    1993-12-31

    The weathering of glass is reviewed by examining processes that affect the reaction of commercial, historical, natural, and nuclear waste glass under conditions of contact with humid air and slowly dripping water, which may lead to immersion in nearly static solution. Radionuclide release data from weathered glass under conditions that may exist in an unsaturated environment are presented and compared to release under standard leaching conditions. While the comparison between the release under weathering and leaching conditions is not exact, due to variability of reaction in humid air, evidence is presented of radionuclide release under a variety of conditions. These results suggest that both the amount and form of radionuclide release can be affected by the weathering of glass.

  1. Effect of composition and temperature on viscosity and electrical conductivity of borosilicate glasses for Hanford nuclear waste immobilization

    SciTech Connect

    Hrma, P.; Piepel, G.F.; Smith, D.E.; Redgate, P.E.; Schweiger, M.J.

    1993-04-01

    Viscosity and electrical conductivity of 79 simulated borosilicate glasses in the expected range of compositions to be produced in the Hanford Waste Vitrification Plant were measured within the temperature span from 950 to 1250[degree]C. The nine major oxide components were SiO[sub 2], B[sub 2]O[sub 3], Li[sub 2]O, Na[sub 2]O, CaO, MgO, Fe[sub 2]O[sub 3], Al[sub 2]O[sub 3], and ZrO[sub 2]. The test compositions were generated statistically. The data were fitted by Fulcher and Arrhenius equations with temperature coefficients being multilinear functions of the mass fractions of the oxide components. Mixture models were also developed for the natural logarithm of viscosity and that of electrical conductivity at 1150[degree]C. Least squares regression was used to obtain component coefficients for all the models.

  2. Glass corrosion in natural environments

    NASA Technical Reports Server (NTRS)

    Thorpe, Arthur N.; Barkatt, Aaron

    1992-01-01

    Experiments carried out during the progress period are summarized. Experiments carried out involving glass samples exposed to solutions of Tris have shown the appearance of 'spikes' upon monitoring glass dissolution as a function of time. The periodic 'spikes' observed in Tris-based media were interpreted in terms of cracking due to excessive stress in the surface region of the glass. Studies of the interactions of silicate glasses with metal ions in buffered media were extended to systems containing Al. Caps buffer was used to establish the pH. The procedures used are described and the results are given. Preliminary studies were initiated as to the feasibility of adding a slowly dissolving solid compound of the additive to the glass-water system to maintain a supply of dissolved additive. It appears that several magnesium compounds have a suitable combination of solubility and affinity towards silicate glass surfaces to have a pronounced retarding effect on the extraction of uranium from the glass. These preliminary findings raise the possibility that introducing a magnesium source into geologic repositories for nuclear waste glass in the form of a sparingly soluble Mg-based backfill material may cause a substantial reduction in the extent of long-term glass corrosion. The studies described also provide mechanistic understanding of the roles of various metal solutes in the leachant. Such understanding forms the basis for developing long-term predictions of nuclear waste glass durability under repository conditions. From what is known about natural highly reduced glasses such as tektites, it is clear that iron is dissolved as ferrous iron with little or no ferric iron. The reducing conditions were high enough to cause metallic iron to exsolve out of the glass in the form of submicroscopic spherules. As the nuclear waste glass is much less reduced, a study was initiated on other natural glasses in addition to the nuclear waste glass. Extensive measurements were

  3. Glass-An Environmental Protector

    SciTech Connect

    MARRA, JAMES

    2004-11-01

    From asbestos abatement to lead paint removal to nuclear waste stabilization and even to heavy metal removal using microorganisms, glass has great potential as a solution to many environmental problems. The ability to accommodate an array of chemical elements within the glass structure has facilitated the use of glass as a medium for the stabilization of numerous hazardous substances. The resulting glasses have proven to be durable enough for direct land disposal. In many cases, the stabilized forms have been deemed suitable for re-use in other applications. As recycling and hazardous material treatment become even more important in the global materials cycle, it is a certainty that glass will assume a prominent role.

  4. MIIT: International in-situ testing of nuclear-waste glasses: Performance of SRS simulated waste glass after five years of burial at the Waste Isolation Pilot Plant (WIPP)

    SciTech Connect

    Wicks, G.G. ); Lodding, A.R. ); Macedo, P.B. ); Clark, D.E. )

    1991-01-01

    In July of 1986, the first in-situ test involving burial of simulated high-level waste (HLW) forms conducted in the United States was started. This program, called the Materials Interface Interactions Test or MIIT, comprises the largest, most cooperative field-testing venture in the international waste management community. In July of 1991, the experimental portion of the 5-year MIIT study was completed on schedule. During this time interval, many in-situ measurements were performed, thousands of brine analyses conducted, and hundreds of waste glass and package components exhumed and evaluated after 6 mo., 1 yr., 2 yr. and 5 yr. burial periods. Although analyses are still in progress, the performance of SRS waste glass based on all data currently available has been seen to be excellent thus far. Initial analyses and assessment of Savannah River (SR) waste glass after burial in WIPP at 90{degrees}C for 5 years are presented in this document.

  5. MIIT: International in-situ testing of nuclear-waste glasses: Performance of SRS simulated waste glass after five years of burial at the Waste Isolation Pilot Plant (WIPP)

    SciTech Connect

    Wicks, G.G.; Lodding, A.R.; Macedo, P.B.; Clark, D.E.

    1991-12-31

    In July of 1986, the first in-situ test involving burial of simulated high-level waste (HLW) forms conducted in the United States was started. This program, called the Materials Interface Interactions Test or MIIT, comprises the largest, most cooperative field-testing venture in the international waste management community. In July of 1991, the experimental portion of the 5-year MIIT study was completed on schedule. During this time interval, many in-situ measurements were performed, thousands of brine analyses conducted, and hundreds of waste glass and package components exhumed and evaluated after 6 mo., 1 yr., 2 yr. and 5 yr. burial periods. Although analyses are still in progress, the performance of SRS waste glass based on all data currently available has been seen to be excellent thus far. Initial analyses and assessment of Savannah River (SR) waste glass after burial in WIPP at 90{degrees}C for 5 years are presented in this document.

  6. Glass lasers.

    PubMed

    Snitzer, E

    1966-10-01

    After a general discussion of the merits of glass vs. crystals as host materials for laser ions, a summary is given of the various glass lasers. Because of its importance as an efficient, room temperature laser the properties of neodymium are considered in greater detail. This includes the nonlaser properties of Nd(3+) in glass, the spectral and temporal emission characteristics of Nd(3+) lasers, and Nd(3+) laser configurations. Separate sections deal with the other two room temperature lasers which use Yb(3+) or Er(3+). The problem of thermal stability of laser cavities is also discussed. Finally, a survey is given of the glasses that are useful as Faraday rotators. PMID:20057584

  7. Photochromic glass

    SciTech Connect

    Hoffmann, H.J.

    1990-12-31

    This article deals with the general properties of photochromic inorganic glasses and the darkening and regeneration dynamics as well as the main photochemical and photophysical reactions occurring in the glasses. It concludes with applications of photochromic systems to self-adjusting window panes. This controlled flow of radiant energy could lead to important energy savings by decreasing the cooling and heating loads in buildings and automobiles.

  8. Failure analysis of the lithium battery: A study of the header deposit on the cell top and diffusion within the electrode glass seal using nuclear microanalysis and FFTIR spectroscopy

    NASA Technical Reports Server (NTRS)

    Hassan, Razi A.

    1991-01-01

    The Solid Rocket Booster Range Safety System (SRBRSS) uses a lithium/poly-carbon monofluoride primary battery as a source of electrical power. After cell fabrication and activation, some battery cells have shown self discharge. One possible source of this cell discharge has been suggested to be the formation and growth of a conducting crystallized chemical compound across the glass bead insulator, electrically shorting the glass bead to the casing. This laboratory has begun an analysis of this compound, the glass seal holding the cathode into place, and the cell electrolyte, using Fast Fourier Transform Infrared (FFTIR) Analysis, Rutherford Backscattering Spectroscopy (RBS), and Nuclear Reaction Microanalysis. Preliminary measurements have confirmed the existence of lithium, nitrogen, fluorine, and oxygen on a reddish-brown deposit covering parts of the glass seal holding the positive electrode in place. Cells using Li metal electrodes, have many advantages over conventional primary batteries. One principal disadvantage of using Li batteries on a commercial basis would be the environmental impact of the fluorocarbon material. Another would be the relatively high expense of (CF)n.

  9. Plutonium dioxide dissolution in glass

    SciTech Connect

    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{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.

  10. Silicate Glass Corrosion Mechanism revisited

    NASA Astrophysics Data System (ADS)

    Geisler, Thorsten; Lenting, Christoph; Dohmen, Lars

    2015-04-01

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

  11. /sup 237/Np and /sup 239/Pu solution behavior during hydrothermal testing of simulated nuclear waste glass with basalt and steel

    SciTech Connect

    Schramke, J.A.; Simonson, S.A.; Coles, D.G.

    1984-09-01

    A series of hydrothermal experiments were carried out on /sup 237/Np- and /sup 239/Pu-doped PNL 76-68 glass, synthetic basalt groundwater, basalt, and cast steel. Experiments of duration were conducted in Dickson-type rocking autoclaves at 200/sup 0/C and 30 MPa, with an initial fluid to solid weight ratio of 10:1. The tests carried out were: glass and groundwater; glass, basalt, and groundwater; glass, steel, and groundwater; and glass, steel, basalt, and groundwater. Unfiltered, 4000 A filtered, and 18 A filtered solutions were analyzed to determine the concentrations of radionuclides in solution and those associated with colloids. In all four experiments, /sup 237/Np and /sup 239/Pu were present in solution in quantities at or below the analytical detection limits. The only detectable differences in radionuclide concentrations between the four experiments were brought about by changes in the amounts of colloidally associated radionuclides. Besalt added to the glass and groundwater system increased the quantities of the colloidally associated /sup 237/Np and /sup 239/Pu by an order of magnitude. The addition of steel to the glass and groundwater system reduced the colloidally associated radionuclides to levels below detection limits. The effects of both steel and basalt on the glass and groundwater system seemed to cancel out, and the colloidally associated radionuclide concentrations were similar to the observed levels in the glass plus groundwater system. These variations in the quantities of the colloidally associated radionuclides did not appear to be correlated with other changes in the quantities or composition of the colloidal material in solution. Other than /sup 237/Np and /sup 239/Pu, silica was the only constituent of the colloids in these experiments. The amounts of colloidal silica did not vary significantly between the four experiments. 7 references, 7 figures.

  12. 27Al magic-angle spinning nuclear magnetic resonance satellite transition spectroscopy of glasses in the system K2O-Al2O3-SiO2.

    PubMed

    Mundus, C; Müller-Warmuth, W

    1995-10-01

    27Al magic-angle spinning nuclear magnetic resonance satellite transition spectroscopy at 78 MHz has been applied to determine (true) chemical shift and quadrupole coupling parameters of glasses in the system K2O-Al2O3-SiO2 with 60-80 mol% SiO2 and K2O concentrations between 0 and 24 mol%. The powdered crystalline aluminosilicates andalusite and sillimanite have also been examined. In the glasses, all Al appears to be tetrahedrally bound in the aluminosilicate network unless x = mol% K2O:mol% Al2O3 becomes extremely small. Upon decreasing x the distortion of the tetrahedral Al(OSi)4 units increases in steps, and possible explanations are discussed. Six-coordinated aluminum observed for x < 0.2 is connected with the occurrence of interstitial Al3+ ions which charge-compensate the AlO4 units in addition to K+. PMID:8748646

  13. The incorporation of P, S, Cr, F, Cl, I, Mn, Ti, U, and Bi into simulated nuclear waste glasses: Literature study

    SciTech Connect

    Langowski, M.H.

    1996-02-01

    Waste currently stored on the Hanford Reservation in underground tanks will be into High Level Waste (HLW) and Low Level Waste (LLW). The HLW melter will high-level and transuranic wastes to a vitrified form for disposal in a geological repository. The LLW melter will vitrify the low-level waste which is mainly a sodium solution. Characterization of the tank wastes is still in progress, and the pretreatment processes are still under development Apart from tank-to-tank variations, the feed delivered to the HLW melter will be subject to process control variability which consists of blending and pretreating the waste. The challenge is then to develop glass formulation models which can produce durable and processable glass compositions for all potential vitrification feed compositions and processing conditions. The work under HLW glass formulation is to study and model glass and melt pro functions of glass composition and temperature. The properties of interest include viscosity, electrical conductivity, liquidus temperature, crystallization, immiscibility durability. It is these properties that determine the glass processability and ac waste glass. Apart from composition, some properties, such as viscosity are affected by temperature. The processing temperature may vary from 1050{degrees}C to 1550{degrees}C dependent upon the melter type. The glass will also experience a temperature profile upon cooling. The purpose of this letter report is to assess the expected vitrification feed compositions for critical components with the greatest potential impact on waste loading for double shell tank (DST) and single shell tank (SST) wastes. The basis for critical component selection is identified along with the planned approach for evaluation. The proposed experimental work is a crucial part of model development and verification.

  14. Effects of MgO on the short- and long-term stability of R7T7 and M7 nuclear waste glass in aqueous media

    SciTech Connect

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

    1993-12-31

    Experiments were conducted in initially pure water at 90{degrees}C and 100{degrees}C with glass specimens enriched in MgO and in alkali metals relative to the standard light water R7T7 reference glass. Three experimental protocols were implemented: Soxhlet testing with leachant renewal, static leaching according to a modified MCC-1 method with an SA/V ratio of 50 m{sup -1}, and static leaching with glass powder for an SA/V ratio of 8000 m{sup -1}. The results clearly show that the short and, especially, the long term dissolution rates depend on the initial glass composition. Higher MgO, Na{sub 2}O, Li{sub 2}O, and B{sub 2}O{sub 3} concentrations reduce the glass resistance to aqueous corrosion, as already indicated by the calculated hydration energy values. These experiment illustrate the importance of the glass composition in insuring long-term material integrity.

  15. DURABLE GLASS FOR THOUSANDS OF YEARS

    SciTech Connect

    Jantzen, C.

    2009-12-04

    The durability of natural glasses on geological time scales and ancient glasses for thousands of years is well documented. The necessity to predict the durability of high level nuclear waste (HLW) glasses on extended time scales has led to various thermodynamic and kinetic approaches. Advances in the measurement of medium range order (MRO) in glasses has led to the understanding that the molecular structure of a glass, and thus the glass composition, controls the glass durability by establishing the distribution of ion exchange sites, hydrolysis sites, and the access of water to those sites. During the early stages of glass dissolution, a 'gel' layer resembling a membrane forms through which ions exchange between the glass and the leachant. The hydrated gel layer exhibits acid/base properties which are manifested as the pH dependence of the thickness and nature of the gel layer. The gel layer ages into clay or zeolite minerals by Ostwald ripening. Zeolite mineral assemblages (higher pH and Al{sup 3+} rich glasses) may cause the dissolution rate to increase which is undesirable for long-term performance of glass in the environment. Thermodynamic and structural approaches to the prediction of glass durability are compared versus Ostwald ripening.

  16. The corrosion behavior of DWPF glasses

    SciTech Connect

    Ebert, W.L.; Bates, J.K.

    1995-06-01

    The authors analyzed the corroded surfaces of reference glasses developed for the Defense Waste Processing Facility (DWPF) to characterize their corrosion behavior. The corrosion mechanism of nuclear waste glasses must be known in order to provide source terms describing radionuclide release for performance assessment calculations. Different DWPF reference glasses were corroded under conditions that highlighted various aspects of the corrosion process and led to different extents of corrosion. The glasses corroded by similar mechanisms, and a phenomenological description of their corrosion behavior is presented here. The initial leaching of soluble glass components results in the formation of an amorphous gel layer on the glass surface. The gel layer is a transient phase that transforms into a layer of clay crystallites, which equilibrates with the solution as corrosion continues. The clay layer does not act as a barrier to either water penetration or glass dissolution, which continues beneath it, and may eventually separate from the glass. Solubility limits for glass components may be established by the eventual precipitation of secondary phases; thus, corrosion of the glass becomes controlled by the chemical equilibrium between the solution and the assemblage of secondary phases. In effect, the solution is an intermediate phase through which the glass transforms to an energetically more favorable assemblage of phases. Implications regarding the prediction of long-term glass corrosion behavior are discussed.

  17. Durability of Silicate Glasses: An Historical Approach

    SciTech Connect

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

    2007-01-02

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

  18. Pinhole Glasses

    NASA Astrophysics Data System (ADS)

    Colicchia, Giuseppe; Hopf, Martin; Wiesner, Hartmut; Zollman, Dean

    2008-01-01

    Eye aberrations are commonly corrected by lenses that restore vision by altering rays before they pass through the cornea. Some modern promoters claim that pinhole glasses are better than conventional lenses in correcting all kinds of refractive defects such as myopia (nearsighted), hyperopia (farsighted), astigmatisms, and presbyopia. Do pinhole glasses really give better vision? Some ways to use this question for motivation in teaching optics have been discussed. For this column we include a series of experiments that students can complete using a model of the eye and demonstrate issues related to pinhole vision correction.

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

    NASA Astrophysics Data System (ADS)

    Greaves, G. N.; Sen, S.

    2007-01-01

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

  20. Glass Ceramic Formulation Data Package

    SciTech Connect

    Crum, Jarrod V.; Rodriguez, Carmen P.; McCloy, John S.; Vienna, John D.; Chung, Chul-Woo

    2012-06-17

    A glass ceramic waste form is being developed for treatment of secondary waste streams generated by aqueous reprocessing of commercial used nuclear fuel (Crum et al. 2012b). The waste stream contains a mixture of transition metals, alkali, alkaline earths, and lanthanides, several of which exceed the solubility limits of a single phase borosilicate glass (Crum et al. 2009; Caurant et al. 2007). A multi-phase glass ceramic waste form allows incorporation of insoluble components of the waste by designed crystallization into durable heat tolerant phases. The glass ceramic formulation and processing targets the formation of the following three stable crystalline phases: (1) powellite (XMoO4) where X can be (Ca, Sr, Ba, and/or Ln), (2) oxyapatite Yx,Z(10-x)Si6O26 where Y is alkaline earth, Z is Ln, and (3) lanthanide borosilicate (Ln5BSi2O13). These three phases incorporate the waste components that are above the solubility limit of a single-phase borosilicate glass. The glass ceramic is designed to be a single phase melt, just like a borosilicate glass, and then crystallize upon slow cooling to form the targeted phases. The slow cooling schedule is based on the centerline cooling profile of a 2 foot diameter canister such as the Hanford High-Level Waste canister. Up to this point, crucible testing has been used for glass ceramic development, with cold crucible induction melter (CCIM) targeted as the ultimate processing technology for the waste form. Idaho National Laboratory (INL) will conduct a scaled CCIM test in FY2012 with a glass ceramic to demonstrate the processing behavior. This Data Package documents the laboratory studies of the glass ceramic composition to support the CCIM test. Pacific Northwest National Laboratory (PNNL) measured melt viscosity, electrical conductivity, and crystallization behavior upon cooling to identify a processing window (temperature range) for melter operation and cooling profiles necessary to crystallize the targeted phases in the

  1. Prediction of glass durability as a function of environmental conditions

    SciTech Connect

    Jantzen, C M

    1988-01-01

    A thermodynamic model of glass durability is applied to natural, ancient, and nuclear waste glasses. The durabilities of over 150 different natural and man-made glasses, including actual ancient Roman and Islamic glasses (Jalame ca. 350 AD, Nishapur 10-11th century AD and Gorgon 9-11th century AD), are compared. Glass durability is a function of the thermodynamic hydration free energy, ..delta..G/sub hyd/, which can be calculated from glass composition and solution pH. The durability of the most durable nuclear waste glasses examined was /approximately/10/sup 6/ years. The least durable waste glass formulations were comparable in durability to the most durable simulated medieval window glasses of /approximately/10/sup 3/ years. In this manner, the durability of nuclear waste glasses has been interpolated to be /approximately/10/sup 6/ years and no less than 10/sup 3/ years. Hydration thermodynamics have been shown to be applicable to the dissolution of glass in various natural environments. Groundwater-glass interactions relative to geologic disposal of nuclear waste, hydration rind dating of obsidians, andor other archeological studies can be modeled, e.g., the relative durabilities of six simulated medieval window glasses have been correctly predicted for both laboratory (one month) and burial (5 years) experiments. Effects of solution pH on glass dissolution has been determined experimentally for the 150 different glasses and can be predicted theoretically by hydration thermodynamics. The effects of solution redox on dissolution of glass matrix elements such as SI and B have shown to be minimal. The combined effects of solution pH and Eh have been described and unified by construction of thermodynamically calculated Pourbaix (pH-Eh) diagrams for glass dissolution. The Pourbaix diagrams have been quantified to describe glass dissolution as a function of environmental conditions by use of the data derived from hydration thermodynamics. 56 refs., 7 figs.

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

    SciTech Connect

    Raman, S.

    1993-12-01

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

  3. Surface reactions of natural glasses

    SciTech Connect

    White, A.F.

    1986-12-31

    Reactions at natural glass surfaces are important in studies involving nuclear waste transport due to chemical control on ground water in host rocks such as basalt and tuff, to potential diffusion into natural hydrated glass surfaces and as natural analogs for waste glass stability. Dissolution kinetics can be described by linear surface reaction coupled with cation interdiffusion with resulting rates similar to those of synthetic silicate glasses. Rates of Cs diffusion into hydrated obsidian surfaces between 25{sup 0} and 75{sup 0}C were determined by XPS depth profiles and loss rates from aqueous solutions. Calculated diffusion coefficients were ten others of magnitude more rapid than predicted from an Arrhenius extrapolation of high temperature tracer diffusion data due to surface hydration reactions.

  4. Pinhole Glasses

    ERIC Educational Resources Information Center

    Colicchia, Giuseppe; Hopf, Martin; Wiesner, Hartmut; Zollman, Dean

    2008-01-01

    Eye aberrations are commonly corrected by lenses that restore vision by altering rays before they pass through the cornea. Some modern promoters claim that pinhole glasses are better than conventional lenses in correcting all kinds of refractive defects such as myopia (nearsighted), hyperopia (farsighted), astigmatisms, and presbyopia. Do pinhole…

  5. Prediction of glass durability as a function of glass composition and test conditions: Thermodynamics and kinetics

    SciTech Connect

    Jantzen, C M

    1988-01-01

    The long-term durability of nuclear waste glasses can be predicted by comparing their performance to natural and ancient glasses. Glass durability is a function of the kinetic and thermodynamic stability of glass in solution. The relationship between the kinetic and thermodynamic aspects of glass durability can be understood when the relative contributions of glass composition and imposed test conditions are delineated. Glass durability has been shown to be a function of the thermodynamic hydration free energy which can be calculated from the glass composition. Hydration thermodynamics also furnishes a quantitative frame of reference to understand how various test parameters affect glass durability. Linear relationships have been determined between the logarithmic extent of hydration and the calculated hydration free energy for several different test geometries. Different test conditions result in different kinetic reactivity parameters such as the exposed glass surface area (SA), the leachant solution volume (V), and the length of time that the glass is in the leachant (t). Leachate concentrations are known to be a function of the kinetic test parameter (SAV)t. The relative durabilities of glasses, including pure silica, obsidians, nuclear waste glasses, medieval window glasses, and frit glasses define a plane in three dimensional ..delta..G/sub hyd/-concentration-(SAV)t space. At constant kinetic conditions, e.g., test geometry and test duration, the three dimensional plane is intersected at constant (SAV)t and the ..delta..G/sub hyd/-concentration plots have similar slopes. The slope represents the natural logarithm of the theoretical slope, (12.303 RT), for the rate of glass dissolution. 53 refs., 4 figs.

  6. Determination of Reactive Surface Area of Melt Glass

    SciTech Connect

    Bourcier,W.L.; Roberts, S.; Smith, D.K.; Hulsey, S.; Newton,L.; Sawvel, A.; Bruton, C.; Papelis, C.; Um, W.; Russell, C. E.; Chapman,J.

    2000-10-01

    A comprehensive investigation of natural and manmade silicate glasses, and nuclear melt glass was undertaken in order to derive an estimate of glass reactive surface area. Reactive surface area is needed to model release rates of radionuclides from nuclear melt glass in the subsurface. Because of the limited availability of nuclear melt glasses, natural volcanic glass samples were collected which had similar textures and compositions as those of melt glass. A flow-through reactor was used to measure the reactive surface area of the analog glasses in the presence of simplified NTS site ground waters. A measure of the physical surface area of these glasses was obtained using the BET gas-adsorption method. The studies on analog glasses were supplemented by measurement of the surface areas of pieces of actual melt glass using the BET method. The variability of the results reflect the sample preparation and measurement techniques used, as well as textural heterogeneity inherent to these samples. Based on measurements of analog and actual samples, it is recommended that the hydraulic source term calculations employ a range of 0.001 to 0.01 m{sup 2}/g for the reactive surface area of nuclear melt glass.

  7. Experimental investigation of aqueous corrosion of R7T7 nuclear glass at 90{degrees}C in the presence of humic acids: A kinetic approach

    SciTech Connect

    Gin, S.; Godon, N.; Mestre, J.P.; Vernaz, E.Y.

    1994-12-31

    The dissolution kinetics of the French {open_quotes}R7T7{close_quotes} nonradioactive LWR reference glass in solutions containing dissolved humic acids were investigated at 9O{degrees}C during static tests with imposed or free pH. Experiments conducted in highly dilute media, with a glass-surface-area-to-solution-volume (SA/V) ratio of 5 m{sup -1}, showed that the glass dissolution surface reaction is catalyzed by humic acids. With higher degrees of reaction progress (SA/V = 100 m{sup -1} and free pH) the humic acids impose pH modifications on the system compared with inorganic media; moreover, they directly or indirectly enhance the dissolution of certain alkali metals and transition elements, forming aqueous complexes with the latter. During experiments with an imposed pH of 8.5 (SA/V = 1300 and 5300 m{sup -1}), the humic acids appear to cause increased silica solubility that cannot be accounted for by the formation of silica complexes. A residual corrosion rate in the humic acid media exceeding the rate measured in inorganic media suggests that, in addition to silica, one or more element complexes formed by humic acids may be a kinetically limiting factor. This hypothesis must be confirmed, however, as the quantity of humic acids per unit glass surface area was too small in this experiment to allow unambiguous characterization of the phenomenon.

  8. Temperature effects on waste glass performance

    SciTech Connect

    Mazer, J.J.

    1991-02-01

    The temperature dependence of glass durability, particularly that of nuclear waste glasses, is assessed by reviewing past studies. The reaction mechanism for glass dissolution in water is complex and involves multiple simultaneous reaction proceeded, including molecular water diffusion, ion exchange, surface reaction, and precipitation. These processes can change in relative importance or dominance with time or changes in temperature. The temperature dependence of each reaction process has been shown to follow an Arrhenius relationship in studies where the reaction process has been isolated, but the overall temperature dependence for nuclear waste glass reaction mechanisms is less well understood, Nuclear waste glass studies have often neglected to identify and characterize the reaction mechanism because of difficulties in performing microanalyses; thus, it is unclear if such results can be extrapolated to other temperatures or reaction times. Recent developments in analytical capabilities suggest that investigations of nuclear waste glass reactions with water can lead to better understandings of their reaction mechanisms and their temperature dependences. Until a better understanding of glass reaction mechanisms is available, caution should be exercised in using temperature as an accelerating parameter. 76 refs., 1 tab.

  9. Structure of rhenium-containing sodium borosilicate glass

    SciTech Connect

    Goel, Ashutosh; McCloy, John S.; Windisch, Charles F.; Riley, Brian J.; Schweiger, Michael J.; Rodriguez, Carmen P.; Ferreira, Jose M.

    2013-03-01

    A series of sodium borosilicate glasses were synthesized with increasing fractions of KReO4 or Re2O7, to 10000 ppm (1 mass%) target Re in glass, to assess the effects of large concentrations of rhenium on glass structure and to estimate the solubility of technetium, a radioactive component in typical low active waste nuclear waste glasses. Magic angle spinning nuclear magnetic resonance (MAS-NMR), Fourier transform infrared (FTIR) spectroscopy, and Raman spectroscopy were performed to characterize the glasses as a function of Re source additions. In general, silicon was found coordinated in a mixture of Q2 and Q3 structural units, while Al was 4-coordinated and B was largely 3-coordinate and partially 4-coordinated. The rhenium source did not appear to have significant effects on the glass structure. Thus, at the up to the concentrations that remain in dissolved in glass, ~3000 ppm Re by mass maximum. , the Re appeared to be neither a glass-former nor a strong glass modifier., Rhenium likely exists in isolated ReO4- anions in the interstices of the glass network, as evidenced by the polarized Raman spectrum of the Re glass in the absence of sulfate. Analogous to SO42-¬ in similar glasses, ReO4- is likely a network modifier and forms alkali salt phases on the surface and in the bulk glass above solubility.

  10. Borosilicate glass alteration driven by magnesium carbonates

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

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

  11. Vitrification chemistry and nuclear waste

    SciTech Connect

    Plodinec, M.J.

    1985-01-01

    The vitrification of nuclear waste offers unique challenges to the glass technologist. The waste contains 50 or 60 elements, and often varies widely in composition. Most of these elements are seldom encountered in processing commercial glasses. The melter to vitrify the waste must be able to tolerate these variations in composition, while producing a durable glass. This glass must be produced without releasing hazardous radionuclides to the environment during any step of the vitrification process. Construction of a facility to convert the nearly 30 million gallons of high-level nuclear waste at the Savannah River Plant into borosilicate glass began in late 1983. In developing the vitrification process, the Savannah River Laboratory has had to overcome all of these challenges to the glass technologist. Advances in understanding in three areas have been crucial to our success: oxidation-reduction phenomena during glass melting; the reaction between glass and natural wastes; and the causes of foaming during glass melting.

  12. Strength of inorganic glass

    SciTech Connect

    Kurkjian, C.R.

    1985-01-01

    This book presents information on the following topics: a look at the history of glass strength; atomistic theory of fracture; surface chemistry in relation to the strength and fracture of silicate glasses; high-speed photographic investigations of the dynamic localized loading of some oxide glasses; a correction for measurements of contact area using Newton's rings; envionmentally enhanced crack growth; fatigue in glass; behavior of flaws in fused silica fibers; fracture toughness of chalcogenide glasses and glass-ceramics; fracture analysis of glass surfaces; and fracture mechanics parameters for glasses - a compilation and correlation.

  13. IMPACT STRENGTH OF GLASS AND GLASS CERAMIC

    SciTech Connect

    Bless, S.; Tolman, J.

    2009-12-28

    Strength of glass and glass ceramic was measured with a bar impact technique. High-speed movies show regions of tensile and compressive failure. The borosilicate glass had a compressive strength of at least 2.2 GPa, and the glass ceramic at least 4 GPa. However, the BSG was much stronger in tension than GC. In ballistic tests, the BSG was the superior armor.

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

    SciTech Connect

    Fluegel, Alex

    2007-02-01

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

  15. Ion-implantation damage in silicate glasses

    NASA Astrophysics Data System (ADS)

    Arnold, G. W.

    Ion implantation is a rapid technique for simulating damage induced by alpha recoil nuclei in nuclear waste forms. The simulation has been found to be quite good in TEM comparisons with natural alpha decay damage in minerals, but leach rate differences have been observed in glass studies and were attributed to dose rate differences. The similarities between ion implantation and recoil nuclei as a means of producing damage suggest that insights into the long term behavior of glass waste forms can be obtained by examination of what is known about ion implantation damage in silicate glasses. This paper briefly reviews these effects and shows that leaching results in certain nuclear waste glasses can be understood as resulting from plastic flow and track overlap. Phase separation is also seen to be a possible consequence of damage induced compositional changes.

  16. Cathodic protection for nuclear waste packaging under gamma ray irradiation by using TiO{sub 2} coating combined with glass scintillators

    SciTech Connect

    Fujisawa, Ryutaro; Tsujikawa, Shigeo

    1995-12-31

    The photoelectrochemical behaviors of a TiO{sub 2} single crystal and TiO{sub 2} coating were studied, for the purposes of cathodic protection of stainless steels and Cu via the TiO{sub 2} coating combined with glass scintillators under gamma ray irradiation. It was confirmed that a TiO{sub 2} coating could protect 304 stainless steel cathodically from crevice corrosion under illumination. A logarithmic relationship between the photopotential of single crystal TiO{sub 2} (rutile) and light intensity was found, moreover, the photopotential was found to be least noble when wavelength equals 375 nm. Under illumination by gamma rays combined with the glass scintillators, the electrode potential of single crystal TiO{sub 2} was found to shift in the less noble direction by about 200 mV. Therefore, the technique of cathodic protection by TiO{sub 2} coating is considered to be applicable to protect the packaging metal from corrosion for a long time.

  17. Gaseous Sulfate Solubility in Glass: Experimental Method

    SciTech Connect

    Bliss, Mary

    2013-11-30

    Sulfate solubility in glass is a key parameter in many commercial glasses and nuclear waste glasses. This report summarizes key publications specific to sulfate solubility experimental methods and the underlying physical chemistry calculations. The published methods and experimental data are used to verify the calculations in this report and are expanded to a range of current technical interest. The calculations and experimental methods described in this report will guide several experiments on sulfate solubility and saturation for the Hanford Waste Treatment Plant Enhanced Waste Glass Models effort. There are several tables of sulfate gas equilibrium values at high temperature to guide experimental gas mixing and to achieve desired SO3 levels. This report also describes the necessary equipment and best practices to perform sulfate saturation experiments for molten glasses. Results and findings will be published when experimental work is finished and this report is validated from the data obtained.

  18. Chemical Principles Revisited: The Chemistry of Glass.

    ERIC Educational Resources Information Center

    Kolb, Doris; Kolb, Kenneth E.

    1979-01-01

    Presents a detailed discussion on the chemistry of glass. Topics discussed include: natural glass, early history, modern glass composition, raw materials for glass melting, chemically modified glasses, modern glass forming, glass ceramics, and new developments in glass research. (BT)

  19. A simple method for tuning the glass transition process in inorganic phosphate glasses.

    PubMed

    Fulchiron, René; Belyamani, Imane; Otaigbe, Joshua U; Bounor-Legaré, Véronique

    2015-01-01

    The physical modification of glass transition temperature (T(g)) and properties of materials via blending is a common practice in industry and academia and has a large economic advantage. In this context, simple production of hitherto unattainable new inorganic glass blends from already existing glass compositions via blending raises much hope with the potential to provide new glasses with new and improved properties, that cannot be achieved with classical glass synthesis, for a plethora of applications such as computers screens, glass-to-metal seals, and storage materials for nuclear wastes. Here, we demonstrate that blends of the specific glass compositions studied are miscible in all proportions, an unreported phenomenon in hard condensed matter like glass. Interestingly, excellent agreement was found between the obtained data and calculated Tgs from theoretical equations (Supplementary information) for predicting the composition dependence of T(g) for miscible blends with weak but significant specific interactions between the blend components. That this blending method is at present not applied to inorganic glasses reflects the fact that water and chemically resistant phosphate glasses with relatively low T(g)s have become available only recently. PMID:25666949

  20. A simple method for tuning the glass transition process in inorganic phosphate glasses

    NASA Astrophysics Data System (ADS)

    Fulchiron, René; Belyamani, Imane; Otaigbe, Joshua U.; Bounor-Legaré, Véronique

    2015-02-01

    The physical modification of glass transition temperature (Tg) and properties of materials via blending is a common practice in industry and academia and has a large economic advantage. In this context, simple production of hitherto unattainable new inorganic glass blends from already existing glass compositions via blending raises much hope with the potential to provide new glasses with new and improved properties, that cannot be achieved with classical glass synthesis, for a plethora of applications such as computers screens, glass-to-metal seals, and storage materials for nuclear wastes. Here, we demonstrate that blends of the specific glass compositions studied are miscible in all proportions, an unreported phenomenon in hard condensed matter like glass. Interestingly, excellent agreement was found between the obtained data and calculated Tgs from theoretical equations (Supplementary information) for predicting the composition dependence of Tg for miscible blends with weak but significant specific interactions between the blend components. That this blending method is at present not applied to inorganic glasses reflects the fact that water and chemically resistant phosphate glasses with relatively low Tgs have become available only recently.

  1. Silicon oxycarbide glass for the immobilisation of irradiated graphite waste

    NASA Astrophysics Data System (ADS)

    Lloyd, James W.; Stennett, Martin C.; Hand, Russell J.

    2016-02-01

    Silicon oxycarbide glass has been investigated as a potential immobilisation medium for irradiated graphite waste from nuclear power generation. The glass was synthesised via sol-gel techniques using alkoxysilane precursors. Attempts to produce a wasteform via conventional sintering were unsuccessful, but dense wasteforms were achieved by spark plasma sintering (SPS). Microstructural investigations showed that the addition of graphite to the glass did not alter the structure of the matrix; no reaction between the graphite and the glass matrix was observed. Silicon oxycarbide glass is a viable candidate for encapsulation of graphite waste prior to disposal.

  2. Repairing cracked glass

    NASA Technical Reports Server (NTRS)

    Helman, D. D.; Holt, J. W.; Smiser, L. V.

    1979-01-01

    Filing procedure consisting of machined lightweight fused-silica tiles coated with thin-layer of borosilicate glass produces homogeneous seal in thin glass. Procedure is useful in repairing glass envelopes, X-ray tub windows, Dewar flasks, and similar thin glass objects.

  3. Inverted glass harp.

    PubMed

    Quinn, Daniel B; Rosenberg, Brian J

    2015-08-01

    We present an analytical treatment of the acoustics of liquid-filled wine glasses, or "glass harps." The solution is generalized such that under certain assumptions it reduces to previous glass harp models, but also leads to a proposed musical instrument, the "inverted glass harp," in which an empty glass is submerged in a liquid-filled basin. The versatility of the solution demonstrates that all glass harps are governed by a family of solutions to Laplace's equation around a vibrating disk. Tonal analyses of recordings for a sample glass are offered as confirmation of the scaling predictions. PMID:26382336

  4. Inverted glass harp

    NASA Astrophysics Data System (ADS)

    Quinn, Daniel B.; Rosenberg, Brian J.

    2015-08-01

    We present an analytical treatment of the acoustics of liquid-filled wine glasses, or "glass harps." The solution is generalized such that under certain assumptions it reduces to previous glass harp models, but also leads to a proposed musical instrument, the "inverted glass harp," in which an empty glass is submerged in a liquid-filled basin. The versatility of the solution demonstrates that all glass harps are governed by a family of solutions to Laplace's equation around a vibrating disk. Tonal analyses of recordings for a sample glass are offered as confirmation of the scaling predictions.

  5. Glass-silicon column

    DOEpatents

    Yu, Conrad M.

    2003-12-30

    A glass-silicon column that can operate in temperature variations between room temperature and about 450.degree. C. The glass-silicon column includes large area glass, such as a thin Corning 7740 boron-silicate glass bonded to a silicon wafer, with an electrode embedded in or mounted on glass of the column, and with a self alignment silicon post/glass hole structure. The glass/silicon components are bonded, for example be anodic bonding. In one embodiment, the column includes two outer layers of silicon each bonded to an inner layer of glass, with an electrode imbedded between the layers of glass, and with at least one self alignment hole and post arrangement. The electrode functions as a column heater, and one glass/silicon component is provided with a number of flow channels adjacent the bonded surfaces.

  6. Comparison of mechanical properties of glass-bonded sodalite and borosilicate glass high-level waste forms

    SciTech Connect

    O'Holleran, T. P.; DiSanto, T.; Johnson, S. G.; Goff, K. M.

    2000-05-09

    Argonne National Laboratory has developed a glass-bonded sodalite waste form to immobilize the salt waste stream from electrometallurgical treatment of spent nuclear fuel. The waste form consists of 75 vol.% crystalline sodalite and 25 vol.% glass. Microindentation fracture toughness measurements were performed on this material and borosilicate glass from the Defense Waste Processing Facility using a Vickers indenter. Palmqvist cracking was confined for the glass-bonded sodalite waste form, while median-radial cracking occurred in the borosilicate glass. The elastic modulus was measured by an acoustic technique. Fracture toughness, microhardness, and elastic modulus values are reported for both waste forms.

  7. Survey of glass plutonium contents and poison selection

    SciTech Connect

    Plodinec, M.J.; Ramsey, W.G.; Ellison, A.J.G.; Shaw, H.

    1996-05-01

    If plutonium and other actinides are to be immobilized in glass, then achieving high concentrations in the glass is desirable. This will lead to reduced costs and more rapid immobilization. However, glasses with high actinide concentrations also bring with them undersirable characteristics, especially a greater concern about nuclear criticality, particularly in a geologic repository. The key to achieving a high concentration of actinide elements in a glass is to formulate the glass so that the solubility of actinides is high. At the same time, the glass must be formulated so that the glass also contains neutron poisons, which will prevent criticality during processing and in a geologic repository. In this paper, the solubility of actinides, particularly plutonium, in three types of glasses are discussed. Plutonium solubilities are in the 2-4 wt% range for borosilicate high-level waste (HLW) glasses of the type which will be produced in the US. This type of glass is generally melted at relatively low temperatures, ca. 1150{degrees}C. For this melting temperature, the glass can be reformulated to achieve plutonium solubilities of at least 7 wt%. This low melting temperature is desirable if one must retain volatile cesium-137 in the glass. If one is not concerned about cesium volatility, then glasses can be formulated which can contain much larger amounts of plutonium and other actinides. Plutonium concentrations of at least 15 wt% have been achieved. Thus, there is confidence that high ({ge}5 wt%) concentrations of actinides can be achieved under a variety of conditions.

  8. Surface layer effects on waste glass corrosion

    SciTech Connect

    Feng, X.

    1993-12-31

    Water contact subjects waste glass to chemical attack that results in the formation of surface alteration layers. Two principal hypotheses have been advanced concerning the effect of surface alteration layers on continued glass corrosion: (1) they act as a mass transport barrier and (2) they influence the chemical affinity of the glass reaction. In general, transport barrier effects have been found to be less important than affinity effects in the corrosion of most high-level nuclear waste glasses. However, they can be important under some circumstances, for example, in a very alkaline solution, in leachants containing Mg ions, or under conditions where the matrix dissolution rate is very low. The latter suggests that physical barrier effect may affect the long-term glass dissolution rate. Surface layers influence glass reaction affinity through the effects of the altered glass and secondary phases on the solution chemistry. The reaction affinity may be controlled by various precipitates and crystalline phases, amorphous silica phases, gel layer, or all the components of the glass. The surface alteration layers influence radionuclide release mainly through colloid formation, crystalline phase incorporation, and gel layer retention. This paper reviews current understanding and uncertainties.

  9. DEVELOPMENT OF GLASS MATRICES FOR HLW RADIOACTIVE WASTES

    SciTech Connect

    Jantzen, C.

    2010-03-18

    Vitrification is currently the most widely used technology for the treatment of high level radioactive wastes (HLW) throughout the world. Most of the nations that have generated HLW are immobilizing in either borosilicate glass or phosphate glass. One of the primary reasons that glass has become the most widely used immobilization media is the relative simplicity of the vitrification process, e.g. melt waste plus glass forming frit additives and cast. A second reason that glass has become widely used for HLW is that the short range order (SRO) and medium range order (MRO) found in glass atomistically bonds the radionuclides and governs the melt properties such as viscosity, resistivity, sulphate solubility. The molecular structure of glass controls contaminant/radionuclide release by establishing the distribution of ion exchange sites, hydrolysis sites, and the access of water to those sites. The molecular structure is flexible and hence accounts for the flexibility of glass formulations to waste variability. Nuclear waste glasses melt between 1050-1150 C which minimizes the volatility of radioactive components such as Tc{sup 99}, Cs{sup 137}, and I{sup 129}. Nuclear waste glasses have good long term stability including irradiation resistance. Process control models based on the molecular structure of glass have been mechanistically derived and have been demonstrated to be accurate enough to control the world's largest HLW Joule heated ceramic melter in the US since 1996 at 95% confidence.

  10. Picture Wall (Glass Structures)

    NASA Technical Reports Server (NTRS)

    1978-01-01

    Photo shows a subway station in Toronto, Ontario, which is entirely glass-enclosed. The all-glass structure was made possible by a unique glazing concept developed by PPG Industries, Pittsburgh, Pennsylvania, one of the largest U.S. manufacturers of flat glass. In the TVS glazing system, transparent glass "fins" replace conventional vertical support members used to provide support for wind load resistance. For stiffening, silicone sealant bonds the fins to adjacent glass panels. At its glass research center near Pittsburgh, PPG Industries uses the NASTRAN computer program to analyze the stability of enclosures made entirely of glass. The company also uses NASTRAN to simulate stresses on large containers of molten glass and to analyze stress effects of solar heating on flat glass.

  11. Reaction cured glass and glass coatings

    NASA Technical Reports Server (NTRS)

    Goldstein, H. E.; Leiser, D. B.; Katvala, V. W. (Inventor)

    1978-01-01

    The invention relates to reaction cured glass and glass coatings prepared by reacting a compound selected from the group consisting of silicon tetraboride, silicon hexaboride, other boron silicides, boron and mixtures with a reactive glass frit composed of a porous high silica borosilicate glass and boron oxide. The glassy composites of the present invention are useful as coatings on low density fibrous porous silica insulations used as heat shields and for articles such as reaction vessels that are subjected to high temperatures with rapid heating and cooling and that require resistance to temperature and repeated thermal shock at temperatures up to about 1482C (2700PF).

  12. Compositional Models of Glass/Melt Properties and their Use for Glass Formulation

    SciTech Connect

    Vienna, John D.; USA, Richland Washington

    2014-12-18

    Nuclear waste glasses must simultaneously meet a number of criteria related to their processability, product quality, and cost factors. The properties that must be controlled in glass formulation and waste vitrification plant operation tend to vary smoothly with composition allowing for glass property-composition models to be developed and used. Models have been fit to the key glass properties. The properties are transformed so that simple functions of composition (e.g., linear, polynomial, or component ratios) can be used as model forms. The model forms are fit to experimental data designed statistically to efficiently cover the composition space of interest. Examples of these models are found in literature. The glass property-composition models, their uncertainty definitions, property constraints, and optimality criteria are combined to formulate optimal glass compositions, control composition in vitrification plants, and to qualify waste glasses for disposal. An overview of current glass property-composition modeling techniques is summarized in this paper along with an example of how those models are applied to glass formulation and product qualification at the planned Hanford high-level waste vitrification plant.

  13. Compositional Models of Glass/Melt Properties and their Use for Glass Formulation

    DOE PAGESBeta

    Vienna, John D.; USA, Richland Washington

    2014-12-18

    Nuclear waste glasses must simultaneously meet a number of criteria related to their processability, product quality, and cost factors. The properties that must be controlled in glass formulation and waste vitrification plant operation tend to vary smoothly with composition allowing for glass property-composition models to be developed and used. Models have been fit to the key glass properties. The properties are transformed so that simple functions of composition (e.g., linear, polynomial, or component ratios) can be used as model forms. The model forms are fit to experimental data designed statistically to efficiently cover the composition space of interest. Examples ofmore » these models are found in literature. The glass property-composition models, their uncertainty definitions, property constraints, and optimality criteria are combined to formulate optimal glass compositions, control composition in vitrification plants, and to qualify waste glasses for disposal. An overview of current glass property-composition modeling techniques is summarized in this paper along with an example of how those models are applied to glass formulation and product qualification at the planned Hanford high-level waste vitrification plant.« less

  14. Hyperpolarized cesium ions doped in a glass material

    NASA Astrophysics Data System (ADS)

    Ishikawa, Kiyoshi

    2014-12-01

    Hyperpolarized (HP) 133 Cs nuclear magnetic resonance signals were measured from borosilicate glass cell walls during optical pumping of cesium vapor at high magnetic field (9.4 T). Significant signal enhancements were observed when additional heating of the cell wall was provided by intense but non-resonant laser irradiation, with integrated HP 133 Cs NMR signals and line widths varying as a function of heating laser power (and hence glass temperature). Given that virtually no Cs ions would originally be present in the glass, absorbed HP Cs atoms rarely met thermally-polarized Cs ions already at the surface; thus, spin-exchange via nuclear dipole interaction cannot be the primary mechanism for injecting spin polarization into the glass. Instead, it is concluded that the absorption and transport of HP atoms into the glass material itself is the dominant mechanism of nuclear spin injection at high temperatures-the first reported experimental demonstration of such a mechanism.

  15. GlassForm

    Energy Science and Technology Software Center (ESTSC)

    2011-09-16

    GlassForm is a software tool for generating preliminary waste glass formulas for a given waste stream. The software is useful because it reduces the number of verification melts required to develop a suitable additive composition. The software includes property models that calculate glass properties of interest from the chemical composition of the waste glass. The software includes property models for glass viscosity, electrical conductivity, glass transition temperature, and leach resistance as measured by the 7-daymore » product consistency test (PCT).« less

  16. 6. Looking glass aircraft in the project looking glass historic ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    6. Looking glass aircraft in the project looking glass historic district. View to north. - Offutt Air Force Base, Looking Glass Airborne Command Post, Looking Glass Avenue between Comstat Drive & Nightwatch Avenue, Offutt Air Force Base, Bellevue, Sarpy County, NE

  17. Oxynitride glass fibers

    NASA Technical Reports Server (NTRS)

    Patel, Parimal J.; Messier, Donald R.; Rich, R. E.

    1991-01-01

    Research at the Army Materials Technology Laboratory (AMTL) and elsewhere has shown that many glass properties including elastic modulus, hardness, and corrosion resistance are improved markedly by the substitution of nitrogen for oxygen in the glass structure. Oxynitride glasses, therefore, offer exciting opportunities for making high modulus, high strength fibers. Processes for making oxynitride glasses and fibers of glass compositions similar to commercial oxide glasses, but with considerable enhanced properties, are discussed. We have made glasses with elastic moduli as high as 140 GPa and fibers with moduli of 120 GPa and tensile strengths up to 2900 MPa. AMTL holds a U.S. patent on oxynitride glass fibers, and this presentation discusses a unique process for drawing small diameter oxynitride glass fibers at high drawing rates. Fibers are drawn through a nozzle from molten glass in a molybdenum crucible at 1550 C. The crucible is situated in a furnace chamber in flowing nitrogen, and the fiber is wound in air outside of the chamber, making the process straightforward and commercially feasible. Strengths were considerably improved by improving glass quality to minimize internal defects. Though the fiber strengths were comparable with oxide fibers, work is currently in progress to further improve the elastic modulus and strength of fibers. The high elastic modulus of oxynitride glasses indicate their potential for making fibers with tensile strengths surpassing any oxide glass fibers, and we hope to realize that potential in the near future.

  18. Glass dissolution rate measurement and calculation revisited

    NASA Astrophysics Data System (ADS)

    Fournier, Maxime; Ull, Aurélien; Nicoleau, Elodie; Inagaki, Yaohiro; Odorico, Michaël; Frugier, Pierre; Gin, Stéphane

    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 (Sgeo) that the rates measured on powders are closest to those found for monoliths. Overestimation of the reactive surface when using the BET model (SBET) 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 SBET/Sgeo ratio of 2.5 ± 0.2 for ISG powders, it is shown here that rates measured on powders and normalized to Sgeo should be divided by 1.3 and rates normalized to SBET 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%.

  19. FOAM GLASS INSULATION FROM WASTE GLASS

    EPA Science Inventory

    Waste glass has proven to be effective for the production of foam glass insulation both in the bulk or rigid board form and pellet form. Problems inherent with the use of water, carbon black and calcium carbonate as the foaming agents, have been identified and many have been solv...

  20. Retention of Halogens in Waste Glass

    SciTech Connect

    Hrma, Pavel R.

    2010-05-01

    In spite of their potential roles as melting rate accelerators and foam breakers, halogens are generally viewed as troublesome components for glass processing. Of five halogens, F, Cl, Br, I, and At, all but At may occur in nuclear waste. A nuclear waste feed may contain up to 10 g of F, 4 g of Cl, and ≤100 mg of Br and I per kg of glass. The main concern is halogen volatility, producing hazardous fumes and particulates, and the radioactive iodine 129 isotope of 1.7x10^7-year half life. Because F and Cl are soluble in oxide glasses and tend to precipitate on cooling, they can be retained in the waste glass in the form of dissolved constituents or as dispersed crystalline inclusions. This report compiles known halogen-retention data in both high-level waste (HLW) and low-activity waste (LAW) glasses. Because of its radioactivity, the main focus is on I. Available data on F and Cl were compiled for comparison. Though Br is present in nuclear wastes, it is usually ignored; no data on Br retention were found.

  1. Weakly supervised glasses removal

    NASA Astrophysics Data System (ADS)

    Wang, Zhicheng; Zhou, Yisu; Wen, Lijie

    2015-03-01

    Glasses removal is an important task on face recognition, in this paper, we provide a weakly supervised method to remove eyeglasses from an input face image automatically. We choose sparse coding as face reconstruction method, and optical flow to find exact shape of glasses. We combine the two processes iteratively to remove glasses more accurately. The experimental results reveal that our method works much better than these algorithms alone, and it can remove various glasses to obtain natural looking glassless facial images.

  2. Critical review of glass performance modeling

    SciTech Connect

    Bourcier, W.L.

    1994-07-01

    Borosilicate glass is to be used for permanent disposal of high-level nuclear waste in a geologic repository. Mechanistic chemical models are used to predict the rate at which radionuclides will be released from the glass under repository conditions. The most successful and useful of these models link reaction path geochemical modeling programs with a glass dissolution rate law that is consistent with transition state theory. These models have been used to simulate several types of short-term laboratory tests of glass dissolution and to predict the long-term performance of the glass in a repository. Although mechanistically based, the current models are limited by a lack of unambiguous experimental support for some of their assumptions. The most severe problem of this type is the lack of an existing validated mechanism that controls long-term glass dissolution rates. Current models can be improved by performing carefully designed experiments and using the experimental results to validate the rate-controlling mechanisms implicit in the models. These models should be supported with long-term experiments to be used for model validation. The mechanistic basis of the models should be explored by using modern molecular simulations such as molecular orbital and molecular dynamics to investigate both the glass structure and its dissolution process.

  3. Accelerated glass reaction under PCT conditions

    SciTech Connect

    Ebert, W.L.; Bates, J.K.; Buck, E.C.; Bradley, C.R.

    1992-01-01

    Static leach tests similar to PCT (Product Consistency Test) were performed for up to 2 years to assess long-term reaction behavior of high-level nuclear waste glasses similar to those at Defense Waste Processing Facility. These tests show the reaction rate to decrease with the reaction time from an initially high rate to a low rate, but then to accelerate to a higher rate after reaction times of about 1 year, depending on glass surface area/leachant volume ratio used. Solution concentrations of soluble glass components increase as the reaction is accelerated, while release of other glass components into solution is controlled by secondary phases. Net result is that transformation of glass to stable phases is accelerated while the solution becomes enriched in soluble components not effectively contained in secondary phases. Rate becomes linear in time after the acceleration and may be similar to the initial forward rate. A current model of glass reaction predicts that the glass reaction will be accelerated upon the formation of secondary phases which lower the silicic acid solution concentration. These tests show total Si concentration to increase upon reaction acceleration, however, which may be due to the slightly higher pH attained with the acceleration. The sudden change in the reaction rate is likely due to secondary phase formation. 17 refs, 2 tabs, 3 figs.

  4. Accelerated glass reaction under PCT conditions

    SciTech Connect

    Ebert, W.L.; Bates, J.K.; Buck, E.C.; Bradley, C.R.

    1992-12-31

    Static leach tests similar to PCT (Product Consistency Test) were performed for up to 2 years to assess long-term reaction behavior of high-level nuclear waste glasses similar to those at Defense Waste Processing Facility. These tests show the reaction rate to decrease with the reaction time from an initially high rate to a low rate, but then to accelerate to a higher rate after reaction times of about 1 year, depending on glass surface area/leachant volume ratio used. Solution concentrations of soluble glass components increase as the reaction is accelerated, while release of other glass components into solution is controlled by secondary phases. Net result is that transformation of glass to stable phases is accelerated while the solution becomes enriched in soluble components not effectively contained in secondary phases. Rate becomes linear in time after the acceleration and may be similar to the initial forward rate. A current model of glass reaction predicts that the glass reaction will be accelerated upon the formation of secondary phases which lower the silicic acid solution concentration. These tests show total Si concentration to increase upon reaction acceleration, however, which may be due to the slightly higher pH attained with the acceleration. The sudden change in the reaction rate is likely due to secondary phase formation. 17 refs, 2 tabs, 3 figs.

  5. WASTE GLASS MELTER PROCESS MONITORING WITH MILLIMETER WAVES

    EPA Science Inventory

    Millimeter-wave technologies can provide novel and reliable online monitoring capability for many important parameters inside nuclear waste glass melters, including temperature, emissivity, density, and viscosity. The physical and analytical basis for millimeter-wave monitoring o...

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

    SciTech Connect

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

    1996-03-19

    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.

  7. Glass in Class

    ERIC Educational Resources Information Center

    Greaves, Neville

    2005-01-01

    Glass is reviewed from fabrication to application, laying emphasis on the wide-ranging physics involved. This begins with liquids and solids and the way in which glasses are defined and can be demonstrated in the classroom. At the atomic level the regular structure of crystals and their irregular counterparts in glasses are explained through…

  8. Technique for Machining Glass

    NASA Technical Reports Server (NTRS)

    Rice, S. H.

    1982-01-01

    Process for machining glass with conventional carbide tools requires a small quantity of a lubricant for aluminum applied to area of glass to be machined. A carbide tool is then placed against workpiece with light pressure. Tool is raised periodically to clear work of glass dust and particles. Additional lubricant is applied as it is displaced.

  9. Oxynitride glass production procedure

    DOEpatents

    Weidner, Jerry R.; Schuetz, Stanley T.; O'Brien, Michael H.

    1991-01-01

    The invention is a process for the preparation of high quality oxynitride glasses without resorting to high pressures. Nitrogen-containing compounds such as Si.sub.3 N.sub.4 are first encapsulated in a low melting temperature glass. Particles of the encapsulated nitrogen-containing compound are mixed with other oxide glass-formers and melted in an atmosphere of flowing nitrogen and in the presence of buffering gas to form the oxynitride glass. Glasses containing up to 15 at % nitrogen have been prepared by this method.

  10. Radiation coloration resistant glass

    DOEpatents

    Tomozawa, Minoru; Watson, E. Bruce; Acocella, John

    1986-01-01

    A radiation coloration resistant glass is disclosed which is used in a radiation environment sufficient to cause coloration in most forms of glass. The coloration resistant glass includes higher proportions by weight of water and has been found to be extremely resistant to color change when exposed to such radiation levels. The coloration resistant glass is free of cerium oxide and has more than about 0.5% by weight water content. Even when exposed to gamma radiation of more than 10.sup.7 rad, the coloration resistant glass does not lose transparency.

  11. Radiation coloration resistant glass

    DOEpatents

    Tomozawa, M.; Watson, E.B.; Acocella, J.

    1986-11-04

    A radiation coloration resistant glass is disclosed which is used in a radiation environment sufficient to cause coloration in most forms of glass. The coloration resistant glass includes higher proportions by weight of water and has been found to be extremely resistant to color change when exposed to such radiation levels. The coloration resistant glass is free of cerium oxide and has more than about 0.5% by weight water content. Even when exposed to gamma radiation of more than 10[sup 7] rad, the coloration resistant glass does not lose transparency. 3 figs.

  12. High-Temperature Studies of Glass Dissolution Rates Close to Saturation

    SciTech Connect

    Zavarin, M; Roberts, S; Zhao, P; Williams, R; Rose, T; Rainer, A; Pawloski, G

    2004-06-14

    Most long-lived radionuclides associated with an underground nuclear test are incorporated into a melt glass and are released by glass dissolution to become part of the hydrologic source term (HST) (Pawloski et al., 2001). Although the rates of rhyolite glass dissolution are well known under conditions where the fluid is far from saturation with respect to glass, the rates are not well known under conditions where the fluid approaches saturation. These rates are commonly much lower than the far-fromsaturation rates, often by a factor greater than 100. In recent HST simulations (Pawloski et al., 2001; Pawloski et al., 2000; Tompson et al., 1999), we conservatively estimated steady-state release rates based on a far-from-saturation fluid conditions. In recent CHESHIRE near-field simulations (Pawloski et al., 2001), it was predicted that {approx}30% of the nuclear melt glass dissolved over 1000 years. Although the ''far-from-saturation rate'' approach provides a conservative estimate of glass dissolution, it may greatly overestimate the rates of melt glass dissolution. At CHESHIRE, less conservative estimates suggest that only {approx}1% of the nuclear melt glass will dissolve in 1000 years. Lower glass dissolution rates result in lower radionuclide release rates from nuclear melt glass. The following report documents glass dissolution experiments performed to measure glass dissolution rates close to saturation.

  13. Acoustics of glass harmonicas

    NASA Astrophysics Data System (ADS)

    Rossing, Thomas D.

    2001-05-01

    Glass musical instruments are probably as old as glassmaking. At least as early as the 17th century it was discovered that wine glasses, when rubbed with a wet finger, produced a musical tone. A collection of glasses played in this manner is called a glass harp. Another type of glass harmonica, called the armonica by its inventor Benjamin Franklin, employs glass bowls or cups turned by a horizontal axle, so the performer need only touch the rim of the bowls as they rotate to set them into vibration. We discuss the modes of vibration of both types of glass harmonica, and describe the different sounds that are emitted by rubbing, tapping, or bowing them. Rubbing with a wet finger tends to excite only the (2,0) mode and its harmonics through a ``stick-slip'' process, while tapping excites the other modes as well.

  14. Nanocrystalline glass ceramics: Structural, physical and optical properties

    NASA Astrophysics Data System (ADS)

    Singh, Satwinder; Singh, K.

    2015-02-01

    Four different transition metals contained nanocrystalline glass ceramics are synthesized by melting and quenching technique. The transition metal oxides play as former, modifier or both the roles depending on their oxidation states, field strength and covalent characteristics. The optical band gaps are observed in the range of 3.2-5.5 eV. The presence of nano-crystalline phases dominates the optical band gap. The softening temperature (Ts) is mainly affected by the residual glass in glass ceramics. These glass ceramics can be used as shielding materials for nuclear waste.

  15. High-temperature glass and glass coatings

    NASA Technical Reports Server (NTRS)

    Goldstein, H. E.; Katvala, V. E.; Leiser, D. B.

    1977-01-01

    Reaction-cured glasses resist thermal shock and maintain properties over range of -100 degrees Centrigrade to +1,480 degrees Centigrade. Stability makes these excellent materials for high-temperature glassware and tubing or as coatings for porous materials.

  16. Correlation of nuclear criticality safety computer codes with plutonium benchmark experiments and derivation of subcritical limits. [MGBS, TGAN, KEFF, HRXN, GLASS, ANISN, SPBL, and KENO

    SciTech Connect

    Clark, H.K.

    1981-10-01

    A compilation of benchmark critical experiments was made for essentially one-dimensional systems containing plutonium. The systems consist of spheres, series of experiments with cylinders and cuboids that permit extrapolation to infinite cylinders and slabs, and large cylinders for which separability of the neutron flux into a product of spatial components is a good approximation. Data from the experiments were placed in a form readily usable as computer code input. Aqueous solutions of Pu(NO/sub 3/)/sub 4/ are treated as solutions of PuO/sub 2/ in nitric acid. The apparent molal volume of PuO/sub 2/ as a function of plutonium concentration was derived from analyses of solution density data and was incorporated in the Savannah River Laboratory computer codes along with density tables for nitric acid. The biases of three methods of calculation were established by correlation with the benchmark experiments. The oldest method involves two-group diffusion theory and has been used extensively at the Savannah River Laboratory. The other two involve S/sub n/ transport theory with, in one method, Hansen-Roach cross sections and, in the other, cross sections derived from ENDF/B-IV. Subcritical limits were calculated by all three methods. Significant differences were found among the results and between the results and limits currently in the American National Standard for Nuclear Criticality Safety in Operations with Fissionable Materials Outside Reactor (ANSI N16.1), which were calculated by yet another method, despite the normalization of all four methods to the same experimental data. The differences were studied, and a set of subcritical limits was proposed to supplement and in some cases to replace those in the ANSI Standard, which is currently being reviewed.

  17. Application of the hydration thermodynamic model for glass durability under saturated tuff repository conditions

    SciTech Connect

    Ramsey, W.G.; Jantzen, C.M.

    1990-12-31

    The effects of tuff repository groundwater on glass dissolution and surface layer formation was examined utilizing the hydration thermodynamic model. A 28 day MCC-1 monolithic durability test was performed on the following glasses: SiO{sub 2}, obsidian, basalt, medieval window glasses, frit glass, and simulated nuclear waste glass. Silica dissolution was compared with the pH corrected free energy of hydration and shown to have the theoretical slope, ln(1/2.303RT), in agreement with MCC-1 tests using deionized water. X-ray diffraction and scanning electron microscopy identified clays of the saponite family and carbonates, on the glass surfaces leached in tuff groundwater. 31 refs.

  18. Weathering of glass in moist and polluted air

    NASA Astrophysics Data System (ADS)

    Cummings, K.; Lanford, W. A.; Feldmann, M.

    1998-03-01

    During the present century, stained glass windows in European cathedrals have shown a rapid deterioration due to weathering. It is widely believed that this rapid deterioration is a result of airborne pollutants not present for most of the 6-8 centuries since these cathedrals were built. To explore this idea, we have exposed soda-lime glass samples to ambients in which temperature, relative humidity (RH), and pollutant (SO 2 and NO 2) concentration were systematically varied. After exposure, the surfaces of these glass samples were analyzed using nuclear reaction analysis (NRA) (to measure hydrogen profiles) and Rutherford backscattering. Glasses subject to cracking during hydration, such as the glass used in many historic stained glass windows, are also discussed.

  19. Liquid Glass: A Facile Soft Replication Method for Structuring Glass.

    PubMed

    Kotz, Frederik; Plewa, Klaus; Bauer, Werner; Schneider, Norbert; Keller, Nico; Nargang, Tobias; Helmer, Dorothea; Sachsenheimer, Kai; Schäfer, Michael; Worgull, Matthias; Greiner, Christian; Richter, Christiane; Rapp, Bastian E

    2016-06-01

    Liquid glass is a photocurable amorphous silica nanocomposite that can be structured using soft replication molds and turned into glass via thermal debinding and sintering. Simple polymer bonding techniques allow the fabrication of complex microsystems in glass like microfluidic chips. Liquid glass is a step toward prototyping of glass microstructures at low cost without requiring cleanroom facilities or hazardous chemicals. PMID:27060964

  20. Plutonium immobilization in glass and ceramics

    SciTech Connect

    Knecht, D.A.; Murphy, W.M.

    1996-05-01

    The Materials Research Society Nineteenth Annual Symposium on the Scientific Basis for Nuclear Waste Management was held in Boston on November 27 to December 1, 1995. Over 150 papers were presented at the Symposium dealing with all aspects of nuclear waste management and disposal. Fourteen oral sessions and on poster session included a Plenary session on surplus plutonium dispositioning and waste forms. The proceedings, to be published in April, 1996, will provide a highly respected, referred compilation of the state of scientific development in the field of nuclear waste management. This paper provides a brief overview of the selected Symposium papers that are applicable to plutonium immobilization and plutonium waste form performance. Waste forms that were described at the Symposium cover most of the candidate Pu immobilization options under consideration, including borosilicate glass with a melting temperature of 1150 {degrees}C, a higher temperature (1450 {degrees}C) lanthanide glass, single phase ceramics, multi-phase ceramics, and multi-phase crystal-glass composites (glass-ceramics or slags). These Symposium papers selected for this overview provide the current status of the technology in these areas and give references to the relevant literature.

  1. Glass Melt Stability

    NASA Astrophysics Data System (ADS)

    Schaeffer, Helmut A.; Müller-Simon, Hayo

    The employment of sensors during glass melting represents a major prerequisite for an improved process control leading to higher production yields. In situ sensoring techniques can be divided into two groups: on the one hand, techniques which extract information of glass melt properties, e.g., oxidation state and concentrations of relevant polyvalent species (such as iron, sulfur, chromium) and on the other hand, techniques which monitor the furnace atmosphere with respect to toxic emissions (e.g., SO2, NO x ) and combustion species (e.g., CO, CO2, H2O). Nowadays it is feasible not only to install early warning systems indicating deviations from target glass properties, but also to implement process control systems which enforce a stable and reproducible glass melting. Examples are given for the redox control of green glass melting utilizing high portions of recycled cullet and the redox control of amber glass melting.

  2. Thermodynamics of Glass Melting

    NASA Astrophysics Data System (ADS)

    Conradt, Reinhard

    First, a model based on linear algebra is described by which the thermodynamic properties of industrial multi-component glasses and glass melts can be accurately predicted from their chemical composition. The model is applied to calculate the heat content of glass melts at high temperatures, the standard heat of formation of glasses from the elements, and the vapor pressures of individual oxides above the melt. An E-fiber glass composition is depicted as an example. Second, the role of individual raw materials in the melting process of E-glass is addressed, with a special focus on the decomposition kinetics and energetic situation of alkaline earth carriers. Finally, the heat of the batch-to-melt conversion is calculated. A simplified reaction path model comprising heat turnover, content of residual solid matter, and an approach to batch viscosity is outlined.

  3. Nonequilibrium viscosity of glass

    NASA Astrophysics Data System (ADS)

    Mauro, John C.; Allan, Douglas C.; Potuzak, Marcel

    2009-09-01

    Since glass is a nonequilibrium material, its properties depend on both composition and thermal history. While most prior studies have focused on equilibrium liquid viscosity, an accurate description of nonequilibrium viscosity is essential for understanding the low temperature dynamics of glass. Departure from equilibrium occurs as a glass-forming system is cooled through the glass transition range. The glass transition involves a continuous breakdown of ergodicity as the system gradually becomes trapped in a subset of the available configurational phase space. At very low temperatures a glass is perfectly nonergodic (or “isostructural”), and the viscosity is described well by an Arrhenius form. However, the behavior of viscosity during the glass transition range itself is not yet understood. In this paper, we address the problem of glass viscosity using the enthalpy landscape model of Mauro and Loucks [Phys. Rev. B 76, 174202 (2007)] for selenium, an elemental glass former. To study a wide range of thermal histories, we compute nonequilibrium viscosity with cooling rates from 10-12 to 1012K/s . Based on these detailed landscape calculations, we propose a simplified phenomenological model capturing the essential physics of glass viscosity. The phenomenological model incorporates an ergodicity parameter that accounts for the continuous breakdown of ergodicity at the glass transition. We show a direct relationship between the nonequilibrium viscosity parameters and the fragility of the supercooled liquid. The nonequilibrium viscosity model is validated against experimental measurements of Corning EAGLE XG™ glass. The measurements are performed using a specially designed beam-bending apparatus capable of accurate nonequilibrium viscosity measurements up to 1016Pas . Using a common set of parameters, the phenomenological model provides an accurate description of EAGLE XG™ viscosity over the full range of measured temperatures and fictive temperatures.

  4. Diamond turning of glass

    SciTech Connect

    Blackley, W.S.; Scattergood, R.O.

    1988-12-01

    A new research initiative will be undertaken to investigate the critical cutting depth concepts for single point diamond turning of brittle, amorphous materials. Inorganic glasses and a brittle, thermoset polymer (organic glass) are the principal candidate materials. Interrupted cutting tests similar to those done in earlier research are Ge and Si crystals will be made to obtain critical depth values as a function of machining parameters. The results will provide systematic data with which to assess machining performance on glasses and amorphous materials

  5. Containerless processing of glass

    NASA Technical Reports Server (NTRS)

    Happe, R. A.

    1981-01-01

    Ground-based research on the containerless melting of glass and experiments performed during a flight on the SPAR 6 are described. Experiments leading to selection of the flight sample composition, a silica-modified gallia/calcia glass, and the preparation of a one quarter inch diameter flight sample are described. During the flight experiment, a sample of the glass was containerless melted and cooled to a clear glass in a single axis acoustic positioning apparatus. The functioning of the flight experimental hardware was evaluated. The evaluation of the sample is presented.

  6. Glass--Sand + Imagination

    NASA Astrophysics Data System (ADS)

    Kolb, Kenneth E.; Kolb, Doris K.

    2000-07-01

    Glass is older than recorded history, and yet it is as new as tomorrow! How, when, or where man first learned to make glass is not known, but we do know that the ancient Egyptians were making glass articles as early as 2,600 B.C.E. (The making of glass beads may have begun as much as 3000 years earlier.) They used it to make jewelry and luxury items, such as decorative bowls and perfume bottles, available only to the wealthy.

  7. Drugstore Reading Glasses

    NASA Astrophysics Data System (ADS)

    Erlichson, Herman

    2006-03-01

    The occasion for this paper was my reading of a paper in the February 2005 issue of TPT. As one gets older the near point of the eye begins to recede.2 This is called presbyopia.3 An alternative to purchasing glasses from an optometrist is to purchase an inexpensive pair of reading glasses in a pharmacy. The pharmacy has these glasses ordered by diopters corresponding to the strength of the lens needed for a particular presbyopic eye. The glasses are, of course, not available for myopic eyes.

  8. Apollo 15 green glasses.

    NASA Technical Reports Server (NTRS)

    Ridley, W. I.; Reid, A. M.; Warner, J. L.; Brown, R. W.

    1973-01-01

    The samples analyzed include 28 spheres, portions of spheres, and angular fragments from soil 15101. Emerald green glasses from other soils are identical to those from 15101. The composition of the green glass is unlike that of any other major lunar glass group. The Fe content is comparable to that in mare basalts, but Ti is much lower. The Mg content is much higher than in most lunar materials analyzed to date, and the Cr content is also high. The low Al content is comparable to that of mare basalt glasses.

  9. Chalcogenide glass microsphere laser.

    PubMed

    Elliott, Gregor R; Murugan, G Senthil; Wilkinson, James S; Zervas, Michalis N; Hewak, Daniel W

    2010-12-01

    Laser action has been demonstrated in chalcogenide glass microsphere. A sub millimeter neodymium-doped gallium lanthanum sulphide glass sphere was pumped at 808 nm with a laser diode and single and multimode laser action demonstrated at wavelengths between 1075 and 1086 nm. The gallium lanthanum sulphide family of glass offer higher thermal stability compared to other chalcogenide glasses, and this, along with an optimized Q-factor for the microcavity allowed laser action to be achieved. When varying the pump power, changes in the output spectrum suggest nonlinear and/or thermal effects have a strong effect on laser action. PMID:21165022

  10. Rare Earth Phosphate Glass and Glass-Ceramic Proton Conductors

    SciTech Connect

    De Jonghe, Lutgard C.; Ray, Hannah L.; Wang, Ruigang

    2008-12-03

    The structure and conductivity of cerium and lanthanum phosphate glasses and glass-ceramics were investigated. The effects of varying the metal to phosphate ratio in the glasses, doping LaP3O9 glasses with Ce, and recrystallization of CeP3O9 glasses, on the glasses' microstructure and total conductivity were investigated using XRD, SEM, and AC impedance techniques. Strong increases in conductivity occurred when the glasses were recrystallized: the conductivity of a cerium metaphosphate glass increased conductivity after recrystallization from 10-7.5 S/cm to 10-6 S/cm at 400oC.

  11. Application of Glass Transition in Food Processing.

    PubMed

    Balasubramanian, S; Devi, Apramita; Singh, K K; Bosco, S J D; Mohite, Ashish M

    2016-04-25

    The phenomenon of glass transition has been employed to food products to study their stability. It can be applied as an integrated approach along with water activity and physical and chemical changes in food in processing and storage to determine the food stability. Also associated with the changes during agglomeration crystallization, caking, sticking, collapse, oxidation reactions, nonenzymatic browning, and microbial stability of food system. Various techniques such as Differential Scanning Calorimetry, Nuclear Magnetic Resonance, etc. have been developed to determine the glass transition temperature (Tg) of food system. Also, various theories have been applied to explain the concept of Tg and its relation to changes in food system. This review summarizes the understanding of concept of glass transition, its measurement, and application in food technology. PMID:25118113

  12. Getting Started with Glass

    ERIC Educational Resources Information Center

    White, Heather

    2007-01-01

    The metamorphosis of glass when heated is a magical process to students, yet teachers are often reluctant to try it in class. The biggest challenge in working with glass in the classroom is to simplify procedures just enough to ensure student success while maintaining strict safety practices so no students are injured. Project concepts and safety…

  13. Dramatic Stained Glass.

    ERIC Educational Resources Information Center

    Prater, Michael

    2002-01-01

    Describes an art project that is appropriate for students in fifth through twelfth grade in which they create Gothic-style stained-glass windows. Discusses how college students majoring in elementary education created stained-glass windows. Addresses how to adapt this lesson for younger students. (CMK)

  14. Proteins and glasses

    SciTech Connect

    Frauenfelder, H.

    1997-12-31

    The structure, the energy landscape, and the dynamics of proteins and glasses are similar. Both types of systems display characteristic nonexponential time dependencies of relaxation phenomena. Experiments suggest that both, proteins and glasses, are heterogeneous and that this fact causes the observed time dependence. This result is discussed in terms of the rough energy landscape characteristic of complex systems.

  15. Glasses and Contact Lenses

    MedlinePlus

    ... Here's Help White House Lunch Recipes Glasses and Contact Lenses KidsHealth > For Kids > Glasses and Contact Lenses Print A A A Text Size What's ... together the way they should. But eyeglasses or contact lenses, also called corrective lenses, can help most ...

  16. Surface Conductive Glass.

    ERIC Educational Resources Information Center

    Tanaka, John; Suib, Steven L.

    1984-01-01

    Discusses the properties of surface-conducting glass and the chemical nature of surface-conducting stannic (tin) oxide. Also provides the procedures necessary for the preparation of surface-conducting stannic oxide films on glass substrates. The experiment is suitable for the advanced inorganic chemistry laboratory. (JN)

  17. Indium fluoride glass fibers

    NASA Astrophysics Data System (ADS)

    Saad, Mohammed

    2012-03-01

    Fluoride glasses are the only material that transmit light from ultraviolet to mid-infrared and can be drawn into industrial optical fibers. The mechanical and optical properties of new indium fluoride glass fibers have been investigated. Multimode fiber 190 microns, has very high mechanical strength greater than 100 kpsi and optical loss as low as 45 dB/km between 2 and 4 microns. Unlike chalcogenide glass fibers, indium fluoride fiber has a wide transmission window from 0.3 to 5.5 microns without any absorption peak. Indium fluoride glass fibers are the technology of choice for all application requiring transmission up to 5 micron such as infrared contour measure (IRCM) and chemical sensing. Furthermore, Indium fluoride glasses have low phonon energy and can be heavily doped and co-doped whit rare-earth elements. Therefore they are very promising candidates for infrared fiber lasers.

  18. Defense HLW Glass Degradation Model

    SciTech Connect

    D. Strachan

    2004-10-20

    The purpose of this report is to document the development of a model for calculating the release rate for radionuclides and other key elements from high-level radioactive waste (HLW) glasses under exposure conditions relevant to the performance of the repository. Several glass compositions are planned for the repository, some of which have yet to be identified (i.e., glasses from Hanford and Idaho National Engineering and Environmental Laboratory). The mechanism for glass dissolution is the same for these glasses and the glasses yet to be developed for the disposal of DOE wastes. All of these glasses will be of a quality consistent with the glasses used to develop this report.

  19. 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

    NASA Astrophysics Data System (ADS)

    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.

  20. Theories of glass formation and glass transition

    SciTech Connect

    Langer, James S.

    2014-03-19

    This key-issues review is a plea for a new focus on simpler and more realistic models of glass-forming fluids. It seems to me that we have too often been led astray by sophisticated mathematical models that beautifully capture some of the most intriguing features of glassy behavior, but are too unrealistic to provide bases for predictive theories. As illustrations of what I mean, the first part of this article is devoted to brief summaries of imaginative, sensible, but disparate and often contradictory ideas for solving glass problems. Almost all of these ideas remain alive today, with their own enthusiastic advocates. I then describe numerical simulations, mostly by H Tanaka and coworkers, in which it appears that very simple, polydisperse systems of hard disks and spheres develop long range, Ising-like, bond-orientational order as they approach glass transitions. Finally, a summary of my recent proposal that topologically ordered clusters of particles, in disordered environments, tend to become aligned with each other as if they were two-state systems, and thus produce the observed Ising-like behavior. Neither Tanaka’s results nor my proposed interpretation of them fit comfortably within any of the currently popular glass theories.

  1. The leaching behavior of borate waste glass SL-1

    SciTech Connect

    Sheng, J.; Luo, S.; Tang, B.

    1999-11-01

    Vitrification is an attractive approach for treatment of the borate waste from nuclear power plants. SL-1 glass is a suitable borosilicate glass form to solidify the borate waste containing relatively high quantities of B and Na. The leaching behavior of SL-1 glass in deionized water has been investigated. Compared to the HLW-glass, the network structure of SL-1 glass is weak. It was found that the ion-exchange reactions dominated the glass corrosion process with water in low temperature leading conditions. The ion-exchange and network hydrolysis reactions together controlled the glass dissolution in high temperature leaching conditions. There was a peak in leach rate at about 70 C and a valley at about 100 C. The surface layer thickness was about 25 {micro}m. Na was almost totally depleted in the surface layer. At low temperature, the glass corrosion increases with leaching time. The glass corrosion remains about constant with leaching time at 90 C. The surface layer formed at 90 C is protective, which is less porous than the surface layer formed at 40 and 70 C.

  2. The leaching behavior of borate waste glass SL-1

    SciTech Connect

    Sheng, J. ); Luo, S.; Tang, B. )

    1999-01-01

    Vitrification is an attractive approach for treatment of the borate waste from nuclear power plants. SL-1 glass is a suitable borosilicate glass form to solidify the borate waste containing relatively high quantities of B and Na. The leaching behavior of SL-1 glass in deionized water has been investigated. Compared to the HLW-glass, the network structure of SL-1 glass is weak. It was found that the ion-exchange reactions dominated the glass corrosion process with water in low temperature leading conditions. The ion-exchange and network hydrolysis reactions together controlled the glass dissolution in high temperature leaching conditions. There was a peak in leach rate at about 70 C and a valley at about 100 C. The surface layer thickness was about 25 [micro]m. Na was almost totally depleted in the surface layer. At low temperature, the glass corrosion increases with leaching time. The glass corrosion remains about constant with leaching time at 90 C. The surface layer formed at 90 C is protective, which is less porous than the surface layer formed at 40 and 70 C.

  3. Development and characterization of basalt-glass ceramics for the immobilization of transuranic wastes

    SciTech Connect

    Lokken, R.O.; Chick, L.A.; Thomas, L.E.

    1982-09-01

    Basalt-based waste forms were developed for the immobilization of transuranic (TRU) contaminated wastes. The specific waste studied is a 3:1 blend of process sludge and incinerator ash. Various amounts of TRU blended waste were melted with Pomona basalt powder. The vitreous products were subjected to a variety of heat treatment conditions to form glass ceramics. The total crystallinity of the glass ceramic, ranging from 20 to 45 wt %, was moderately dependent on composition and heat treatment conditions. Three parent glasses and four glass ceramics with varied composition and heat treatment were produced for detailed phase characterization and leaching. Both parent glasses and glass ceramics were mainly composed of a continuous, glassy matrix phase. This glass matrix entered into solution during leaching in both types of materials. The Fe-Ti rich dispersed glass phase was not significantly degraded by leaching. The glass ceramics, however, exhibited four to ten times less elemental releases during leaching than the parent glasses. The glass ceramic matrix probably contains higher Fe and Na and lower Ca and Mg relative to the parent glass matrix. The crystallization of augite in the glass ceramics is believed to contribute to the improved leach rates. Leach rates of the basalt glass ceramic are compared to those of other TRU nuclear waste forms containing /sup 239/Pu.

  4. Engineering Glass Passivation Layers -Model Results

    SciTech Connect

    Skorski, Daniel C.; Ryan, Joseph V.; Strachan, Denis M.; Lepry, William C.

    2011-08-08

    The immobilization of radioactive waste into glass waste forms is a baseline process of nuclear waste management not only in the United States, but worldwide. The rate of radionuclide release from these glasses is a critical measure of the quality of the waste form. Over long-term tests and using extrapolations of ancient analogues, it has been shown that well designed glasses exhibit a dissolution rate that quickly decreases to a slow residual rate for the lifetime of the glass. The mechanistic cause of this decreased corrosion rate is a subject of debate, with one of the major theories suggesting that the decrease is caused by the formation of corrosion products in such a manner as to present a diffusion barrier on the surface of the glass. Although there is much evidence of this type of mechanism, there has been no attempt to engineer the effect to maximize the passivating qualities of the corrosion products. This study represents the first attempt to engineer the creation of passivating phases on the surface of glasses. Our approach utilizes interactions between the dissolving glass and elements from the disposal environment to create impermeable capping layers. By drawing from other corrosion studies in areas where passivation layers have been successfully engineered to protect the bulk material, we present here a report on mineral phases that are likely have a morphological tendency to encrust the surface of the glass. Our modeling has focused on using the AFCI glass system in a carbonate, sulfate, and phosphate rich environment. We evaluate the minerals predicted to form to determine the likelihood of the formation of a protective layer on the surface of the glass. We have also modeled individual ions in solutions vs. pH and the addition of aluminum and silicon. These results allow us to understand the pH and ion concentration dependence of mineral formation. We have determined that iron minerals are likely to form a complete incrustation layer and we plan

  5. Fiber-reinforced glass

    SciTech Connect

    Beier, W.; Markman, S.

    1997-12-01

    Fiber-reinforced glass composites are glass or glass ceramic matrices reinforced with long fibers of carbon or silicon carbide. These composites are lighter than steel but just as strong as many steel grades, and can resist higher temperatures. They also have outstanding resistance to impact, thermal shock, and wear, and can be formulated to control thermal and electrical conductivity. With proper tooling, operations such as drilling, grinding, and turning can be completed in half the time required for non-reinforced glass. Currently, fiber-reinforced glass components are primarily used for handling hot glass or molten aluminum during manufacturing operations. But FRG is also under test as an engineering material in a variety of markets, including the aerospace, automotive, and semiconductor industries. Toward this end, research is being carried out to increase the size of components that can be delivered on a production basis, to develop economical methods of achieving complex near-net shapes, and to reduce the cycle time for production of specific shapes. This article focuses on the properties and applications of fiber-reinforced glass composites.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2015-01-01

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

  9. Structure and dynamics of glasses and glass formers

    SciTech Connect

    Angell, C.A.; Ngai, K.L.; Kieffer, J.; Egami, T.; Nienhaus, G.U.

    1997-12-31

    This book was divided into the following parts: (1) short-time dynamics; (2) relaxation dynamics of glasses and glass formers; (3) glasslike systems, simulations, and models; (4) contrasting metallic, ionic, bio, and polymer systems; (5) structure, energetics, and polyamorphism; and (6) structure and dynamics of glasses and glass formers. Separate abstracts were prepared for most papers in this volume.

  10. Glass electrolyte composition

    DOEpatents

    Kucera, Gene H.; Roche, Michael F.

    1985-01-01

    An ionically conductive glass is disclosed for use as electrolyte in a high temperature electrochemical cell, particularly a cell with sodium anode and sulfur cathode. The glass includes the constituents Na.sub.2 O, ZrO.sub.2, Al.sub.2 O.sub.3 and SiO.sub.2 in selected proportions to be a single phase solid solution substantially free of crystalline regions and undissolved constituents. Other advantageous properties are an ionic conductivity in excess of 2.times.10.sup.-3 (ohm-cm).sup.-1 at 300.degree. C. and a glass transition temperature in excess of 500.degree. C.

  11. Glass electrolyte composition

    DOEpatents

    Kucera, G.H.; Roche, M.F.

    1985-01-08

    An ionically conductive glass is disclosed for use as electrolyte in a high temperature electrochemical cell, particularly a cell with sodium anode and sulfur cathode. The glass includes the constituents Na/sub 2/O, ZrO/sub 2/, Al/sub 2/O/sub 3/ and SiO/sub 2/ in selected proportions to be a single phase solid solution substantially free of crystalline regions and undissolved constituents. Other advantageous properties are an ionic conductivity in excess of 2 x 10/sup -3/ (ohm-cm)/sup -1/ at 300/sup 0/C and a glass transition temperature in excess of 500/sup 0/C.

  12. Nanocone array glass

    NASA Astrophysics Data System (ADS)

    D'Urso, Brian; Simpson, John T.; Kalyanaraman, Meenaa

    2007-04-01

    We report a novel method of producing ordered arrays of glass nanocones with precisely controlled height, lattice constant and aspect ratio. As with nanochannel glass, fibre drawing, bundling and redrawing are used to produce structured glass composite material. The surface of the composite is etched to form nanocones through a differential etching process. The lattice constant of the arrays ranges from 40 µm to 1.6 µm, while the aspect ratio of the nanocones is varied from 0.4 to 13 by simple changes in the chemistry of the hydrofluoric acid etching solution.

  13. PbO-free glasses for low temperature packaging

    SciTech Connect

    Brow, R.K.; Bencoe, D.N.; Tallant, D.R.

    1997-10-01

    Zinc polyphosphate glasses were examined as potential candidates for low temperature sealing applications. Glass-formation and properties were determined for the ZnO-P{sub 2}O{sub 5}, ZnO-B{sub 2}O{sub 3}-P{sub 2}O{sub 5} and ZnO-SnO-P{sub 2}O{sub 5} systems, and information about the short-range structures of these glasses was obtained by Raman and solid state nuclear magnetic resonance spectroscopies. In general, the most durable polyphosphate glasses have structures based on relatively short pyrophosphate chain lengths (i.e., 2 P-tetrahedra). Modified phosphate compositions are given, including compositions used to seal float glass substrates at temperatures as low as 500{degrees}C.

  14. Examination of subaerially altered basaltic glass with TEM and EELS

    SciTech Connect

    Luo, J.-S.

    1998-06-17

    We have examined the weathered surfaces of 720 year old Hawaiian basalt glasses that were recovered from a subaerial environment with high-resolution transmission electron microscopy (TEM) and energy filtered imaging and electron energy loss spectroscopy (EELS) techniques. Whereas the alteration products (palagonite) were physically detached from the underlying glass in most samples, a gel-like amorphous layer was observed adjacent to the glass in a few samples. To our knowledge, this is the first time a gel layer has been observed on weathered basalt. This is significant because analogous gel layers have been observed on nuclear waste glasses reacted in laboratory tests, and this demonstrates an important similarity in the mechanisms of the weathering of basalt and the corrosion of waste glasses.

  15. Assessment of water/glass interactions in waste glass melter operation

    SciTech Connect

    Postma, A.K.; Chapman, C.C.; Buelt, J.L.

    1980-04-01

    A study was made to assess the possibility of a vapor explosion in a liquid-fed glass melter and during off-standard conditions for other vitrification processes. The glass melter considered is one designed for the vitrification of high-level nuclear wastes and is comprised of a ceramic-lined cavity with electrodes for joule heating and processing equipment required to add feed and withdraw glass. Vapor explosions needed to be considered because experience in other industrial processes has shown that violent interactions can occur if a hot liquid is mixed with a cooler, vaporizable liquid. Available experimental evidence and theoretical analyses indicate that destructive glass/water interactions are low probability events, if they are possible at all. Under standard conditions, aspects of liquid-fed melter operation which work against explosive interactions include: (1) the aqueous feed is near its boiling point; (2) the feed contains high concentrations of suspended particles; (3) molten glass has high viscosity (greater than 20 poise); and (4) the glass solidifies before film boiling can collapse. While it was concluded that vapor explosions are not expected in a liquid-fed melter, available information does not allow them to be ruled out altogether. Several precautionary measures which are easily incorporated into melter operation procedures were identified and additional experiments were recommended.

  16. The Fate Of Silicon During Glass Corrosion Under Alkaline Conditions: A Mechanistic And Kinetic Study With The International Simple Glass

    SciTech Connect

    Gin, Stephane; Jollivet, Patrick; Fournie, Maxime; Berthon, Claude; Wang, Zhaoying; Mitroshkov, Alexandre V.; Zhu, Zihua; Ryan, Joseph V.

    2015-02-01

    International Simple Glass - a six oxide borosilicate glass selected by the international nuclear glass community to improve the understanding of glass corrosion mechanisms and kinetics - was altered at 90°C in a solution initially saturated with respect to amorphous 29-SiO2. The pH90°C, was fixed at 9 at the start of the experiment and raised to 11.5 after 209 d by the addition of KOH. Isotope sensitive analytical techniques were used to analyze the solution and altered glass samples, helping to understand the driving forces and rate limiting processes controlling long-term glass alteration. At pH 9, the corrosion rate continuously drops and the glass slowly transforms into a uniform, homogeneous and isovolumic amorphous alteration layer. The mechanisms responsible for this transformation are water diffusion through the growing alteration layer and ion exchange. We demonstrate that this amorphous alteration layer is not a precipitate resulting from the hydrolysis of the silicate network; it inherits from the glass structure from which the most weakly bonded cations (Na, Ca and B) have been released. At pH 11.5, the alteration process is very different: the high solubility of glass network formers (Si, Al, Zr) triggers the rapid and complete dissolution of the glass (dissolution becomes congruent) and precipitation of amorphous and crystalline phases. Unlike at pH 9 where glass corrosion rate decreased by 3 orders of magnitude likely due to transport-limiting phenomenon within the amorphous alteration layer, the rate at pH 11.5 is maintained at a value close to the forward rate due to both the hydrolysis of the silicate network and the precipitation of CSH and zeolites. This study provides key information for a unified model for glass dissolution.

  17. The fate of silicon during glass corrosion under alkaline conditions: A mechanistic and kinetic study with the International Simple Glass

    NASA Astrophysics Data System (ADS)

    Gin, Stéphane; Jollivet, Patrick; Fournier, Maxime; Berthon, Claude; Wang, Zhaoying; Mitroshkov, Alexandre; Zhu, Zihua; Ryan, Joseph V.

    2015-02-01

    International Simple Glass - a six oxide borosilicate glass selected by the international nuclear glass community to improve the understanding of glass corrosion mechanisms and kinetics - was altered at 90 °C in a solution initially saturated with respect to amorphous 29SiO2. The pH90°C, was fixed at 9 at the start of the experiment and raised to 11.5 after 209 d by the addition of KOH. Isotope sensitive analytical techniques were used to analyze the solution and altered glass samples, helping to understand the driving forces and rate limiting processes controlling long-term glass alteration. At pH 9, the corrosion rate continuously drops and the glass slowly transforms into a uniform, homogeneous amorphous alteration layer. The mechanisms responsible for this transformation are water penetration through the growing alteration layer and ion exchange. We demonstrate that this amorphous alteration layer is not a precipitate resulting from the hydrolysis of the silicate network; it is mostly inherited from the glass structure from which the most weakly bonded cations (Na, Ca and B) have been released. At pH 11.5, the alteration process is very different: the high solubility of glass network formers (Si, Al, Zr) triggers the rapid and complete dissolution of the glass (dissolution becomes congruent) and precipitation of amorphous and crystalline phases. Unlike at pH 9 where glass corrosion rate decreased by 3 orders of magnitude likely due to the retroaction of the alteration layer on water dynamics/reactivity at the reaction front, the rate at pH 11.5 is maintained at a value close to the forward rate due to both the hydrolysis of the silicate network promoted by OH- and the precipitation of CSH and zeolites. This study provides key information for a unified model for glass dissolution.

  18. Phase coexistence in proton glass

    SciTech Connect

    Schmidt, V.H.; Trybula, Z.; Pinto, N.J.; Shapiro, S.M.

    1996-11-01

    Proton glasses are crystals of composition M{sub 1{minus}x}(NW{sub 4}){sub x}W{sub 2}AO{sub 4}, where M = K,Rb, W = H,D, A = P,As. For x = 0 there is a ferroelectric (FE) transition, while for x = 1 there is an antiferroelectric (AFE) transition. In both cases, the transition is from a paraelectric (PE) state of tetragonal structure with dynamically disordered hydrogen bonds to an ordered state of orthorhombic structure. For an intermediate x range there is no transition, but the hydrogen rearrangements slow down, and eventually display nonergodic behavior characteristic of glasses. The authors and other have shown from spontaneous polarization, dielectric permittivity, nuclear magnetic resonance, and neutron diffraction experiments that for smaller x there is coexistence of ferroelectric and paraelectric phases, and for larger x there is coexistence of antiferroelectric and paraelectric phases. The authors present a method for analytically describing this coexistence, and the degree to which this coexistence is spatial or temporal.

  19. Glass Stronger than Steel

    DOE R&D Accomplishments Database

    Yarris, Lynn

    2011-03-28

    A new type of damage-tolerant metallic glass, demonstrating a strength and toughness beyond that of steel or any other known material, has been developed and tested by a collaboration of researchers from Berkeley Lab and Caltech.

  20. Whisker reinforced glass ceramic

    SciTech Connect

    Hirschfeld, D.A.; Brown, J.J. Jr.

    1996-06-03

    The process for making an in-situ whisker reinforced glass-ceramic that is up to 1.5 times as strong as conventional glass-ceramics was developed at Virginia Tech and patented in 1993. This technology has been identified as having commercial potential for use in high temperature heat exchanger applications for the electric power generation field by the National Center for Appropriate Technology (NCAT). This technology was licensed by MATVA, Inc., a small Virginia business, for further development. In particular, the goal of this project was to develop a property database and conduct initial testing of heat exchanger prototypes to demonstrate its potential application. This final report describes how the glass precursor was formed, physical properties of the glass-ceramic, techniques for making heat exchanger prototypes.

  1. Super ionic conductive glass

    DOEpatents

    Susman, Sherman; Volin, Kenneth J.

    1984-01-01

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

  2. Super ionic conductive glass

    DOEpatents

    Susman, S.; Volin, K.J.

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

  3. Seeing Glass Contractors Clearly.

    ERIC Educational Resources Information Center

    Deliberato, Jerry

    2003-01-01

    Offers seven tips for finding and working with an effective glass contractor. For example, schools should consider the company's reputation and longevity of service, and whether it has in-house engineering capabilities. (EV)

  4. Glass formation in microgravity

    NASA Technical Reports Server (NTRS)

    Ray, C. S.; Day, D. E.

    1987-01-01

    An account is given of containerless glass-forming experiments conducted aboard the Space Shuttle in 1985, using a single-axis acoustic levitator furnace apparatus. An attempt was made to obtain quantitative evidence for the suppression of heterogeneous nucleation/crystallization in containerless melts under microgravity conditions, as well as to study melt homogenization in the absence of gravity-driven convection and assess the feasibility of laser fusion target glass microsphere preparation with a microgravity apparatus of the present type. A ternary calcia-gallia-silica glass thus obtained indicated a 2-3-fold increase in glass-formation tendency for this material composition in microgravity, by comparison with 1g.

  5. Experimental hydration studies of natural and synthetic glasses

    SciTech Connect

    Bates, J.K.; Abrajano, T.A. Jr.; Ebert, W.L.; Mazer, J.J.; Gerding, T.J.

    1988-01-01

    The results of a series of hydration experiments on natural glasses (Hawaiian basalt, obsidian) and the nuclear waste glass WV-44 done to examine laboratory methods of accelerating reaction processes are summarized. The glasses were reacted in hydrothermal solution and in saturated vapor water. It was found that different reaction rates and processes were found using the differing conditions, and that laboratory efforts to accelerate and duplicate natural processes must amount for the physical processes that occur naturally. 18 refs., 5 figs., 1 tab.

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

    SciTech Connect

    Epstein, S.; Stolper, E.

    1992-01-01

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

  7. Reference commercial high-level waste glass and canister definition.

    SciTech Connect

    Slate, S.C.; Ross, W.A.; Partain, W.L.

    1981-09-01

    This report presents technical data and performance characteristics of a high-level waste glass and canister intended for use in the design of a complete waste encapsulation package suitable for disposal in a geologic repository. The borosilicate glass contained in the stainless steel canister represents the probable type of high-level waste product that will be produced in a commercial nuclear-fuel reprocessing plant. Development history is summarized for high-level liquid waste compositions, waste glass composition and characteristics, and canister design. The decay histories of the fission products and actinides (plus daughters) calculated by the ORIGEN-II code are presented.

  8. Pressure dependence of glass transition temperature of elastomeric glasses

    NASA Astrophysics Data System (ADS)

    Pae, K. D.; Tang, C.-L.; Shin, E.-S.

    1984-11-01

    The pressure dependence of the glass transition temperature Tg of two elastomers, Solithane 113 and 3,3-bis(azidomethyl)oxetane/tetrahydrofuran (BAMO/THF) has been determined, employing high-pressure differential thermal analysis (HP-DTA) and dielectric techniques, up to 8.5 kbar. The glasses of the elastomers were named the specific (or Pi glass) or the general glass depending on how the glasses were formed. A Pi glass was formed by lowering temperature under a constant pressure (Pi) and the pressure dependency of the Pi glass was determined after changing pressure only in the glassy state. The general glass consists of a series of specific glasses but the Tg is determined only at pressures under which the glass is formed. The Tg for both glasses increased with increasing pressure. However, the Tg for the Pi glass appears to level off at very high pressures while the Tg does not level off for the general glass. Thermodynamic analysis was made to show that for many general glasses dTg/dP=Δβ/(1+n)Δα holds, in which n=1 for Solithane and many other glasses. It is also shown that a modified Gibbs and DiMarzio theory can be used effectively to predict the observed experimental results.

  9. Method for making glass nonfogging

    DOEpatents

    Lord, David E.; Carter, Gary W.; Petrini, Richard R.

    1979-01-01

    A method for rendering glass nonfogging (to condensation fog) by sandwiching the glass between two electrodes such that the glass functions as the dielectric of a capacitor, a large alternating current (AC) voltage is applied across the electrodes for a selected time period causing the glass to absorb a charge, and the electrodes are removed. The glass absorbs a charge from the electrodes rendering it nonfogging. The glass surface is undamaged by application of the AC voltage, and normal optical properties are unaffected. This method can be applied to optical surfaces such as lenses, auto windshields, mirrors, etc., wherever condensation fog on glass is a problem.

  10. Baseline LAW Glass Formulation Testing

    SciTech Connect

    Kruger, Albert A.; Mooers, Cavin; Bazemore, Gina; Pegg, Ian L.; Hight, Kenneth; Lai, Shan Tao; Buechele, Andrew; Rielley, Elizabeth; Gan, Hao; Muller, Isabelle S.; Cecil, Richard

    2013-06-13

    The major objective of the baseline glass formulation work was to develop and select glass formulations that are compliant with contractual and processing requirements for each of the LAW waste streams. Other objectives of the work included preparation and characterization of glasses with respect to the properties of interest, optimization of sulfate loading in the glasses, evaluation of ability to achieve waste loading limits, testing to demonstrate compatibility of glass melts with melter materials of construction, development of glass formulations to support ILAW qualification activities, and identification of glass formulation issues with respect to contract specifications and processing requirements.

  11. Metallic glass composition

    DOEpatents

    Kroeger, Donald M.; Koch, Carl C.

    1986-01-01

    A metallic glass alloy that is either iron-based or nickel-based or based on a mixture of iron and nickel, containing lesser amounts of elements selected from the group boron, silicon carbon and phosphorous to which is added an amount of a ductility enhancing element selected from the group cerium, lanthanum, praseodymium and neodymium sufficient to increase ductility of the metallic glass upon annealing.

  12. Display innovations through glass

    NASA Astrophysics Data System (ADS)

    Hamilton, Lori L.

    2016-03-01

    Prevailing trends in thin, lightweight, high-resolution, and added functionality, such as touch sensing, continue to drive innovation in the display market. While display volumes grow, so do consumers’ need for portability, enhanced optical performance, and mechanical reliability. Technical advancements in glass design and process have enabled display innovations in these areas while supporting industry growth. Opportunities for further innovation remain open for glass manufacturers to drive new applications, enhanced functionality, and increased demand.

  13. Glasses formed by hypervelocity impact

    NASA Technical Reports Server (NTRS)

    Stoeffler, D.

    1984-01-01

    This paper presents description, classification, and geological setting of impact glasses, which are formed as a result of meteorite impacts with the planetary surface, and discusses the impact-glass formation process in the context of cratering mechanics. Impact glasses can be classified as belonging to two major groups: (1) mineral glasses, which are identical in composition to a mineral, and (2) rock glasses, which have the composition of a rock or a mixture of various rocks. Rock glasses may be (1) melt ejecta, (2) parts of a coherent melt layer inside the crater cavity, or (3) dikes or veins. The composition of rock glasses at a particular crater can be matched by that of the target. In nonporous rocks, the formation of rock glasses requires peak pressures in excess of 60-80 GPa, while mineral glasses are formed in the pressure range of about 25 to 55 GPa; in porous rocks, interstitial glass forms at pressures as low as 5 GPa.

  14. Volcanic Glasses: Construction Materials

    NASA Astrophysics Data System (ADS)

    Moskowitz, Samuel E.

    1998-01-01

    Natural glass is the product of rapidly cooled molten rock. Two natural sources of the melt are volcanic eruption and meteoritic impact. Pure glass is an amorphous aggregate. Volcanic glass is a material that could be utilized in the construction of extraterrestrial outposts. Pumice and perlite are volcanic glasses currently used in the building industry. Samples of natural volcanic glass found in the lunar regolith were returned to Earth as part of the Apollo and Luna programs. An alpha proton X-ray spectrometer onboard the Pathfinder recently examined martian rocks located in the vicinity of the lander craft. Preliminary results of chemical composition by weight of SiO2 50-55%, Al203 11-13%, K20 1-2%, Na20 2-5%, CaO 4-6%, MgO 3-7%, FeO 12-14%, S03 2-5%, and MnO <1% were given for two rocks. Parenthetically, the values for K and Mn were perhaps too high, and the analysis was based on X-ray data only. The appreciable amount of silica already found on Mars and empirical evidence to support the hypothesis that the planet once had water sufficient to rapidly cool magma imply the possibility of discovering natural glass of volcanic origin in subsequent missions.

  15. Containerless synthesis of interesting glasses

    NASA Technical Reports Server (NTRS)

    Weinberg, Michael C.

    1990-01-01

    One aspect of containerless glass experimentation was thoroughly examined: glass forming ability. It is argued that although containerless processing will abet glass formation, other ground-based methods can do the job better. However, these methods have limitations, such as sample dimensions and concomitant ability to make property measurements. Most importantly, perhaps, is the observation that glass properties are a function of preparation procedure. Thus, it seems as though there still is an argument for use of containerless processing for glass forming.

  16. Glass and Glass-Ceramic Materials from Simulated Composition of Lunar and Martian Soils: Selected Properties and Potential Applications

    NASA Technical Reports Server (NTRS)

    Ray, C. S.; Sen, S.; Reis, S. T.; Kim, C. W.

    2005-01-01

    In-situ resource processing and utilization on planetary bodies is an important and integral part of NASA's space exploration program. Within this scope and context, our general effort is primarily aimed at developing glass and glass-ceramic type materials using lunar and martian soils, and exploring various applications of these materials for planetary surface operations. Our preliminary work to date have demonstrated that glasses can be successfully prepared from melts of the simulated composition of both lunar and martian soils, and the melts have a viscosity-temperature window appropriate for drawing continuous glass fibers. The glasses are shown to have the potential for immobilizing certain types of nuclear wastes without deteriorating their chemical durability and thermal stability. This has a direct impact on successfully and economically disposing nuclear waste generated from a nuclear power plant on a planetary surface. In addition, these materials display characteristics that can be manipulated using appropriate processing protocols to develop glassy or glass-ceramic magnets. Also discussed in this presentation are other potential applications along with a few selected thermal, chemical, and structural properties as evaluated up to this time for these materials.

  17. Glass microsphere lubrication

    NASA Technical Reports Server (NTRS)

    Geiger, Michelle; Goode, Henry; Ohanlon, Sean; Pieloch, Stuart; Sorrells, Cindy; Willette, Chris

    1991-01-01

    The harsh lunar environment eliminated the consideration of most lubricants used on earth. Considering that the majority of the surface of the moon consists of sand, the elements that make up this mixture were analyzed. According to previous space missions, a large portion of the moon's surface is made up of fine grained crystalline rock, about 0.02 to 0.05 mm in size. These fine grained particles can be divided into four groups: lunar rock fragments, glasses, agglutinates (rock particles, crystals, or glasses), and fragments of meteorite material (rare). Analysis of the soil obtained from the missions has given chemical compositions of its materials. It is about 53 to 63 percent oxygen, 16 to 22 percent silicon, 10 to 16 percent sulfur, 5 to 9 percent aluminum, and has lesser amounts of magnesium, carbon, and sodium. To be self-supporting, the lubricant must utilize one or more of the above elements. Considering that the element must be easy to extract and readily manipulated, silicon or glass was the most logical choice. Being a ceramic, glass has a high strength and excellent resistance to temperature. The glass would also not contaminate the environment as it comes directly from it. If sand entered a bearing lubricated with grease, the lubricant would eventually fail and the shaft would bind, causing damage to the system. In a bearing lubricated with a solid glass lubricant, sand would be ground up and have little effect on the system. The next issue was what shape to form the glass in. Solid glass spheres was the only logical choice. The strength of the glass and its endurance would be optimal in this form. To behave as an effective lubricant, the diameter of the spheres would have to be very small, on the order of hundreds of microns or less. This would allow smaller clearances between the bearing and the shaft, and less material would be needed. The production of glass microspheres was divided into two parts, production and sorting. Production includes the

  18. DWPF GLASS BEADS AND GLASS FRIT TRANSPORT DEMONSTRATION

    SciTech Connect

    Adamson, D; Bradley Pickenheim, B

    2008-11-24

    DWPF is considering replacing irregularly shaped glass frit with spherical glass beads in the Slurry Mix Evaporator (SME) process to decrease the yield stress of the melter feed (a non-Newtonian Bingham Plastic). Pilot-scale testing was conducted on spherical glass beads and glass frit to determine how well the glass beads would transfer when compared to the glass frit. Process Engineering Development designed and constructed the test apparatus to aid in the understanding and impacts that spherical glass beads may have on the existing DWPF Frit Transfer System. Testing was conducted to determine if the lines would plug with the glass beads and the glass frit slurry and what is required to unplug the lines. The flow loop consisted of vertical and horizontal runs of clear PVC piping, similar in geometry to the existing system. Two different batches of glass slurry were tested: a batch of 50 wt% spherical glass beads and a batch of 50 wt% glass frit in process water. No chemicals such as formic acid was used in slurry, only water and glass formers. The glass beads used for this testing were commercially available borosilicate glass of mesh size -100+200. The glass frit was Frit 418 obtained from DWPF and is nominally -45+200 mesh. The spherical glass beads did not have a negative impact on the frit transfer system. The transferring of the spherical glass beads was much easier than the glass frit. It was difficult to create a plug with glass bead slurry in the pilot transfer system. When a small plug occurred from setting overnight with the spherical glass beads, the plug was easy to displace using only the pump. In the case of creating a man made plug in a vertical line, by filling the line with spherical glass beads and allowing the slurry to settle for days, the plug was easy to remove by using flush water. The glass frit proved to be much more difficult to transfer when compared to the spherical glass beads. The glass frit impacted the transfer system to the point

  19. Competitive formation of glasses and glass-matrix composites

    SciTech Connect

    Lu, Zhao Ping; Ma, D.; Liu, Chain T; Chang, Y. Austin

    2007-01-01

    By systematically investigating the effect of chemical composition on the competitive formation of glasses in various systems, we attempt to address two long-standing scientific puzzles upon metallic glasses, i.e., (i) which composition is the best for forming glasses and glass-matrix composites and (ii) what determines the easy glass-forming composition range in a given alloy system. Our findings have led to the construction of a qualitative microstructure selection map, which is useful for guiding the design of bulkier metallic glasses and glass-matrix composites. In addition, our analysis demonstrates that the classical kinetic treatment of glass formation is insufficient; to analyze glass formation properly, it is necessary to go beyond simple assumptions of single polymorphic solidification during crystallization.

  20. Pourbaix diagram for the prediction of waste glass durability in geologic environments

    SciTech Connect

    Jantzen, C M

    1987-01-01

    Dissolution of nuclear waste glass occurs by corrosion mechanisms similar to those of metallurgical and mineralogic systems albeit on different time scales. The effects of imposed pH and oxidation potential (Eh) conditions existing in natural environments on metals and minerals have been quantitatively and phenomenologically described in compendiums of Pourbaix (pH-potential) diagrams. Construction of Pourbaix diagrams to quantify the response of nuclear waste glasses to repository specific pH and Eh conditions is demonstrated. The expected long-term effects of groundwater contact on the durability of nuclear waste glasses can then be unified. 40 refs., 4 figs., 1 tab.

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

    NASA Astrophysics Data System (ADS)

    Loiseau, P.; Caurant, D.; Baffier, N.; Mazerolles, L.; Fillet, C.

    2004-10-01

    Glass-ceramic waste forms such as zirconolite (nominally CaZrTi 2O 7) based ones can be envisaged as good candidates for minor actinides or Pu immobilization. Such materials, in which the actinides (or lanthanides used as actinide surrogates) would be preferentially incorporated into zirconolite crystals homogeneously dispersed in a durable glassy matrix, can be prepared by controlled crystallization (nucleation + crystal growth) of parent glasses belonging to the SiO 2-Al 2O 3-CaO-ZrO 2-TiO 2 system. In this work we present the effects of the nature of the minor actinide surrogate (Ce, Nd, Eu, Gd, Yb, Th) on the structure, the microstructure and the composition of the zirconolite crystals formed in the bulk of the glass-ceramics. The amount of lanthanides and thorium incorporated into zirconolite crystals is discussed in relation with the capacity of the glass to accommodate these elements and of the crystals to incorporate them in the calcium and zirconium sites of their structure.

  2. Glass matrix armor

    DOEpatents

    Calkins, Noel C.

    1991-01-01

    An armor system which utilizes glass. A plurality of constraint cells are mounted on a surface of a substrate, which is metal armor plate or a similar tough material, such that the cells almost completely cover the surface of the substrate. Each constraint cell has a projectile-receiving wall parallel to the substrate surface and has sides which are perpendicular to and surround the perimeter of the receiving wall. The cells are mounted such that, in one embodiment, the substrate surface serves as a sixth side or closure for each cell. Each cell has inside of it a plate, termed the front plate, which is parallel to and in contact with substantially all of the inside surface of the receiving wall. The balance of each cell is completely filled with a projectile-abrading material consisting of glass and a ceramic material and, in certain embodiments, a polymeric material. The glass may be in monolithic form or particles of ceramic may be dispersed in a glass matrix. The ceramic material may be in monolithic form or may be in the form of particles dispersed in glass or dispersed in said polymer.

  3. Jet penetration in glass

    SciTech Connect

    Moran, B.; Glenn, L.A.; Kusubov, A.

    1991-05-01

    We describe a phenomenological model which accounts for the mechanical response of glass to intense impulsive loading. An important aspect of this response is the dilatancy accompanying fracture. We have also conducted a number of experiments with 38.1-mm diameter precision shaped charges to establish the performance against various targets and to allow evaluation of our model. At 3 charge diameters standoff, the data indicate that both virgin and damaged glass offer better (Bernoulli-scaled) resistance to penetration than either of 4340 steel, or 6061-T6 aluminum alloy. Time-resolved measurements indicate two distinct phases of jet penetration in glass: An initial hydrodynamic phase, and a second phase characterized by a slower penetration velocity. Our calculations show that at early time, a crater is formed around the jet and only the tip of the undisturbed jet interacts with the glass. At late time the glass has collapsed on the jet and degraded penetration continues via a disturbed and fragmented jet.

  4. Sol-Gel Glasses

    NASA Technical Reports Server (NTRS)

    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.

  5. Modifier coordination and phosphate glass networks

    SciTech Connect

    Brow, R.; Click, C.A.; Alam, T.M.

    1999-11-30

    The addition of up to approximately 16 mole% Cs{sub 2}O to vitreous P{sub 2}O{sub 5} reduces the glass transition temperature (T{sub g}) by 150 K, whereas further additions up to 50 mole% produce little additional change in T{sub g}. {sup 31}P magic angle spinning nuclear magnetic resonance spectra indicate that the phosphate network is progressively dipolymerized over the entire range of compositions. The property trend is explained by a transition in the Cs{sup +} coordination environment, from isolated Cs-polyhedra below {approximately}16 mole% Cs{sub 2}O to a corner-sharing Cs-polyhedral sub-structure in the glasses with greater Cs{sub 2}O contents. This modifier transition does not occur in Al-phosphate glasses. {sup 27}Al MAS NMR spectra indicate that the average Al coordination number decreases with increasing Al{sub 2}O{sub 3} content to avoid the formation of Al-O-Al bonds in these binary phosphate glasses.

  6. Glass strengthening and patterning methods

    DOEpatents

    Harper, David C; Wereszczak, Andrew A; Duty, Chad E

    2015-01-27

    High intensity plasma-arc heat sources, such as a plasma-arc lamp, are used to irradiate glass, glass ceramics and/or ceramic materials to strengthen the glass. The same high intensity plasma-arc heat source may also be used to form a permanent pattern on the glass surface--the pattern being raised above the glass surface and integral with the glass (formed of the same material) by use of, for example, a screen-printed ink composition having been irradiated by the heat source.

  7. SETTLING OF SPINEL IN A HIGH-LEVEL WASTE GLASS MELTER

    SciTech Connect

    Pavel Hrma; Pert Schill; Lubomir Nemec

    2002-01-07

    High-level nuclear waste is being vitrified, i.e., converted to a durable glass that can be stored in a safe repository for hundreds of thousands of years. Waste vitrification is accomplished in reactors called melters to which the waste is charged together with glass-forming additives. The mixture is electrically heated to a temperature as high as 1150 decrees C to create a melt that becomes glass on cooling.

  8. Transient nucleation in glasses

    NASA Technical Reports Server (NTRS)

    Kelton, K. F.

    1991-01-01

    Nucleation rates in condensed systems are frequently not at their steady state values. Such time dependent (or transient) nucleation is most clearly observed in devitrification studies of metallic and silicate glasses. The origin of transient nucleation and its role in the formation and stability of desired phases and microstructures are discussed. Numerical models of nucleation in isothermal and nonisothermal situations, based on the coupled differential equations describing cluster evolution within the classical theory, are presented. The importance of transient nucleation in glass formation and crystallization is discussed.

  9. Crystallization of fluorozirconate glasses

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Doremus, Robert H.; Bruce, A. J.; Moynihan, C. T.

    1984-01-01

    The crystallization of a number of glasses of the fluorozirconate family has been studied (using powder X-ray diffraction and DSC) as a function of time and temperature of heating. The main crystalline phases were beta BaZrF6 and beta BaZr2F10. Stable and metastble transformations to the low-temperature alpha phases were also investigated. The size of crystallites in fully devitrified glasses was calculated (from line broadening of the X-ray diffraction peaks) to be about 60 nm.

  10. Characterization of Analytical Reference Glass-1 (ARG-1)

    SciTech Connect

    Smith, G.L.

    1993-12-01

    High-level radioactive waste may be immobilized in borosilicate glass at the West Valley Demonstration Project, West Valley, New York, the Defense Waste Processing Facility (DWPF), Aiken, South Carolina, and the Hanford Waste Vitrification Project (HWVP), Richland, Washington. The vitrified waste form will be stored in stainless steel canisters before its eventual transfer to a geologic repository for long-term disposal. Waste Acceptance Product Specifications (WAPS) (DOE 1993), Section 1.1.2 requires that the waste form producers must report the measured chemical composition of the vitrified waste in their production records before disposal. Chemical analysis of glass waste forms is receiving increased attention due to qualification requirements of vitrified waste forms. The Pacific Northwest Laboratory (PNL) has been supporting the glass producers` analytical laboratories by a continuing program of multilaboratory analytical testing using interlaboratory ``round robin`` methods. At the PNL Materials Characterization Center Analytical Round Robin 4 workshop ``Analysis of Nuclear Waste Glass and Related Materials,`` January 16--17, 1990, Pleasanton, California, the meeting attendees decided that simulated nuclear waste analytical reference glasses were needed for use as analytical standards. Use of common standard analytical reference materials would allow the glass producers` analytical laboratories to calibrate procedures and instrumentation, to control laboratory performance and conduct self-appraisals, and to help qualify their various waste forms.

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

    SciTech Connect

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

    1995-12-31

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

  12. Characterizing glass frits for slurries

    NASA Technical Reports Server (NTRS)

    Nakano, H. N.

    1979-01-01

    Glass frit can be mixed with consistently reproducible properties even from different batches of glass frit using technique to measure one quantity that determines integrated properties of frit for combination with given liquid.

  13. Containerless processing of fluoride glass

    NASA Technical Reports Server (NTRS)

    Doremus, Robert H.

    1990-01-01

    Ground-based experiments on glass formation, crystallization, surface tension, vaporization, and chemical durability of a zirconium-barium-lanthanum (ZBL) fluoride glass are summarized. In a container large, columnar grains grew out from the container-glass interface during cooling. The main crystalline phase was alpha BaZrF6. A ZBL glass sphere was levitated acoustically during Shuttle flight STS-11. The glass was melted and then cooled while being levitated (containerless). Crystallization in the recovered sample was very fine and mainly beta BaZr2F10, showing the influence of the container on the nucleation and microstructure of crystallization in the glass. Glass formation should be easier for a containerless glass than in a container.

  14. Prediction of radioactive waste glass durability by the hydration thermodynamic model: Application to saturated repository environments

    SciTech Connect

    Jantzen, C.M. ); Ramsey, W.G. . Dept. of Ceramic Engineering)

    1989-01-01

    The effects of groundwater chemistry on glass durability were examined using the hydration thermodynamic model. The relative durabilities of SiO{sub 2}, obsidians, basalts, nuclear waste glasses, medieval window glasses, and a frit glass were determined in tuffaceous groundwater, basaltic groundwater, WIPP-A brine, and Permian-A brine using the monolithic MCC-1 durability test. For all the groundwaters, the free energy of hydration, calculated from the glass composition and the final experimental pH, was linearly related to the logarithm of the measured silica concentration. The linear equation was identical to that observed previously for these glasses during MCC-1 testing in deionized water. In the groundwater-dominated MCC-1 experiments, the pH values for all the glasses tested appeared to be buffered by the groundwater-precipitate chemistry. The behavior of poorly durable glasses demonstrated that the silica release is a function of the ionic strength of the solution. The ionic strength, in turn, reflects the effect of the groundwater chemistry on the pH. Using the hydration thermodynamic model, nuclear waste glass durability in saturated repository environments can be predicted from the glass composition and the groundwater and the groundwater pH. 47 refs., 3 figs. 1 tab.

  15. Glass ceramic toughened with tetragonal zirconia

    DOEpatents

    Keefer, K.D.

    1984-02-10

    A phase transformation-toughened glass ceramic and a process for making it are disclosed. A mixture of particulate network-forming oxide, network-modifying oxide, and zirconium oxide is heated to yield a homogeneous melt, and this melt is then heat treated to precipitate an appreciable quantity of tetragonal zirconia, which is retained at ambient temperature to form a phase transformation-toughened glass ceramic. Nuclearing agents and stabilizing agents may be added to the mixture to facilitate processing and improve the ceramic's properties. Preferably, the mixture is first melted at a temperature from 1200 to 1700/sup 0/C and is then heat-treated at a temperature within the range of 800 to 1200/sup 0/C in order to precipitate tetragonal ZrO/sub 2/. The composition, as well as the length and temperature of the heat treatment, must be carefully controlled to prevent solution of the precipitated tetragonal zirconia and subsequent conversion to the monoclinic phase.

  16. Effects of alteration product precipitation on glass dissolution

    SciTech Connect

    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

  17. Ion-implantation-induced stress in glasses: Variation of damage mode efficiency with changes in glass structure

    NASA Astrophysics Data System (ADS)

    Arnold, G. W.

    1988-05-01

    Ion implantation induces lateral stress in glass due to the volume dilatation in the implanted near-surface region. Cantilever-beam experiments allow these quantities to be measured as a function of fluence. For fused silica the stress data for various incident ions are found to scale with atomic collision energy deposition. In sharp contrast, Pyrex (alkali-borosilicate) glass, (1 - x)(Na, K) 2O· xB 2O 3·3SiO 2 glass, and a sodalime (microscope slide) glass, yield stress values which scale with energy deposition into electronic processes. More significantly, this mode of damage production is dominant for the nuclear waste glasses PNL 76-68 and SRP. The void space in fused silica allows room for displaced Si and/or O. For the complex alkali-containing silicates, the interstitial volume is restricted. In the latter case, the probability increases that permanent defects can be formed by ionization-induced bond-breaking and network relaxation. These data imply that alpha-particle ionization energy deposition may be an important factor in nuclear waste glass radiation damage production, but the magnitude of this contribution has not yet been evaluated.

  18. Making Highly Pure Glass Rods

    NASA Technical Reports Server (NTRS)

    Naumann, R. J.

    1986-01-01

    Proposed quasi-containerless method for making glass rods or fibers minimizes contact between processing equipment and product. Method allows greater range of product sizes and shapes than achieved in experiments on containerless processing. Molten zone established in polycrystalline rod. Furnace sections separated, and glass rod solidifies between them. Clamp supports solid glass as it grows in length. Pulling clamp rapidly away from melt draws glass fiber. Fiber diameter controlled by adjustment of pulling rate.

  19. Glass and ceramics. [lunar resources

    NASA Technical Reports Server (NTRS)

    Haskin, Larry A.

    1992-01-01

    A variety of glasses and ceramics can be produced from bulk lunar materials or from separated components. Glassy products include sintered regolith, quenched molten basalt, and transparent glass formed from fused plagioclase. No research has been carried out on lunar material or close simulants, so properties are not known in detail; however, common glass technologies such as molding and spinning seem feasible. Possible methods for producing glass and ceramic materials are discussed along with some potential uses of the resulting products.

  20. Toward acceptance of DWPF glass at a Federal Repository

    SciTech Connect

    Plodinec, M.J.; Stevens, W.R. III; Hacker, B.A.; Baxter, R.G.

    1987-01-01

    Construction of the nations's first facility to immobilize defense high-level nuclear waste, the Defense Waste Processing Facility (DWPF) at the Savannah River Plant, is scheduled to be completed soon. The Department of Energy's Office of Civilian Radioactive Waste Management (OCRWM) has set up a Waste Acceptance Process to provide reasonable assurance that the waste glass produced in the DWPF will be acceptable for permanent storage in a federal repository. As part of this process, detailed specifications have been developed for the waste glass itself, the canister which will contain the waste glass, the sealed canister after it is filled with waste glass, and quality assurance of the product. Savannah River has developed a detailed strategy for demonstrating compliance with each of the specifications, which is documented in a Waste Compliance Plan (WCP). In this paper, the compliance strategy, and progress in implementing the WCP are presented. 12 refs., 3 figs.

  1. Glass ceramic development for the combined fission products streams

    SciTech Connect

    Kossoy-simakov, Anna-eden; Tang, Ming; Valdez, James A; Usov, Igor O; Sickafus, Kurt E; Crum, Jarrod; Turo, Laura; Riley, Brian

    2011-01-18

    After immobilization, nuclear waste is stored for minimally hundreds of years. In waste-forms {beta}, {gamma}-radiation are main causes for damage. The objectives is to test radiation stability of PNNL synthesized glass-ceramics. Monitoring was done looking for changes in the microstructure or phase composition. These are designed for immobilization of: lanthanides, alkaline metals, alkaline arths, transition metals, high molybdenum content - 6.94%, and multi-phase glass-ceramic. The conclusion on aqueous stability is the PNNL glass ceramics - glass phase erodes but crystalline phases don't and it's more resistant to corrosion than vitrified waste. Leachability tests in accordance with standards will be performed and the results will be compared to XRD.

  2. Attenuation of Glass Dissolution in the Presence of Natural Additives

    NASA Technical Reports Server (NTRS)

    Sang, Jing C.; Barkatt, Aaron; OKeefe, John A.

    1993-01-01

    The study described here explored the dissolution kinetics of glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase. The results demonstrated 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. The 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.

  3. Interactions between the glass fiber coating and oxidized carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Ku-Herrera, J. J.; Avilés, F.; Nistal, A.; Cauich-Rodríguez, J. V.; Rubio, F.; Rubio, J.; Bartolo-Pérez, P.

    2015-03-01

    Chemically oxidized multiwall carbon nanotubes (MWCNTs) were deposited onto commercial E-glass fibers using a dipping procedure assisted by ultrasonic dispersion. In order to investigate the role of the fiber coating (known as "sizing"), MWCNTs were deposited on the surface of as-received E-glass fibers preserving the proprietary coating as well as onto glass fibers which had the coating deliberately removed. Scanning electron microscopy and Raman spectroscopy were used to assess the distribution of MWCNTs onto the fibers. A rather homogeneous coverage with high density of MWCNTs onto the glass fibers is achieved when the fiber coating is maintained. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance (NMR) analyses of the chemical composition of the glass fiber coating suggest that such coating is a complex mixture with multiple oxygen-containing functional groups such as hydroxyl, carbonyl and epoxy. FTIR and XPS of MWCNTs over the glass fibers and of a mixture of MWCNTs and fiber coating provided evidence that the hydroxyl and carboxyl groups of the oxidized MWCNTs react with the oxygen-containing functional groups of the glass fiber coating, forming hydrogen bonding and through epoxy ring opening. Hydrogen bonding and ester formation between the functional groups of the MWCNTs and the silane contained in the coating are also possible.

  4. Parametric effects on glass reaction in the unsaturated test method

    SciTech Connect

    Woodland, A.B.; Bates, J.K.; Gerding, T.J.

    1991-12-01

    The Unsaturated Test Method has been applied to study glass reaction under conditions that may be present at the potential Yucca Mountain site, currently under evaluation for storage of reprocessed high-level nuclear waste. The results from five separate sets of parametric experiments are presented wherein test parameters ranging from water contact volume to sensitization of metal in contact with the glass were examined. The most significant effect was observed when the volume of water, as controlled by the water inject volume and interval period, was such to allow exfoliation of reacted glass to occur. The extent of reaction was also influenced to a lesser extent by the degree of sensitization of the 304L stainless steel. For each experiment, the release of cations from the glass and alteration of the glass were examined. The major alteration product is a smectite clay that forms both from precipitation from solution and from in-situ alteration of the glass itself. It is this clay that undergoes exfoliation as water drips from the glass. A comparison is made between the results of the parametric experiments with those of static leach tests. In the static tests the rates of release become progressively reduced through 39 weeks while, in contrast, they remain relatively constant in the parametric experiments for at least 300 weeks. This differing behavior may be attributable to the dripping water environment where fresh water is periodically added and where evaporation can occur.

  5. Stained-Glass Pastels

    ERIC Educational Resources Information Center

    Laird, Shirley

    2009-01-01

    The author has always liked the look of stained-glass windows. Usually the designs are simplified and the shapes are easier for younger students to draw. This technique seemed to be the perfect place for her fifth-graders to try their hand at color mixing. The smaller spaces and simple shapes were just what she needed for this group. Her students…

  6. "Stained Glass" Landscape Windows

    ERIC Educational Resources Information Center

    Vannata, Janine

    2008-01-01

    Both adults and children alike marvel at the grand vivid stained-glass windows created by American artist Louis Comfort Tiffany. Today he is commonly recognized as one of America's most influential designers and artists throughout the last nineteenth and early twentieth century. In the lesson described in this article, students created their own…

  7. Shimmering Stained Glass.

    ERIC Educational Resources Information Center

    Simon, Gail Murray

    1998-01-01

    Presents an art lesson for fifth- and sixth-graders where they create a translucent design of colored cellophane on black paper inspired by the stained-glass windows of the Middle Ages and the artwork of Lewis Comfort Tiffany. Enables the students to become crafts people rather than just observers of the past. (CMK)

  8. CADMIUM PHOSPHATE GLASS

    DOEpatents

    Carpenter, H.W.; Johnson, P.D.

    1963-04-01

    A method of preparing a cadmium phosphate glass that comprises providing a mixture of solid inorganic compounds of cadmuim and phosphate having vaporizable components and heating the resulting composition to a temperature of at least 850 un. Concent 85% C is presented. (AEC)

  9. What Glass Ceiling?

    ERIC Educational Resources Information Center

    Lynch, Michael; Post, Katherine

    1996-01-01

    A recent study drawing on data from the Census Bureau and the Bureau of Labor Statistics suggests that the wage gap between men and women has virtually disappeared, and that the so-called "glass ceiling" results more from age and qualifications than from explicit discrimination. (SLD)

  10. Glass ceilings of professionalisation.

    PubMed

    Stott, Dawn L

    2016-04-01

    The term glass ceiling is a political term often used to describe an unbreakable barrier that isnot visible with the human eye, but it keeps minorities from rising up i.e. it is a barrier to minoritygroups, in the past (and sometimes still) for women, that stops them from achieving theirtrue potential. PMID:27290754

  11. THE INFLUENCE OF RADIATION AND MULTIVALENT CATION ADDITIONS ON PHASE SEPARATION AND CRYSTALLIZATION OF GLASS

    EPA Science Inventory

    Recent reviews which have dealt with critical issues regarding the suitability of glasses for nuclear waste disposal have identified liquid-liquid immiscibility and crystallization processes as having the potential to alter significantly storage behavior, especially chemical corr...

  12. Yesterday's Trash Makes Tomorrow's "Glass"

    ERIC Educational Resources Information Center

    Wayne, Dale

    2010-01-01

    In this article, the author describes a glass art project inspired by Dale Chihuly. This project uses two-liter plastic soda bottles which are cut apart and trimmed. Applying heat using a hair dryer, the plastic curls and takes an uneven blown-glass quality. The "glass" is then painted using acrylic paint. (Contains 2 resources and 1 online…

  13. Neutron-sensing scintillating glass optical fiber detectors

    SciTech Connect

    Bliss, M.; Reeder, P.L.; Craig, R.A.

    1994-07-01

    Pacific Northwest Laboratory (PNL) has developed and tested the highest-transmission neutron-sensing glass fibers reported in the open literature to date. By developing glass compositions specifically for fiber drawing and by using superior oxidationstate controls and rapid quenching, PNL produces, fiber with useful lengths in excess of 200 cm. These long fibers can be used in detectors. Test results on the fibers used as a form-fitting detector around a small storage container containing neutron and gamma ray sources are reported. Excellent neutron-gamma ray discrimination has been achieved. These neutron-sensing glass optical fibers provide for new methods for monitoring the inventory of, preventing the diversion of, and detecting the unauthorized transport of sensitive nuclear materials. As such, it represents a significant potential element in countering the threat of nuclear terrorism.

  14. Volcanic glass as a natural analog for borosilicate waste glass

    SciTech Connect

    Morgenstein, M.E.; Shettel, D.L.

    1994-12-31

    Obsidian and basaltic glass are opposite end-members of natural volcanic glass compositions. Syngenetic and diagenetic tensile failure in basaltic glass (low silica glass) is pervasive and provides abundant alteration fronts deep into the glass structure. Perlitic fracturing in obsidian (high silica glass) limits the alteration zones to an {open_quotes}onion skin{close_quotes} geometry. Borosilicate waste glass behaves similarly to the natural analog of basaltic glass (sideromelane). During geologic time, established and tensile fracture networks form glass cells (a three-dimensional reticulated pattern) where the production of new fracture surfaces increases through time by geometric progression. This suggests that borosilicate glass monoliths will eventually become rubble. Rates of reaction appear to double for every 12C{degrees} of temperature increase. Published leach rates suggest that the entire inventory of certain radionuclides may be released during the 10,000 year regulatory time period. Steam alteration prior to liquid attack combined with pervasive deep tensile failure behavior may suggest that the glass waste form is not license defensible without a metallic- and/or ceramic-type composite barrier as an overpack.

  15. Glass transition and stable glass formation of tetrachloromethane.

    PubMed

    Chua, Y Z; Tylinski, M; Tatsumi, S; Ediger, M D; Schick, C

    2016-06-28

    Physical vapor deposition (PVD) has been used to prepare organic glasses with very high kinetic stability and it has been suggested that molecular anisotropy is a prerequisite for stable glass formation. Here we use PVD to prepare glasses of tetrachloromethane, a simple organic molecule with a nearly isotropic molecular structure. In situ AC nanocalorimetry was used to characterize the vapor-deposited glasses. Glasses of high kinetic stability were produced by deposition near 0.8 Tg. The isothermal transformation of the vapor-deposited glasses into the supercooled liquid state gave further evidence that tetrachloromethane forms glasses with high kinetic stability, with the transformation time exceeding the structural relaxation time of the supercooled liquid by a factor of 10(3). The glass transition temperature of liquid-cooled tetrachloromethane is determined as Tg ≈ 78 K, which is different from previously reported values. The frequency dependence of the glass transition was also determined and the fragility was estimated as m ≈ 118. The successful formation of PVD glasses of tetrachloromethane which have high kinetic stability argues that molecular asymmetry is not a prerequisite for stable glass formation. PMID:27369523

  16. Glass transition and stable glass formation of tetrachloromethane

    NASA Astrophysics Data System (ADS)

    Chua, Y. Z.; Tylinski, M.; Tatsumi, S.; Ediger, M. D.; Schick, C.

    2016-06-01

    Physical vapor deposition (PVD) has been used to prepare organic glasses with very high kinetic stability and it has been suggested that molecular anisotropy is a prerequisite for stable glass formation. Here we use PVD to prepare glasses of tetrachloromethane, a simple organic molecule with a nearly isotropic molecular structure. In situ AC nanocalorimetry was used to characterize the vapor-deposited glasses. Glasses of high kinetic stability were produced by deposition near 0.8 Tg. The isothermal transformation of the vapor-deposited glasses into the supercooled liquid state gave further evidence that tetrachloromethane forms glasses with high kinetic stability, with the transformation time exceeding the structural relaxation time of the supercooled liquid by a factor of 103. The glass transition temperature of liquid-cooled tetrachloromethane is determined as Tg ≈ 78 K, which is different from previously reported values. The frequency dependence of the glass transition was also determined and the fragility was estimated as m ≈ 118. The successful formation of PVD glasses of tetrachloromethane which have high kinetic stability argues that molecular asymmetry is not a prerequisite for stable glass formation.

  17. Potential utilization of glass experiments in space

    NASA Technical Reports Server (NTRS)

    Kreidl, N. J.

    1984-01-01

    Materials processing in space utilizing the microgravity environment is discussed; glass processing in particular is considered. Attention is given to the processing of glass shells, critical cooling rate and novel glasses, gel synthesis of glasses, immiscibility, surface tension, and glass composites. Soviet glass experiments in space are also enumerated.

  18. Glass products for the vitrification of HLLW in a joule-heated ceramic melter and the effects of platinoids on the glass properties

    SciTech Connect

    Luckscheiter, B.

    1993-12-31

    A vitrification process was developed at KfK/INE for the solidification of HLW-solutions from the nuclear fuel cycle as borosilicate glasses. To optimize melter operation the glass melt should have a flat viscosity curve and a relatively high specific electrical resistance of > 6 {Omega} {center_dot} cm at 1,150 C. Further requirements are: no liquid-liquid immiscibility and no crystallization of the glass, waste loading > 15 wt.% and with a view to final storage of the HLW glass a chemical durability comparable to other HLW glasses. Experimental work was geared to adjusting the viscosity and the electrical resistance to the required values by varying the chemical composition of the glass. By use of mixed-alkali glasses containing Li{sub 2}O and Na{sub 2}O, glasses can be prepared which meet the required properties. In the technical vitrification process the platinoids Ru, Rh and Pd form precipitates and accumulate on the bottom of the melter. Dense sediments are formed with a lower resistance and a higher viscosity than those of the rest of the glass melt. Glass samples with about 16 wt.% platinoids have a very low resistance of only 0.1 {Omega} {center_dot} cm and show a non-Newtonian, pseudoplastic flow behavior.

  19. THE DEVELOPMENT OF RADIOACTIVE GLASS SURROGATES FOR FALLOUT DEBRIS

    SciTech Connect

    Martha R. Finck; Leigh R. Martin; Russel R. Lewis; Kevin P. Carney; Christopher A. McGrath

    2014-01-01

    The production of glass that emulates fallout is desired for the nuclear forensics community for training and measurement exercises. The composition of nuclear fallout is complex varying isotopic compositions . As the gaseous cloud traverses from hotter to cooler regions of the atmosphere, the processes of condensation and nucleation entrain environmental materials, vaporized nuclear materials and fission products. The elemental and isotopic composition of the fission products is altered due to chemical fractionation (i.e. the fission product composition that would be expected from fission of the original nuclear material is altered by differences in condensation rates of the elements); the fallout may be enriched or depleted in volatile or refractory fission products. This work describes preliminary results to synthesize, irradiate and fractionate the fission product content of irradiated particulate glass using a thermal distillation two hours after irradiation. The glass was synthesized using a solution-based polymerization of tetraethyl orthosilicate. Uranium was incorporated into the glass particulate at trace concentrations during polymerization. The particulate was subjected to a short thermal neutron irradiation then heated to 1273 K approximately 2 hours after the end of irradiation. Fission products of 133, 134, 135I, 132, 134Te, 135Xe, 138Cs and 91, 92Sr were observed to be distilled from the particulate. The results of these preliminary studies are discussed.

  20. Shedding Synchrotron Light on a Puzzle of Glasses

    ScienceCinema

    Chumakov, Aleksandr [European Synchrotron Radiation Facility, Grenoble, France

    2010-01-08

    Vibrational dynamics of glasses remains a point of controversial discussions. In particular, the density of vibrational states (DOS) reveals an excess of states above the Debye model called "boson peak." Despite the fact that this universal feature for all glasses has been known for more than 35 years, the nature of the boson peak is still not understood. The application of nuclear inelastic scattering via synchrotron radiation perhaps provides a clearer, more consistent picture of the subject. The distinguishing features of nuclear inelastic scattering relative to, e.g., neutron inelastic scattering, are ideal momentum integration and exact scaling of the DOS in absolute units. This allows for reliable comparison to data from other techniques such as Brillouin light scattering. Another strong point is ideal isotope selectivity: the DOS is measured for a single isotope with a specific low-energy nuclear transition. This allows for special "design" of an experiment to study, for instance, the dynamics of only center-of-mass motions. Recently, we have investigated the transformation of the DOS as a function of several key parameters such as temperature, cooling rate, and density. In all cases the transformation of the DOS is sufficiently well described by a transformation of the continuous medium, in particular, by changes of the macroscopic density and the sound velocity. These results suggest a collective sound-like nature of vibrational dynamics in glasses and cast doubts on microscopic models of glass dynamics. Further insight can be obtained in combined studies of glass with nuclear inelastic and inelastic neutron scattering. Applying two techniques, we have measured the energy dependence of the characteristic correlation length of atomic motions. The data do not reveal localization of atomic vibrations at the energy of the boson peak. Once again, the results suggest that special features of glass dynamics are related to extended motions and not to local models.

  1. The performance of Glass GEM

    NASA Astrophysics Data System (ADS)

    Fujiwara, T.; Mitsuya, Y.; Takahashi, H.; Fushie, T.; Kishimito, S.; Guèrard, B.; Uesaka, M.

    2014-11-01

    Here we report the performance of Glass gas electron multipliers (Glass GEMs), which were fabricated with photo-etchable glass. The photo-etchable glass used for substrate is called PEG3 (Hoya Corporation). With this material, we succeeded in fabricating a Glass GEM that was 680 μ m-thick with a hole diameter of 170 μ m and Cr and Cu layer electrodes. A Glass GEM has advantages such as good uniformity, high gain, a flat surface without stretching, cylindrical holes, and the absence of outgassing from the material. We successfully operated a Glass GEM having 100 × 100 m 2 effective area with various gas mixtures. The energy resolution for 5.9 keV X-rays was 18%, obtained by uniform irradiation of the entire effective area. The gas gain of the Glass GEM reached up to 90,000 with a gas mixture of Ne/C 4 (90:10). The Glass GEM was also operated with Ar/C 4 and Ar/C 4 gas. The gain stability measured for Glass GEM showed no significant increase or decrease as a function of elapsed time from applying high voltage. The gain stability over 15 hours of operation was about 10% in high-count-rate irradiation. Gain mapping across the Glass GEM showed good uniformity with a standard deviation of about 10%.

  2. Profiles in garbage glass containers

    SciTech Connect

    Miller, C.

    1997-09-01

    Glass containers are made from sand, limestone, soda ash, cullet (crushed bottles), and various additives, including those used to color brown, green, or blue bottles. Sixty percent of the glass used in the US is clear (flint) and one-fourth is brown (amber). Almost half of the green bottles are imported wind and beer bottles. Other glass products include flat glass such as windows; fiberglass insulation; and glassware. These products use different manufacturing processes and different additives than container glass. This profile covers only container glass. Glass bottles are commonly collected in curb-side programs. Losses due to breakage and the abrasiveness of glass during collection and processing offset their low collection and processing costs. Breakage solutions include installation of interior baffles or nets in the collection trucks, special glass-only truck compartments, and limiting the number of times glass is transferred after collection before final processing. Ten states require deposits on glass bottles for beer and soft drinks and related items.

  3. Commercial and Experimental Glass Fibers

    NASA Astrophysics Data System (ADS)

    Wallenberger, Frederick T.

    Continuous glass fibers can be formed from melts with a wide range of compositions and viscosities. This chapter reviews pure silica fibers which are formed from highly viscous melts, silicate glass fibers with 50-70% SiO2 which are formed from moderately viscous melts, aluminate glass fibers with 50-80% Al2O3, as well as yttria-alumina-garnet (YAG) glass fibers which are formed from inviscid (literally non-viscous) melts. Commercial glass fibers are made for a variety of applications from pure silica rods and from silicate melts containing 50-70% SiO2 and 10-25% Al2O3. Boron-free, essentially boron-free, and borosilicate E-glass are general-purpose fibers. ERC-glass offers high corrosion resistance, HS-glass offers high-strength composites, D-glass offers a low dielectric constant, and A-glass offers the possibility of using waste container glass for less demanding applications.

  4. Fluoride glass: Crystallization, surface tension

    NASA Technical Reports Server (NTRS)

    Doremus, R. H.

    1988-01-01

    Fluoride glass was levitated acoustically in the ACES apparatus on STS-11, and the recovered sample had a different microstructure from samples cooled in a container. Further experiments on levitated samples of fluoride glass are proposed. These include nucleation, crystallization, melting observations, measurement of surface tension of molten glass, and observation of bubbles in the glass. Ground experiments are required on sample preparation, outgassing, and surface reactions. The results should help in the development and evaluation of containerless processing, especially of glass, in the development of a contaminent-free method of measuring surface tensions of melts, in extending knowledge of gas and bubble behavior in fluoride glasses, and in increasing insight into the processing and properties of fluoride glasses.

  5. Atomistic Model of Physical Ageing in Se-rich As-Se Glasses

    SciTech Connect

    Golovchak,R.; Shpotyuk, O.; Kozdras, A.; Bureau, B.; Vlcek, M.; Ganjoo, A.; Jain, H.

    2007-01-01

    Thermal, optical, X-ray excited and magnetic methods were used to develop a microstructural model of physical ageing in Se-rich glasses. The glass composition As10Se90, possessing a typical cross-linked chain structure, was chosen as a model object for the investigations. The effect of physical ageing in this glass was revealed by differential scanning calorimetry, whereas the corresponding changes in its atomic arrangement were studied by extended X-ray absorption fine structure, Raman and solid-state 77Se nuclear magnetic resonance spectroscopy. Straightening-shrinkage processes are shown to be responsible for the physical ageing in this Se-rich As-Se glass.

  6. Simulation of alpha decay of actinides in iron phosphate glasses by ion irradiation

    NASA Astrophysics Data System (ADS)

    Dube, Charu L.; Stennett, Martin C.; Gandy, Amy S.; Hyatt, Neil C.

    2016-03-01

    A surrogate approach of ion beam irradiation is employed to simulate alpha decay of actinides in iron phosphate nuclear waste glasses. Bismuth and helium ions of different energies have been selected for simulating glass matrix modification owing to radiolysis and ballistic damage due to recoil atoms. Structural modification and change in coordination number of network former were probed by employing Reflectance Fourier-Transform Infrared (FT-IR), and Raman spectroscopies as a consequence of ion irradiation. Depolymerisation is observed in glass sample irradiated at intermediate energy of 2 MeV. Helium blisters of micron size are seen in glass sample irradiated at low helium ion energy of 30 keV.

  7. Production of glass or glass-ceramic to metal seals with the application of pressure

    DOEpatents

    Kelly, M.D.; Kramer, D.P.

    1985-01-04

    In a process for preparing a glass or glass-ceramic to metal seal comprising contacting the glass with the metal and heat-treating the glass and metal under conditions whereby the glass to metal seal is effected and, optionally, the glass is converted to a glass-ceramic, an improvement comprises carrying out the heat-treating step using hot isostatic pressing.

  8. Production of glass or glass-ceramic to metal seals with the application of pressure

    DOEpatents

    Kelly, Michael D.; Kramer, Daniel P.

    1987-11-10

    In a process for preparing a glass or glass-ceramic to metal seal comprising contacting the glass with the metal and heat-treating the glass and metal under conditions whereby the glass to metal seal is effected and, optionally, the glass is converted to a glass-ceramic, an improvement comprises carrying out the heat-treating step using hot isostatic pressing.

  9. Using small glass catalogs

    NASA Astrophysics Data System (ADS)

    Tesar, John C.

    2000-07-01

    Changes in glass catalogs from the major manufacturers, Schott, Ohara, Hoya, Corning, and Summita, are a future certainty. The ongoing efforts of these companies to eliminate arsenic, lead, and other environmentally unfriendly materials may well have an additional effect on the size of their catalogs also. We should not assume a zero-sum game, however. Environmental concerns may not lead to permanently smaller catalogs, though many have speculated that in the near term this might be so. However, from the designer's perspective, very small, abbreviated class catalogs, constructed for special purposes, can speed the glass selection process. Several examples will be discussed, based on derivative libraries suggested by Zhang, Shannon, and Walker. Streamlined libraries tailored for special purposes can be used effectively in the latest lens design software. Future software tools may speed this selection process by the use of algorithms that treat the problem as a `black box' using logic tools derived from probability studies of the patent literature.

  10. The formation of crystals in glasses containing rare earth oxides

    NASA Astrophysics Data System (ADS)

    Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod; Siong, Khoo Kok; Ngatiman, Mohammad Fadzlee; Said, Riduan Mt

    2014-02-01

    Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd2O3-22.7CeO2-11.7La2O3-10.9PrO2-1.3Eu2O3-1.3Gd2O3-8.1Sm2O3-4.8Y2O3 with a baseline glass of composition 60.2SiO2-16.0B2O3-12.6Na2O-3.8Al2O3-5.7CaO-1.7ZrO2. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La2O3 and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO5) and oxyapatite (Ca2La8Si6O26) were found in glasses containing La2O3, while oxyapatite (Ca2La8Si6O26 and NaNd9Si6O26) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (TL) of the glasses containing 5%, 10% and 15% La2O3 were 800°C, 959°C and 986°C, respectively; while TL was 825°C, 1059°C and 1267°C for glasses with 5%, 10% and 15% addition of mixed rare earth oxides. The component coefficients TB2O3, TSiO2, TCaO, and TRE2O3 were also evaluated using a recently published study.

  11. Athermal photofluidization of glasses.

    PubMed

    Fang, G J; Maclennan, J E; Yi, Y; Glaser, M A; Farrow, M; Korblova, E; Walba, D M; Furtak, T E; Clark, N A

    2013-01-01

    Azobenzene and its derivatives are among the most important organic photonic materials, with their photo-induced trans-cis isomerization leading to applications ranging from holographic data storage and photoalignment to photoactuation and nanorobotics. A key element and enduring mystery in the photophysics of azobenzenes, central to all such applications, is athermal photofluidization: illumination that produces only a sub-Kelvin increase in average temperature can reduce, by many orders of magnitude, the viscosity of an organic glassy host at temperatures more than 100 K below its thermal glass transition. Here we analyse the relaxation dynamics of a dense monolayer glass of azobenzene-based molecules to obtain a measurement of the transient local effective temperature at which a photo-isomerizing molecule attacks its orientationally confining barriers. This high temperature (T(loc)~800 K) leads directly to photofluidization, as each absorbed photon generates an event in which a local glass transition temperature is exceeded, enabling collective confining barriers to be attacked with near 100% quantum efficiency. PMID:23443549

  12. Liquidus temperature and chemical durability of selected glasses to immobilize rare earth oxides waste

    NASA Astrophysics Data System (ADS)

    Mohd Fadzil, Syazwani; Hrma, Pavel; Schweiger, Michael J.; Riley, Brian J.

    2015-10-01

    Pyroprocessing is are processing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl-KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the glass matrix at high loadings. Crystallization that occurs in waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (TL): the International Simple Glass designed by the International Working Group, sodium borosilicate glass developed by Korea Hydro and Nuclear Power, and the lanthanide aluminoborosilicate (LABS) glass established in the United States. The LABS glass allows the highest waste loadings (over 50 mass% RE2O3) while possessing an acceptable chemical durability.

  13. Molten Glass for Thermal Storage: Advanced Molten Glass for Heat Transfer and Thermal Energy Storage

    SciTech Connect

    2012-01-01

    HEATS Project: Halotechnics is developing a high-temperature thermal energy storage system using a new thermal-storage and heat-transfer material: earth-abundant and low-melting-point molten glass. Heat storage materials are critical to the energy storage process. In solar thermal storage systems, heat can be stored in these materials during the day and released at night—when the sun is not out—to drive a turbine and produce electricity. In nuclear storage systems, heat can be stored in these materials at night and released to produce electricity during daytime peak-demand hours. Halotechnics new thermal storage material targets a price that is potentially cheaper than the molten salt used in most commercial solar thermal storage systems today. It is also extremely stable at temperatures up to 1200°C—hundreds of degrees hotter than the highest temperature molten salt can handle. Being able to function at high temperatures will significantly increase the efficiency of turning heat into electricity. Halotechnics is developing a scalable system to pump, heat, store, and discharge the molten glass. The company is leveraging technology used in the modern glass industry, which has decades of experience handling molten glass.

  14. Laser Glass Frit Sealing for Encapsulation of Vacuum Insulation Glasses

    NASA Astrophysics Data System (ADS)

    Kind, H.; Gehlen, E.; Aden, M.; Olowinsky, A.; Gillner, A.

    Laser glass frit sealing is a joining method predestined in electronics for the sealing of engineered materials housings in dimensions of some 1 mm2 to several 10 mm2. The application field ranges from encapsulation of display panels to sensor housings. Laser glass frit sealing enables a hermetical closure excluding humidity and gas penetration. But the seam quality is also interesting for other applications requiring a hermetical sealing. One application is the encapsulation of vacuum insulation glass. The gap between two panes must be evacuated for reducing the thermal conductivity. Only an efficient encapsulating technique ensures durable tight joints of two panes for years. Laser glass frit sealing is an alternative joining method even though the material properties of soda lime glass like sensitivity to thermal stresses are much higher as known from engineered materials. An adapted thermal management of the process is necessary to prevent the thermal stresses within the pane to achieve crack free and tight glass frit seams.

  15. Mixed polyanion glass cathodes: Glass-state conversion reactions

    SciTech Connect

    Kercher, Andrew K.; Kolopus, James A.; Carroll, Kyler; Unocic, Raymond R.; Kirklin, S.; Wolverton, C.; Stooksbury, Shelby L.; Boatner, Lynn A.; Dudney, Nancy J.

    2015-01-01

    Mixed polyanion (MP) glasses can undergo glass-state conversion (GSC) reactions to provide an alternate class of high-capacity cathode materials. GSC reactions have been demonstrated in phosphate/vanadate glasses with Ag, Co, Cu, Fe, and Ni cations. These MP glasses provided high capacity and good high power performance, but suffer from moderate voltages, large voltage hysteresis, and significant capacity fade with cycling. Details of the GSC reaction have been revealed by x-ray absorption spectroscopy, electron microscopy, and energy dispersive x-ray spectroscopy of ex situ cathodes at key states of charge. Using the Open Quantum Materials Database (OQMD), a computational thermodynamic model has been developed to predict the near-equilibrium voltages of glass-state conversion reactions in MP glasses.

  16. Mixed polyanion glass cathodes: Glass-state conversion reactions

    DOE PAGESBeta

    Kercher, Andrew K.; Kolopus, James A.; Carroll, Kyler; Unocic, Raymond R.; Kirklin, S.; Wolverton, C.; Stooksbury, Shelby L.; Boatner, Lynn A.; Dudney, Nancy J.

    2015-01-01

    Mixed polyanion (MP) glasses can undergo glass-state conversion (GSC) reactions to provide an alternate class of high-capacity cathode materials. GSC reactions have been demonstrated in phosphate/vanadate glasses with Ag, Co, Cu, Fe, and Ni cations. These MP glasses provided high capacity and good high power performance, but suffer from moderate voltages, large voltage hysteresis, and significant capacity fade with cycling. Details of the GSC reaction have been revealed by x-ray absorption spectroscopy, electron microscopy, and energy dispersive x-ray spectroscopy of ex situ cathodes at key states of charge. Using the Open Quantum Materials Database (OQMD), a computational thermodynamic model hasmore » been developed to predict the near-equilibrium voltages of glass-state conversion reactions in MP glasses.« less

  17. Behaviour of ruthenium dioxide particles in borosilicate glasses and melts

    NASA Astrophysics Data System (ADS)

    Pflieger, Rachel; Lefebvre, Leila; Malki, Mohammed; Allix, Mathieu; Grandjean, Agnès

    2009-06-01

    Ruthenium-glass systems are formed during the vitrification of nuclear waste. They are also widely used in micro-electronics because of their unique electrical properties. However, the interaction of this element with the glass matrix remains poorly understood. This work focuses on a RuO 2 particles-nuclear alumino-borosilicate glass system in which the electrical conductivity is known to vary considerably with the RuO 2 content and to become electronic above about 0.5-0.7 vol.% RuO 2 [R. Pflieger, M. Malki, Y. Guari, J. Larionova, A. Grandjean, J. Am. Ceram. Soc., accepted for publication]. Some RuO 2 segregation was observed in SEM/TEM investigations but no continuous chain of RuO 2 particles could be seen. Electron relays between the particles are then necessary for a low-rate percolation, such as the nanoclusters suggested by Adachi et al. [K. Adachi, S. Iida, K. Hayashi, J. Mater. Res. 9 (7) (1994) 1866; K. Adachi, H. Kuno, J. Am. Ceram. Soc. 83 (10) (2000) 2441], which could consist in dissolved ruthenium. Indeed, several observations made here clearly indicate the presence of dissolved ruthenium in the glass matrix, like the modification of the glass density in presence of RuO 2 particles or the diffusion-limited growth of RuO 2 particles in the melt.

  18. Laboratory testing of LITCO glasses

    SciTech Connect

    Ellison, A.; Wolf, S.; Buck, E.; Luo, J.S.; Dietz, N.; Bates, J.K.; Ebert, W.L.

    1995-06-01

    The purpose of this program is to measure, the intermediate and long-term durability of glasses developed by Lockheed Idaho Technology Co. (LITCO) for the immobilization of calcined radioactive wastes. The objective is to use accelerated corrosion tests as an aid in developing durable waste form compositions. This is a report of tests performed on two LITCO glass compositions, Formula 127 and Formula 532. The main avenue for release of radionuclides into the environment in a geologic repository is the reaction of a waste glass with ground water, which alters the glass and releases its components into solution. These stages in glass corrosion are analyzed by using accelerated laboratory tests in which the ratio of sample surface area to solution volume, SA/V, is varied. At low SA/V, the solution concentrations of glass corrosion products remain low and the reaction approaches the forward rate. At higher SA/V the solution approaches saturation levels for glass corrosion products. At very high SA/V the solution is rapidly saturated in glass corrosion products and secondary crystalline phases precipitate. Tests at very high SA/V provide information about the composition of the solution at saturation or, when no solution is recovered, the identities and the order of appearance of secondary crystalline phases. Tests were applied to Formula 127 and Formula 532 glasses to provide information about the interim and long-term stages in glass corrosion.

  19. Analytical Plan for Roman Glasses

    SciTech Connect

    Strachan, Denis M.; Buck, Edgar C.; Mueller, Karl T.; Schwantes, Jon M.; Olszta, Matthew J.; Thevuthasan, Suntharampillai; Heeren, Ronald M.

    2011-01-01

    Roman glasses that have been in the sea or underground for about 1800 years can serve as the independent “experiment” that is needed for validation of codes and models that are used in performance assessment. Two sets of Roman-era glasses have been obtained for this purpose. One set comes from the sunken vessel the Iulia Felix; the second from recently excavated glasses from a Roman villa in Aquileia, Italy. The specimens contain glass artifacts and attached sediment or soil. In the case of the Iulia Felix glasses quite a lot of analytical work has been completed at the University of Padova, but from an archaeological perspective. The glasses from Aquileia have not been so carefully analyzed, but they are similar to other Roman glasses. Both glass and sediment or soil need to be analyzed and are the subject of this analytical plan. The glasses need to be analyzed with the goal of validating the model used to describe glass dissolution. The sediment and soil need to be analyzed to determine the profile of elements released from the glass. This latter need represents a significant analytical challenge because of the trace quantities that need to be analyzed. Both pieces of information will yield important information useful in the validation of the glass dissolution model and the chemical transport code(s) used to determine the migration of elements once released from the glass. In this plan, we outline the analytical techniques that should be useful in obtaining the needed information and suggest a useful starting point for this analytical effort.

  20. Impact resistance of bar glasses.

    PubMed

    Shepherd, J P; Huggett, R H; Kidner, G

    1993-12-01

    Bar glasses are often used as weapons in interpersonal violence. Violence often erupts spontaneously and assailants use objects close to hand as weapons. After an initial national Accident and Emergency Department study to identify glass designs most often implicated in interpersonal violence, the impact resistance of 1-pint beer glasses was tested in a materials laboratory with a Zwick 5102 pendulum impact tester. Both straight-sided (nonik) glasses (annealed and tempered) and handled tankards (annealed) were tested to destruction. The impact resistance of new glasses was compared with that of glasses subjected to wear. The mean impact resistance of new annealed noniks did not differ significantly although new glasses were significantly more resistant than worn glasses (p < 0.01). It was not possible to break any of the tempered glasses with the pendulum used (maximum impact energy, 4 J). When noniks had been scratched at the rim to mimic wear, tempered glasses also had the highest impact resistance (p < 0.01) whereas the mean resistance of the annealed noniks was not significantly different. When tempered glasses failed during testing, they all disintegrated into relatively harmless cubes of glass, particularly the thicker bases of glasses. In contrast, annealed designs fractured leaving sharp shards although the thicker bases remained intact. The mean impact resistance of new annealed noniks was 0.5 J, of worn annealed noniks 0.08 J, of tempered new noniks > 4 J, of worn tempered noniks 0.18 J, and of tankards, 1.7 J.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8263994

  1. Bioactive glass in tissue engineering

    PubMed Central

    Rahaman, Mohamed N.; Day, Delbert E.; Bal, B. Sonny; Fu, Qiang; Jung, Steven B.; Bonewald, Lynda F.; Tomsia, Antoni P.

    2011-01-01

    This review focuses on recent advances in the development and use of bioactive glass for tissue engineering applications. Despite its inherent brittleness, bioactive glass has several appealing characteristics as a scaffold material for bone tissue engineering. New bioactive glasses based on borate and borosilicate compositions have shown the ability to enhance new bone formation when compared to silicate bioactive glass. Borate-based bioactive glasses also have controllable degradation rates, so the degradation of the bioactive glass implant can be more closely matched to the rate of new bone formation. Bioactive glasses can be doped with trace quantities of elements such as Cu, Zn and Sr, which are known to be beneficial for healthy bone growth. In addition to the new bioactive glasses, recent advances in biomaterials processing have resulted in the creation of scaffold architectures with a range of mechanical properties suitable for the substitution of loaded as well as non-loaded bone. While bioactive glass has been extensively investigated for bone repair, there has been relatively little research on the application of bioactive glass to the repair of soft tissues. However, recent work has shown the ability of bioactive glass to promote angiogenesis, which is critical to numerous applications in tissue regeneration, such as neovascularization for bone regeneration and the healing of soft tissue wounds. Bioactive glass has also been shown to enhance neocartilage formation during in vitro culture of chondrocyte-seeded hydrogels, and to serve as a subchondral substrate for tissue-engineered osteochondral constructs. Methods used to manipulate the structure and performance of bioactive glass in these tissue engineering applications are analyzed. PMID:21421084

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

    SciTech Connect

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

    1998-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Hopf, J.; Kerisit, S. N.; Angeli, F.; Charpentier, T.; Icenhower, J. P.; McGrail, B. P.; Windisch, C. F.; Burton, S. D.; Pierce, E. M.

    2016-05-01

    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 with higher Si

  4. Mixed polyanion glass cathodes: Iron phosphate vanadate glasses

    SciTech Connect

    Kercher, Andrew K; Ramey, Joanne Oxendine; Carroll, Kyler J; Kiggans Jr, James O; Veith, Gabriel M; Meisner, Roberta; Boatner, Lynn A; Dudney, Nancy J

    2014-01-01

    Mixed polyanion (MP) glasses have been investigated for use as cathodes in lithium ion batteries. MP glass cathodes are similar in composition to theoretically promising crystalline polyanionic (CP) cathodes (e.g., lithium cobalt phosphate, lithium manganese silicate), but with proper polyanion substitution, they can be designed to overcome the key shortcomings of CP cathodes, such as poor electrical conductivity and irreversible phase changes. Iron phosphate/vanadate glasses were chosen as a first demonstration of the MP glass concept. Polyanion substitution with vanadate was shown to improve the intercalation capacity of an iron phosphate glass from almost zero to full theoretical capacity. In addition, the MP glass cathodes also exhibited an unexpected second high-capacity electrochemical reaction. X-ray absorption near-edge structure (XANES) and x-ray diffraction (XRD) of cathodes from cells having different states of charge suggested that this second electrochemical reaction is a glass-state conversion reaction. With a first demonstration established, MP glass materials utilizing an intercalation and/or glass-state conversion reaction are promising candidates for future high-energy cathode research.

  5. Structure and Chemistry in Halide Lead-Tellurite Glasses

    SciTech Connect

    McCloy, John S.; Riley, Brian J.; Lipton, Andrew S.; Windisch, Charles F.; Washton, Nancy M.; Olszta, Matthew J.; Rodriguez, Carmen P.

    2013-02-11

    A series of TeO2-PbO glasses were fabricated with increasing fractions of mixed alkali, alkaline earth, and lanthanide chlorides. The glass and crystal structure was studied with Raman spectroscopy, nuclear magnetic resonance (NMR), X-ray diffraction, and electron microscopy. As the chloride fraction increased, the medium-range order in the glass decreased up to a critical point (~14 mass% of mixed chlorides), above which the glasses became phase-separated. Resulting phases are a TeO2/PbO-rich phase and a crystalline phase rich in alkali chlorides. The 125Te NMR indicates, contrary to previous studies, that Te site distribution did not change with increased concentrations of M+, M2+, and M3+ cations, but rather is controlled by the Te/Pb molar ratio. The 207Pb NMR shows that two Pb species exist and their relative concentration changes nearly linearly with addition of the mixed chlorides, indicating that the additives to the TeO2-PbO glass are accommodated by changing the Pb species. The 23Na and 35Cl NMR indicate that Na and Cl are distributed in the single-phase glass phase up to the critical point, and at higher concentrations partition to crystalline phases. Transmission electron microscopy shows that the sample at the critical point contains ~10 nm seed nuclei that increase in size and concentration with exposure to the electron beam.

  6. Letter report on PCT/Monolith glass ceramic corrosion tests

    SciTech Connect

    Crawford, Charles L.

    2015-09-24

    The Savannah River National Laboratory (SRNL) is collaborating with personnel from Pacific Northwest National Laboratory (PNNL) to study advanced waste form glass ceramics for immobilization of waste from Used Nuclear Fuel (UNF) separations processes. The glass ceramic waste forms take advantage of both crystalline and glassy phases where ‘troublesome’ elements (e.g., low solubility in glass or very long-lived) partition to highly durable ceramic phases with the remainder of elements residing in the glassy phase. The ceramic phases are tailored to create certain minerals or unique crystalline structures that can host the radionuclides by binding them in their specific crystalline network while not adversely impacting the residual glass network (Crum et al., 2011). Glass ceramics have been demonstrated using a scaled melter test performed in a pilot scale (1/4 scale) cold crucible induction melter (CCIM) (Crum et al., 2014; Maio et al., 2015). This report summarizes recent results from both Phase I and Phase II bench scale tests involving crucible fabrication and corrosion testing of glass ceramics using the Product Consistency Test (PCT). Preliminary results from both Phase I and Phase II bench scale tests involving statistically designed matrices have previously been reported (Crawford, 2013; Crawford, 2014).

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

    PubMed

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

    2014-07-01

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

  8. Fracture mechanics of cellular glass

    NASA Technical Reports Server (NTRS)

    Zwissler, J. G.; Adams, M. A.

    1981-01-01

    The fracture mechanics of cellular glasses (for the structural substrate of mirrored glass for solr concentrator reflecting panels) are discussed. Commercial and developmental cellular glasses were tested and analyzed using standard testing techniques and models developed from linear fracture mechanics. Two models describing the fracture behavior of these materials were developed. Slow crack growth behavior in cellular glass was found to be more complex than that encountered in dense glasses or ceramics. The crack velocity was found to be strongly dependent upon water vapor transport to the tip of the moving crack. The existence of a static fatigue limit was not conclusively established, however, it is speculated that slow crack growth behavior in Region 1 may be slower, by orders of magnitude, than that found in dense glasses.

  9. Dynamic scaling in spin glasses

    NASA Astrophysics Data System (ADS)

    Pappas, C.; Mezei, F.; Ehlers, G.; Manuel, P.; Campbell, I. A.

    2003-08-01

    We present neutron spin echo (NSE) results and a revisited analysis of historical data on spin glasses, which reveal a pure power-law time decay of the spin autocorrelation function s(Q,t)=S(Q,t)/S(Q) at the glass temperature Tg. The power law exponent is in excellent agreement with that calculated from dynamic and static critical exponents deduced from macroscopic susceptibility measurements made on a quite different time scale. This scaling relation involving exponents of different physical quantities determined by completely independent experimental methods is stringently verified experimentally in a spin glass. As spin glasses are a subgroup of the vast family of glassy systems also comprising structural glasses and other noncrystalline systems the observed strict critical scaling behavior is important. Above the phase transition the strikingly nonexponential relaxation, best fitted by the Ogielski (power-law times stretched exponential) function, appears as an intrinsic, homogeneous feature of spin glasses.

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

    PubMed

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

    2014-11-01

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

  11. Space processing of chalcogenide glass

    NASA Technical Reports Server (NTRS)

    Larsen, D. C.; Ali, M. I.

    1977-01-01

    The manner in which the weightless, containerless nature of in-space processing can be successfully utilized to improve the quality of infrared transmitting chalcogenide glasses is determined. The technique of space processing chalcogenide glass was developed, and the process and equipment necessary to do so was defined. Earthbound processing experiments with As2S3 and G28Sb12Se60 glasses were experimented with. Incorporated into these experiments is the use of an acoustic levitation device.

  12. Electronic structure of metallic glasses

    SciTech Connect

    Oelhafen, P.; Lapka, R.; Gubler, U.; Krieg, J.; DasGupta, A.; Guentherodt, H.J.; Mizoguchi, T.; Hague, C.; Kuebler, J.; Nagel, S.R.

    1981-01-01

    This paper is organized in six sections and deals with (1) the glassy transition metal alloys, their d-band structure, the d-band shifts on alloying and their relation to the alloy heat of formation (..delta..H) and the glass forming ability, (2) the glass to crystal phase transition viewed by valence band spectroscopy, (3) band structure calculations, (4) metallic glasses prepared by laser glazing, (5) glassy normal metal alloys, and (6) glassy hydrides.

  13. PLZT capacitor on glass substrate

    DOEpatents

    Fairchild, M. Ray; Taylor, Ralph S.; Berlin, Carl W.; Wong, Celine W. K.; Ma, Beihai; Balachandran, Uthamalingam

    2016-01-05

    A lead-lanthanum-zirconium-titanate (PLZT) capacitor on a substrate formed of glass. The first metallization layer is deposited on a top side of the substrate to form a first electrode. The dielectric layer of PLZT is deposited over the first metallization layer. The second metallization layer deposited over the dielectric layer to form a second electrode. The glass substrate is advantageous as glass is compatible with an annealing process used to form the capacitor.

  14. PLZT capacitor on glass substrate

    DOEpatents

    Fairchild, Manuel Ray; Taylor, Ralph S.; Berlin, Carl W.; Wong, Celine Wk; Ma, Beihai; Balachandran, Uthamalingam

    2016-03-29

    A lead-lanthanum-zirconium-titanate (PLZT) capacitor on a substrate formed of glass. The first metallization layer is deposited on a top side of the substrate to form a first electrode. The dielectric layer of PLZT is deposited over the first metallization layer. The second metallization layer deposited over the dielectric layer to form a second electrode. The glass substrate is advantageous as glass is compatible with an annealing process used to form the capacitor.

  15. Structural color from colloidal glasses

    NASA Astrophysics Data System (ADS)

    Magkiriadou, Sofia

    When a material has inhomogeneities at a lengthscale comparable to the wavelength of light, interference can give rise to structural colors: colors that originate from the interaction of the material's microstructure with light and do not require absorbing dyes. In this thesis we study a class of these materials, called photonic glasses, where the inhomogeneities form a dense and random arrangement. Photonic glasses have angle-independent structural colors that look like those of conventional dyes. However, when this work started, there was only a handful of colors accessible with photonic glasses, mostly hues of blue. We use various types of colloidal particles to make photonic glasses, and we study, both theoretically and experimentally, how the optical properties of these glasses relate to their structure and constituent particles. Based on our observations from glasses of conventional particles, we construct a theoretical model that explains the scarcity of yellow, orange, and red photonic glasses. Guided by this model, we develop novel colloidal systems that allow a higher degree of control over structural color. We assemble glasses of soft, core-shell particles with scattering cores and transparent shells, where the resonant wavelength can be tuned independently of the reflectivity. We then encapsulate glasses of these core-shell particles into emulsion droplets of tunable size; in this system, we observe, for the first time, angle-independent structural colors that cover the entire visible spectrum. To enhance color saturation, we begin experimenting with inverse glasses, where the refractive index of the particles is lower than the refractive index of the medium, with promising results. Finally, based on our theoretical model for scattering from colloidal glasses, we begin an exploration of the color gamut that could be achieved with this technique, and we find that photonic glasses are a promising approach to a new type of long-lasting, non-toxic, and

  16. Microsheet Glass In Solar Concentrators

    NASA Technical Reports Server (NTRS)

    Richter, Scott W.

    1993-01-01

    Microsheet glass used as highly protective covering material for developmental concentrating reflectors for solar power systems. Together with other materials, possible to fabricate lightweight, highly reflective, accurate, and long-lived concentrators. Desirable properties include durability and smoothness. Glass not affected by ultraviolet radiation, and not degraded by atomic oxygen, found in low orbits around Earth. Though concentrators intended for use in outer space, noteworthy that terrestrial concentrator fabricated with glass sheet 0.7 mm thick.

  17. Crystallization of copper metaphosphate glass

    NASA Technical Reports Server (NTRS)

    Bae, Byeong-Soo; Weinberg, Michael C.

    1993-01-01

    The effect of the valence state of copper in copper metaphosphate glass on the crystallization behavior and glass transition temperature has been investigated. The crystallization of copper metaphosphate is initiated from the surface and its main crystalline phase is copper metaphosphate (Cu(PO)3),independent of the (Cu sup 2+)/(Cu(total)). However, the crystal morphology, the relative crystallization rates, and their temperature dependences are affected by the (Cu sup 2+)/(Cu (total)) ratio in the glass. On the other hand, the totally oxidized glass crystallizes from all over the surface. The relative crystallization rate of the reduced glass to the totally oxidized glass is large at low temperature, but small at high temperature. The glass transition temperature of the glass increases as the (Cu sup 2+)/(Cu(total)) ratio is raised. It is also found that the atmosphere used during heat treatment does not influence the crystallization of the reduced glass, except for the formation of a very thin CuO surface layer when heated in air.

  18. Glass corrosion in natural environment

    NASA Technical Reports Server (NTRS)

    Thorpe, Arthur N.

    1989-01-01

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

  19. Halide laser glasses

    SciTech Connect

    Weber, M.J.

    1982-01-14

    Energy storage and energy extraction are of prime importance for efficient laser action and are affected by the line strengths and linewidths of optical transitions, excited-state lifetimes, nonradiative decay processes, spectroscopic inhomogeneities, nonlinear refractive index, and damage threshold. These properties are all host dependent. To illustrate this, the spectroscopic properties of Nd/sup 3 +/ have been measured in numerous oxide, oxyhalide, and halide glasses. A table summarizes the reported ranges of stimulated emission cross sections, peak wavelengths, linewidths, and radiative lifetimes associated with the /sup 4/F/sub 3/2/ ..-->.. /sup 4/I/sub 11/2/ lasing transition.

  20. Glass rupture disk

    DOEpatents

    Glass, S. Jill; Nicolaysen, Scott D.; Beauchamp, Edwin K.

    2002-01-01

    A frangible rupture disk and mounting apparatus for use in blocking fluid flow, generally in a fluid conducting conduit such as a well casing, a well tubing string or other conduits within subterranean boreholes. The disk can also be utilized in above-surface pipes or tanks where temporary and controllable fluid blockage is required. The frangible rupture disk is made from a pre-stressed glass with controllable rupture properties wherein the strength distribution has a standard deviation less than approximately 5% from the mean strength. The frangible rupture disk has controllable operating pressures and rupture pressures.

  1. Method for heating a glass sheet

    DOEpatents

    Boaz, P.T.

    1998-07-21

    A method for heating a glass sheet includes the steps of heating a glass sheet to a first predetermined temperature and applying microwave energy to the glass sheet to heat the glass sheet to at least a second predetermined temperature to allow the glass sheet to be formed. 5 figs.

  2. Method for heating a glass sheet

    DOEpatents

    Boaz, Premakaran Tucker

    1998-01-01

    A method for heating a glass sheet includes the steps of heating a glass sheet to a first predetermined temperature and applying microwave energy to the glass sheet to heat the glass sheet to at least a second predetermined temperature to allow the glass sheet to be formed.

  3. Examination of glass-silicon and glass-glass bonding techniques for microfluidic systems

    SciTech Connect

    Raley, N.F.; Davidson, J.C.; Balch, J.W.

    1995-10-23

    We report here on the results of experiments concerning particular bonding processes potentially useful for ultimate miniaturization of microfluidic systems. Direct anodic bonding of continuous thin pyrex glass of 250 {mu}m thickness to silicon substrates gives multiple, large voids in the glass. Etchback of thick glass of 1200 {mu}m thickness bonded to silicon substrates gives thin continuous glass layers of 189 {mu}m thickness without voids over areas of 5 cm {times} 12 cm. Glass was also successfully bonded to glass by thermal bonding at 800{degrees}C over a 5 cm {times} 7 cm area. Anticipated applications include microfabricated DNA sequencing, flow injection analysis, and liquid and gas chromatography microinstruments.

  4. POROUS WALL, HOLLOW GLASS MICROSPHERES

    SciTech Connect

    Sexton, W.

    2012-06-30

    Hollow Glass Microspheres (HGM) is not a new technology. All one has to do is go to the internet and Google{trademark} HGM. Anyone can buy HGM and they have a wide variety of uses. HGM are usually between 1 to 100 microns in diameter, although their size can range from 100 nanometers to 5 millimeters in diameter. HGM are used as lightweight filler in composite materials such as syntactic foam and lightweight concrete. In 1968 a patent was issued to W. Beck of the 3M{trademark} Company for 'Glass Bubbles Prepared by Reheating Solid Glass Particles'. In 1983 P. Howell was issued a patent for 'Glass Bubbles of Increased Collapse Strength' and in 1988 H. Marshall was issued a patent for 'Glass Microbubbles'. Now Google{trademark}, Porous Wall, Hollow Glass Microspheres (PW-HGMs), the key words here are Porous Wall. Almost every article has its beginning with the research done at the Savannah River National Laboratory (SRNL). The Savannah River Site (SRS) where SRNL is located has a long and successful history of working with hydrogen and its isotopes for national security, energy, waste management and environmental remediation applications. This includes more than 30 years of experience developing, processing, and implementing special ceramics, including glasses for a variety of Department of Energy (DOE) missions. In the case of glasses, SRS and SRNL have been involved in both the science and engineering of vitreous or glass based systems. As a part of this glass experience and expertise, SRNL has developed a number of niches in the glass arena, one of which is the development of porous glass systems for a variety of applications. These porous glass systems include sol gel glasses, which include both xerogels and aerogels, as well as phase separated glass compositions, that can be subsequently treated to produce another unique type of porosity within the glass forms. The porous glasses can increase the surface area compared to 'normal glasses of a 1 to 2 order of

  5. Quinary metallic glass alloys

    DOEpatents

    Lin, Xianghong; Johnson, William L.

    1998-01-01

    At least quinary alloys form metallic glass upon cooling below the glass transition temperature at a rate less than 10.sup.3 K/s. Such alloys comprise zirconium and/or hafnium in the range of 45 to 65 atomic percent, titanium and/or niobium in the range of 4 to 7.5 atomic percent, and aluminum and/or zinc in the range of 5 to 15 atomic percent. The balance of the alloy compositions comprise copper, iron, and cobalt and/or nickel. The composition is constrained such that the atomic percentage of iron is less than 10 percent. Further, the ratio of copper to nickel and/or cobalt is in the range of from 1:2 to 2:1. The alloy composition formula is: (Zr,Hf).sub.a (Al,Zn).sub.b (Ti,Nb).sub.c (Cu.sub.x Fe.sub.y (Ni,Co).sub.z).sub.d wherein the constraints upon the formula are: a ranges from 45 to 65 atomic percent, b ranges from 5 to 15 atomic percent, c ranges from 4 to 7.5 atomic percent, d comprises the balance, d.multidot.y is less than 10 atomic percent, and x/z ranges from 0.5 to 2.

  6. Quinary metallic glass alloys

    DOEpatents

    Lin, X.; Johnson, W.L.

    1998-04-07

    At least quinary alloys form metallic glass upon cooling below the glass transition temperature at a rate less than 10{sup 3}K/s. Such alloys comprise zirconium and/or hafnium in the range of 45 to 65 atomic percent, titanium and/or niobium in the range of 4 to 7.5 atomic percent, and aluminum and/or zinc in the range of 5 to 15 atomic percent. The balance of the alloy compositions comprise copper, iron, and cobalt and/or nickel. The composition is constrained such that the atomic percentage of iron is less than 10 percent. Further, the ratio of copper to nickel and/or cobalt is in the range of from 1:2 to 2:1. The alloy composition formula is: (Zr,Hf){sub a}(Al,Zn){sub b}(Ti,Nb){sub c}(Cu{sub x}Fe{sub y}(Ni,Co){sub z}){sub d} wherein the constraints upon the formula are: a ranges from 45 to 65 atomic percent, b ranges from 5 to 15 atomic percent, c ranges from 4 to 7.5 atomic percent, d comprises the balance, d{hor_ellipsis}y is less than 10 atomic percent, and x/z ranges from 0.5 to 2.

  7. Metallic glass velocity sensor

    SciTech Connect

    Butler, J.L.; Butler, S.C.; Massa, D.P.; Cavanagh, G.H.

    1996-04-01

    A metallic glass accelerometer has been developed for use as an underwater sound velocity sensor. The device uses the metallic glass material Metglas 2605SC which has been processed to achieve a virgin coupling coefficient of 0.96. The mechanical to electrical conversion is based on the detection of the change in the inductance of the device as a result of bending motion. The detection method uses a carrier frequency signal which is amplitude modulated by the received signal. This scheme was originally described by Wun-Fogle, Savage and Clark [{open_quote}{open_quote}Sensitive wide frequency range magnetostrictive strain gauge,{close_quote}{close_quote} Sensors and Actuators, 1{underscore}2{underscore}, 323{endash}331 (1987)]. The bender is in the form of a three layered laminate with a closed magnetic path window frame structure. The theory of operation along with measured and calculated results are presented for a prototype element with approximate dimensions 1.5{times}1.0{times}0.1 inches. Calculated and measured results agree for a reduced effective coupling coefficient of 0.72 and operation with a carrier field intensity of 0.87 Oe and carrier frequency of 20 kHz. {copyright} {ital 1996 American Institute of Physics.}

  8. Glass Formulation Development for INEEL Sodium-Bearing Waste

    SciTech Connect

    J.D. Vienna; M.J. Schweiger; D.E. Smith; H.D. Smith; J.V. Crum; D.K. Peeler; I.A. Reamer; C.A. Musick; R.D. Tillotson

    1999-08-03

    For about four decades, radioactive wastes have been collected and calcined from nuclear fuels reprocessing at the Idaho Nuclear Technology and Engineering Center (INTEC), formerly Idaho Chemical Processing Plant (ICPP). Over this time span, secondary radioactive wastes have also been collected and stored as liquid from decontamination, laboratory activities, and fuel-storage activities. These liquid wastes are collectively called sodium-bearing wastes (SBW). About 5.7 million liters of these wastes are temporarily stored in stainless steel tanks at the Idaho National Engineering and Environmental Laboratory (INEEL). Vitrification is being considered as an immobilization step for SBW with a number of treatment and disposal options. A systematic study was undertaken to develop a glass composition to demonstrate direct vitrification of INEEL's SBW. The objectives of this study were to show the feasibility of SBW vitrification, not a development of an optimum formulation. The waste composition is relatively high in sodium, aluminum, and sulfur. A specific composition and glass property restrictions, discussed in Section 2, were used as a basis for the development. Calculations based on first-order expansions of selected glass properties in composition and some general tenets of glass chemistry led to an additive (fit) composition (68.69 mass % SiO{sub 2}, 14.26 mass% B{sub 2}O{sub 3}, 11.31 mass% Fe{sub 2}O{sub 3}, 3.08 mass% TiO{sub 2}, and 2.67 mass % Li{sub 2}O) that meets all property restrictions when melted with 35 mass % of SBW on an oxide basis, The glass was prepared using oxides, carbonates, and boric acid and tested to confirm the acceptability of its properties. Glass was then made using waste simulant at three facilities, and limited testing was performed to test and optimize processing-related properties and confirm results of glass property testing. The measured glass properties are given in Section 4. The viscosity at 1150 C, 5 Pa{center_dot}s, is

  9. Mechanical failure and glass transition in metallic glasses

    SciTech Connect

    Egami, Takeshi

    2011-01-01

    The current majority view on the phenomenon of mechanical failure in metallic glasses appears to be that it is caused by the activity of some structural defects, such as free-volumes or shear transformation zones, and the concentration of such defects is small, only of the order of 1%. However, the recent results compel us to revise this view. Through molecular dynamics simulation it has been shown that mechanical failure is the stress-induced glass transition. According to our theory the concentration of the liquid-like sites (defects) is well over 20% at the glass transition. We suggest that the defect concentration in metallic glasses is actually very high, and percolation of such defects causes atomic avalanche and mechanical failure. In this article we discuss the glass transition, mechanical failure and viscosity from such a point of view.

  10. Thermochemical study of rare earth and nitrogen incorporation in glasses

    NASA Astrophysics Data System (ADS)

    Zhang, Yahong

    Rare earth containing aluminosilicate, borosilicate, aluminate and nitrogen containing aluminosilicate glasses are technically important materials. They have extraordinary physical and chemical properties such as high glass transition temperature, very low electrical conductivity, and excellent chemical stability. These unique properties lead to applications as coatings on metals and ceramics, optical fibers, semiconductors, and nuclear waste containment materials. In addition, such systems contain the most widely used additives for sintering of Si3N4, SiAlON and SiC ceramics for high temperature applications. Thermodynamic properties and the relations among energetics, structure and bonding are essential to controlling processing parameters to synthesize, at lower cost, materials having better properties. Earlier investigations mainly pertained to specific physical properties of rare-earth doped oxide and oxynitride glasses. Work on the thermodynamic stability and materials compatibility has been very sparse. High temperature solution calorimetry in molten oxide solvents is a powerful tool for the thermodynamic study of refractory materials. With implementation and improvement, this technique has been applied to the first measurement of enthalpies of formation of RE-Si-Al-O glasses, REAlO3 glasses, RE-Si-Al-O-N glasses, and Si3N 4 and Ge3N4 with high pressure spinel structure. The first successful synthesis of REAlO3 glasses has been achieved by containerless melting. Their large enthalpies of crystallization confirm that they are reluctant glass formers. For glasses along the 2REAlO3 -3SiO2 join, the strongly negative heats of mixing support the absence of miscibility gaps except possibly at very high silica content. Energetic evidence has been presented for incipient phase-ordered regions in Gd- or Hf-containing sodium alumino-borosilicate glasses for plutonium immobilization. Linear relations between enthalpies of formation of RESiAlON glasses from elements and

  11. Studies on the effect of Li{sub 2}SO{sub 4} on the structure of lithium borate glasses

    SciTech Connect

    Ganguli, M.; Rao, K.J.

    1999-02-11

    Thermal and spectroscopic investigations have been carried out on a number of glasses with a wide range of compositions in the pseudoternary glass system, Li{sub 2}SO{sub 4}-Li{sub 2}O-B{sub 2}O{sub 3}, to understand the role of sulfate ions in modifying the borate glass structure. Both nuclear magnetic resonance (NMR) and infrared (IR) spectroscopic results indicate that four-coordinate boron atoms are retained in the glass structure to a greater extent in sulfate-containing glasses than in pure lithium borate glasses. There seems to be some evidence for the existence of sulfoborate-type units in Raman spectra in the region of 800--960 cm{sup {minus}1}. These conclusions are supported by the observed behavior of glass transition temperatures and molar volumes. The possibility of formation of sulfoborate-type units is discussed from bonding and thermodynamic points of view.

  12. Liquidus temperature and chemical durability of selected glasses to immobilize rare earth oxides waste

    SciTech Connect

    Mohd Fadzil, Syazwani Binti; Hrma, Pavel R.; Schweiger, Michael J.; Riley, Brian J.

    2015-06-30

    Pyroprocessing is a reprocessing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl-KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the matrix at high loadings. Crystallization that occurs in waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (TL): the International Simple Glass designed by the International Working Group, sodium borosilicate glass developed by Korea Hydro and Nuclear Power, and the lanthanide aluminoborosilicate (LABS) glass established in the United States. The LABS glass allows the highest waste loadings (over 50 mass% RE2O3) while possessing an acceptable chemical durability.

  13. Solution of naturally-ocurring glasses in the geological environment

    NASA Technical Reports Server (NTRS)

    Glass, B. P.

    1982-01-01

    As part of a study to investigate the feasibility of putting nuclear wastes in glass containers and burying them on land or dumping them in the ocean, the amount of solution experience by naturally occurring glasses from two land sites and thirty-four deep sea sites was studied. The glasses are microtektites from three strewn fields and from the Zhamanshin impact crater. The microtektites range in age from 0.7 to 35 m.y. and have a wide range in composition. The weight percent SiO2, for example, ranges from 44.8 to 81.7. Although several criteria for determining the amount of solution were considered, most of the conclusions are based on two criteria: (1) width of cracks, and (2) elevation of silica rich inclusions above the adjacent microtektite surface. All the measurements were made on scanning electron microscope photomicrographs of the microtektites.

  14. Ion-beam depth-profiling studies of leached glasses

    SciTech Connect

    Houser, C.A.; Tsong, I.S.T.; White, W.B.; Wintenberg, A.L.; Miller, P.D.; Moak, C.D.

    1981-01-01

    Ion-beam depth-profiling was carried out on three different glasses leached (or hydrated) in deionized water using /sup 1/H(/sup 19/F,..cap alpha gamma..)/sup 16/O nuclear reaction, secondary ion mass spectrometry (SIMS) and sputter-induced photon spectrometry (SIPS) techniques. The depth-profiles show an interdiffusion mechanism in which the sodium ions in the glass are depleted and replaced by hydrogen (H/sup +/) or hydronium (H/sub 3/O/sup +/) ions from the solution. The leaching behavior does not show significant difference whether the glass surface is fractured or polished. Problems of mobile ion migration caused by ion bombardment and loss of hydrogen during analysis are discussed.

  15. Commercial Ion Exchange Resin Vitrification in Borosilicate Glass

    SciTech Connect

    Cicero-Herman, C.A.; Workman, P.; Poole, K.; Erich, D.; Harden, J.

    1998-05-01

    Bench-scale studies were performed to determine the feasibility of vitrification treatment of six resins representative of those used in the commercial nuclear industry. Each resin was successfully immobilized using the same proprietary borosilicate glass formulation. Waste loadings varied from 38 to 70 g of resin/100 g of glass produced depending on the particular resin, with volume reductions of 28 percent to 68 percent. The bench-scale results were used to perform a melter demonstration with one of the resins at the Clemson Environmental Technologies Laboratory (CETL). The resin used was a weakly acidic meth acrylic cation exchange resin. The vitrification process utilized represented a approximately 64 percent volume reduction. Glass characterization, radionuclide retention, offgas analyses, and system compatibility results will be discussed in this paper.

  16. Method of determining glass durability

    DOEpatents

    Jantzen, C.M.; Pickett, J.B.; Brown, K.G.; Edwards, T.B.

    1998-12-08

    A process is described for determining one or more leachate concentrations of one or more components of a glass composition in an aqueous solution of the glass composition by identifying the components of the glass composition, including associated oxides, determining a preliminary glass dissolution estimator, {Delta}G{sub p}, based upon the free energies of hydration for the component reactant species, determining an accelerated glass dissolution function, {Delta}G{sub a}, based upon the free energy associated with weak acid dissociation, {Delta}G{sub a}{sup WA}, and accelerated matrix dissolution at high pH, {Delta}G{sub a}{sup SB} associated with solution strong base formation, and determining a final hydration free energy, {Delta}G{sub f}. This final hydration free energy is then used to determine leachate concentrations for elements of interest using a regression analysis and the formula log{sub 10}(N C{sub i}(g/L))=a{sub i} + b{sub i}{Delta}G{sub f}. The present invention also includes a method to determine whether a particular glass to be produced will be homogeneous or phase separated. The present invention is also directed to methods of monitoring and controlling processes for making glass using these determinations to modify the feedstock materials until a desired glass durability and homogeneity is obtained. 4 figs.

  17. Refractory Glass Seals for SOFC

    SciTech Connect

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

    2011-07-01

    One of the critical challenges facing planar solid oxide fuel cell (SOFC) technology is the need for reliable sealing technology. Seals must exhibit long-term stability and mechanical integrity in the high temperature SOFC environment during normal and transient operation. Several different approaches for sealing SOFC stacks are under development, including glass or glass-ceramic seals, metallic brazes, and compressive seals. Among glass seals, rigid glass-ceramics, self-healing glass, and composite glass approaches have been investigated under the SECA Core Technology Program. The U.S. Department of Energy's Pacific Northwest National Laboratory (PNNL) has developed the refractory glass approach in light of the fact that higher sealing temperatures (e.g., 930-1000 degrees C) may enhance the ultimate in-service bulk strength and electrical conductivity of contact materials, as well as the bonding strength between contact materials and adjacent SOFC components, such as interconnect coatings and electrodes. This report summarizes the thermal, chemical, mechanical, and electrical properties of the refractory sealing glass.

  18. Training Guidelines: Glass Furnace Operators.

    ERIC Educational Resources Information Center

    Ceramics, Glass, and Mineral Products Industry Training Board, Harrow (England).

    Technological development in the glass industry is constantly directed towards producing high quality glass at low operating costs. Particularly, changes have taken place in melting methods which mean that the modern furnace operator has greater responsibilities than any of his predecessors. The complexity of control systems, melting rates, tank…

  19. Method of determining glass durability

    DOEpatents

    Jantzen, Carol Maryanne; Pickett, John Butler; Brown, Kevin George; Edwards, Thomas Barry

    1998-01-01

    A process for determining one or more leachate concentrations of one or more components of a glass composition in an aqueous solution of the glass composition by identifying the components of the glass composition, including associated oxides, determining a preliminary glass dissolution estimator, .DELTA.G.sub.p, based upon the free energies of hydration for the component reactant species, determining an accelerated glass dissolution function, .DELTA.G.sub.a, based upon the free energy associated with weak acid dissociation, .DELTA.G.sub.a.sup.WA, and accelerated matrix dissolution at high pH, .DELTA.G.sub.a.sup.SB associated with solution strong base formation, and determining a final hydration free energy, .DELTA.G.sub.f. This final hydration free energy is then used to determine leachate concentrations for elements of interest using a regression analysis and the formula log.sub.10 (N C.sub.i (g/L))=a.sub.i +b.sub.i .DELTA.G.sub.f. The present invention also includes a method to determine whether a particular glass to be produced will be homogeneous or phase separated. The present invention is also directed to methods of monitoring and controlling processes for making glass using these determinations to modify the feedstock materials until a desired glass durability and homogeneity is obtained.

  20. Space processing of chalcogenide glass

    NASA Technical Reports Server (NTRS)

    Firestone, R. F.; Schramm, S. W.

    1978-01-01

    A program was conducted to develop the technique of space processing for chalcogenide glass, and to define the process and equipment necessary. In the course of this program, successful long term levitation of objects in a 1-g environment was achieved. Glass beads 4 mm diameter were containerless melted and fused together.

  1. Degradable borate glass polyalkenoate cements.

    PubMed

    Shen, L; Coughlan, A; Towler, M; Hall, M

    2014-04-01

    Glass polyalkenoate cements (GPCs) containing aluminum-free borate glasses having the general composition Ag2O-Na2O-CaO-SrO-ZnO-TiO2-B2O3 were evaluated in this work. An initial screening study of sixteen compositions was used to identify regions of glass formation and cement compositions with promising rheological properties. The results of the screening study were used to develop four model borate glass compositions for further study. A second round of rheological experiments was used to identify a preferred GPC formulation for each model glass composition. The model borate glasses containing higher levels of TiO2 (7.5 mol %) tended to have longer working times and shorter setting times. Dissolution behavior of the four model GPC formulations was evaluated by measuring ion release profiles as a function of time. All four GPC formulations showed evidence of incongruent dissolution behavior when considering the relative release profiles of sodium and boron, although the exact dissolution profile of the glass was presumably obscured by the polymeric cement matrix. Compression testing was undertaken to evaluate cement strength over time during immersion in water. The cements containing the borate glass with 7.5 mol % TiO2 had the highest initial compressive strength, ranging between 20 and 30 MPa. No beneficial aging effect was observed-instead, the strength of all four model GPC formulations was found to degrade with time. PMID:24435528

  2. Holder for rotating glass body

    DOEpatents

    Kolleck, Floyd W.

    1978-04-04

    A device is provided for holding and centering a rotating glass body such as a rod or tube. The device includes a tubular tip holder which may be held in a lathe chuck. The device can utilize a variety of centering tips each adapted for a particular configuration, such as a glass O-ring joint or semi-ball joint.

  3. Making a Better Beer Glass.

    ERIC Educational Resources Information Center

    Hoffer, Alan R.

    1982-01-01

    A class activity is detailed in which alternative designs for glasses are examined. The goal is to design a glass which is built tilted, so that beer can be poured in without creating a foam problem. The activity is viewed as one leading to interesting questions. (MP)

  4. Combined Experimental and Computational Approach to Predict the Glass-Water Reaction

    SciTech Connect

    Pierce, Eric M.; Bacon, Diana H.

    2011-10-01

    The use of mineral and glass dissolution rates measured in laboratory experiments to predict the weathering of primary minerals and volcanic and nuclear waste glasses in field studies requires the construction of rate models that accurately describe the weathering process over geologic timescales. Additionally, the need to model the long-term behavior of nuclear waste glass for the purpose of estimating radionuclide release rates requires that rate models be validated with long-term experiments. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test B, and pressurized unsaturated flow (PUF)], thereby reducing the duration required to evaluate long-term performance. Currently, the PUF test is the only method that mimics the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitors the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior. A one-dimensional reactive chemical transport simulation of glass dissolution and secondary phase formation during a 1.5-year-long PUF experiment was conducted with the Subsurface Transport Over Reactive Multiphases (STORM) code. Results show that parameterization of the computer model by combining direct bench scale laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over the length of the experiment. Over the 1.5-year-long test duration, the rate decreased from 0.2 to 0.01 g/(m2 day) based on B release for low-activity waste glass LAWA44. The observed decrease is approximately two orders of magnitude higher than the decrease observed under static conditions with the SON68 glass (estimated to be a decrease by four orders of magnitude) and suggests that the gel-layer properties are less protective under these dynamic

  5. Silver Valence and Local Environments in Borosilicate and Calcium Aluminoborate Waste Glasses as determined from X-ray Absorption Spectroscopy

    SciTech Connect

    McKeown,D.; Gan, H.; Pegg, I.

    2005-01-01

    Silver K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data were collected and analyzed to characterize silver (Ag) environments in borosilicate and Ca-aluminoborate glass formulations developed as potential candidates for the immobilization of certain nuclear wastes. Silver is found in some nuclear waste streams and must be encapsulated in glass during waste vitrification processes. A related concern deals with phase separation within these glasses and whether colloidal silver would be present in the glass melt, which could present processing issues, or in the waste glass product. Characterization of the silver environments provides useful information for optimizing the silver incorporation ability of such glasses. Data were also gathered on four crystalline standards: Ag-foil, Ag{sub 2}O, argentojarosite (AgFe{sub 3}(SO{sub 4}){sub 2}(OH){sub 6}), and AgO. XANES data indicate Ag{sup +} as the dominant species in the glasses. XANES and EXAFS data show that the average Ag environment in the Ca-aluminoborate glass is different compared with those in the two borosilicate glasses investigated. EXAFS analyses show that Ag in the borosilicate glasses is coordinated by two oxygens in a similar environment to that in crystalline Ag{sub 2}O, except that the associated Ag-O distances are approximately 0.10 Angstroms longer in the glass. Silver in the Ca-aluminoborate glass may be within one highly disordered site, or possibly, several different sites, where the average Ag-O distance, coordination number, and Debye-Waller factor are larger than those determined for the borosilicate glasses. Despite their relatively high silver contents, there is no evidence from XANES or EXAFS of colloidal silver in the glasses investigated.

  6. CHEMICAL ANALYSIS OF SIMULATED HIGH LEVEL WASTE GLASSES TO SUPPORT SULFATE SOLUBILITY MODELING

    SciTech Connect

    Fox, K.; Marra, J.

    2014-08-14

    The U.S. Department of Energy (DOE), Office of Environmental Management (EM) is sponsoring an international, collaborative project to develop a fundamental model for sulfate solubility in nuclear waste glass. The solubility of sulfate has a significant impact on the achievable waste loading for nuclear waste forms both within the DOE complex and to some extent at U.K. sites. The development of enhanced borosilicate glass compositions with improved sulfate solubility will allow for higher waste loadings and accelerated cleanup missions. Much of the previous work on improving sulfate retention in waste glasses has been done on an empirical basis, making it difficult to apply the findings to future waste compositions despite the large number of glass systems studied. A more fundamental, rather than empirical, model of sulfate solubility in glass, under development at Sheffield Hallam University (SHU), could provide a solution to the issues of sulfate solubility. The model uses the normalized cation field strength index as a function of glass composition to predict sulfate capacity, and has shown early success for some glass systems. The objective of the current scope is to mature the sulfate solubility model to the point where it can be used to guide glass composition development for DOE waste vitrification efforts, allowing for enhanced waste loadings and waste throughput. A series of targeted glass compositions was selected to resolve data gaps in the current model. SHU fabricated these glasses and sent samples to the Savannah River National Laboratory (SRNL) for chemical composition analysis. SHU will use the resulting data to enhance the sulfate solubility model and resolve any deficiencies. In this report, SRNL provides chemical analyses for simulated waste glasses fabricated SHU in support of sulfate solubility model development. A review of the measured compositions revealed that there are issues with the B{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} concentrations

  7. Energetics of glass fragmentation: Experiments on synthetic and natural glasses

    NASA Astrophysics Data System (ADS)

    Kolzenburg, S.; Russell, J. K.; Kennedy, L. A.

    2013-11-01

    Natural silicate glasses are an essential component of many volcanic rock types including coherent and pyroclastic rocks; they span a wide range of compositions, occur in diverse environments, and form under a variety of pressure-temperature conditions. In subsurface volcanic environments (e.g., conduits and feeders), melts intersect the thermodynamically defined glass transition temperature to form glasses at elevated confining pressures and under differential stresses. We present a series of room temperature experiments designed to explore the fundamental mechanical and fragmentation behavior of natural (obsidian) and synthetic glasses (Pyrex™) under confining pressures of 0.1-100 MPa. In each experiment, glass cores are driven to brittle failure under compressive triaxial stress. Analysis of the load-displacement response curves is used to quantify the storage of energy in samples prior to failure, the (brittle) release of elastic energy at failure, and the residual energy stored in the post-failure material. We then establish a relationship between the energy density within the sample at failure and the grain-size distributions (D-values) of the experimental products. The relationship between D-values and energy density for compressive fragmentation is significantly different from relationships established by previous workers for decompressive fragmentation. Compressive fragmentation is found to have lower fragmentation efficiency than fragmentation through decompression (i.e., a smaller change in D-value with increasing energy density). We further show that the stress storage capacity of natural glasses can be enhanced (approaching synthetic glasses) through heat treatment.

  8. Database and Interim Glass Property Models for Hanford HLW Glasses

    SciTech Connect

    Hrma, Pavel R.; Piepel, Gregory F.; Vienna, John D.; Cooley, Scott K.; Kim, Dong-Sang; Russell, Renee L.

    2001-07-24

    The purpose of this report is to provide a methodology for an increase in the efficiency and a decrease in the cost of vitrifying high-level waste (HLW) by optimizing HLW glass formulation. This methodology consists in collecting and generating a database of glass properties that determine HLW glass processability and acceptability and relating these properties to glass composition. The report explains how the property-composition models are developed, fitted to data, used for glass formulation optimization, and continuously updated in response to changes in HLW composition estimates and changes in glass processing technology. Further, the report reviews the glass property-composition literature data and presents their preliminary critical evaluation and screening. Finally the report provides interim property-composition models for melt viscosity, for liquidus temperature (with spinel and zircon primary crystalline phases), and for the product consistency test normalized releases of B, Na, and Li. Models were fitted to a subset of the screened database deemed most relevant for the current HLW composition region.

  9. High level nuclear waste

    SciTech Connect

    Crandall, J L

    1980-01-01

    The DOE Division of Waste Products through a lead office at Savannah River is developing a program to immobilize all US high-level nuclear waste for terminal disposal. DOE high-level wastes include those at the Hanford Plant, the Idaho Chemical Processing Plant, and the Savannah River Plant. Commercial high-level wastes, for which DOE is also developing immobilization technology, include those at the Nuclear Fuel Services Plant and any future commercial fuels reprocessing plants. The first immobilization plant is to be the Defense Waste Processing Facility at Savannah River, scheduled for 1983 project submission to Congress and 1989 operation. Waste forms are still being selected for this plant. Borosilicate glass is currently the reference form, but alternate candidates include concretes, calcines, other glasses, ceramics, and matrix forms.

  10. Containerless glass fiber processing

    NASA Technical Reports Server (NTRS)

    Ethridge, E. C.; Naumann, R. J.

    1986-01-01

    An acoustic levitation furnace system is described that was developed for testing the feasibility of containerless fiber pulling experiments. It is possible to levitate very dense materials such as platinum at room temperature. Levitation at elevated temperatures is much more difficult. Samples of dense heavy metal fluoride glass were levitated at 300 C. It is therefore possible that containerless fiber pulling experiments could be performed. Fiber pulling from the melt at 650 C is not possible at unit gravity but could be possible at reduced gravities. The Acoustic Levitation Furnace is described, including engineering parameters and processing information. It is illustrated that a shaped reflector greatly increases the levitation force aiding the levitation of more dense materials.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  12. Iodine valence and local environments in borosilicate waste glasses using X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    McKeown, David A.; Muller, Isabelle S.; Pegg, Ian L.

    2015-01-01

    The radioisotope 129I, a fission product in spent nuclear fuel, has a long half-life, and can be highly mobile in the environment. Iodine K-edge X-ray absorption spectra were collected to characterize the iodine valence and coordination environment in simulated Hanford low activity waste glasses. Both iodine XANES and EXAFS data for eleven borosilicate glasses indicate iodide-like environments within the glass structure, where I- has Na or Li nearest-neighbors, and where the nearest-neighbor cation-type correlates to the most common network-modifying cation in the glass. This is further supported by the systematic increase of iodine incorporation with the combined Na2O + Li2O content in the glass. EXAFS analyses determined I-Na distances near 3.04 Å with coordination numbers near 4.0 and I-Li distances near 2.80 Å with coordination numbers near 3.0. I-Na environments determined for the glasses are similar to the tetrahedral INa4 coordination found in NaI-sodalite. These weakly bound iodine-alkali configurations may be the only pathways for iodine to be retained in the glass. These environments may be precursors to NaI-sodalite crystallization in Na-rich glass. Iodine also shows distinct differences from chlorine in terms of the preferred sites in the glass structure.

  13. A literature review of surface alteration layer effects on waste glass behavior

    SciTech Connect

    Feng, X.; Cunnane, J.C.; Bates, J.K.

    1993-01-01

    When in contact with an aqueous solution, nuclear waste glass is subject to a chemical attack that results in progressive alteration. During tills alteration, constituent elements of the glass pass into the solution; elements initially in solution diffuse into, or are adsorbed onto, the solid; and new phases appear. This results in the formation of surface layers on the reacted glass. The glass corrosion and radionuclide release can be better understood by investigating these surface layer effects. In the past decade, there have been numerous studies regarding the effects of surface layers on glass reactions. This paper presents a systematic analysis and summary of the past knowledge regarding the effects of surface layers on glass-water interaction. This paper describes the major formation mechanisms of surface layers; reviews the role of surface layers in controlling mass transport and glass reaction affinity (through crystalline phases, an amorphous silica, a gel layer, or all the components in the glass); and discusses how the surface layers contribute to the retention of radionuclides during glass dissolution.

  14. A literature review of surface alteration layer effects on waste glass behavior

    SciTech Connect

    Feng, X.; Cunnane, J.C.; Bates, J.K.

    1993-05-01

    When in contact with an aqueous solution, nuclear waste glass is subject to a chemical attack that results in progressive alteration. During tills alteration, constituent elements of the glass pass into the solution; elements initially in solution diffuse into, or are adsorbed onto, the solid; and new phases appear. This results in the formation of surface layers on the reacted glass. The glass corrosion and radionuclide release can be better understood by investigating these surface layer effects. In the past decade, there have been numerous studies regarding the effects of surface layers on glass reactions. This paper presents a systematic analysis and summary of the past knowledge regarding the effects of surface layers on glass-water interaction. This paper describes the major formation mechanisms of surface layers; reviews the role of surface layers in controlling mass transport and glass reaction affinity (through crystalline phases, an amorphous silica, a gel layer, or all the components in the glass); and discusses how the surface layers contribute to the retention of radionuclides during glass dissolution.

  15. Structure-topology-property correlations of sodium phosphosilicate glasses

    SciTech Connect

    Hermansen, Christian; Smedskjaer, Morten M.; Guo, Xiaoju; Youngman, Randall E.; Mauro, John C.; Yue, Yuanzheng

    2015-08-14

    In this work, we investigate the correlations among structure, topology, and properties in a series of sodium phosphosilicate glasses with [SiO{sub 2}]/[SiO{sub 2} + P{sub 2}O{sub 5}] ranging from 0 to 1. The network structure is characterized by {sup 29}Si and {sup 31}P magic-angle spinning nuclear magnetic resonance and Raman spectroscopy. The results show the formation of six-fold coordinated silicon species in phosphorous-rich glasses. Based on the structural data, we propose a formation mechanism of the six-fold coordinated silicon, which is used to develop a quantitative structural model for predicting the speciation of the network forming units as a function of chemical composition. The structural model is then used to establish a temperature-dependent constraint description of phosphosilicate glass topology that enables prediction of glass transition temperature, liquid fragility, and indentation hardness. The topological constraint model provides insight into structural origin of the mixed network former effect in phosphosilicate glasses.

  16. [Respiratory function in glass blowers].

    PubMed

    Zuskin, E; Butković, D; Mustajbegović, J

    1992-01-01

    The prevalence of chronic and acute respiratory symptoms and diseases and changes in lung function in a group of 80 glass blowers have been investigated. In addition a group of 80 not exposed workers was used as a control group for respiratory symptoms and diseases. In glass blowers, there was significant increase in prevalence of chronic bronchitis, nasal catarrh, and sinusitis than in the controls. Glass blowers exposed for more and less than 10 years had similar prevalences of respiratory symptoms. A large number of glass blowers complained of acute across-shift symptoms. Significant increase in FVC, FEF50 and FEF25 was documented at the end of the work shift. Comparison with predicted normal values showed that glass blowers had FVC and FEF25 significantly lower than predicted. RV and RV/TLC were significantly increased compared with the predicted normal values. DLCO was within the normal values in most glass blowers. It is concluded that work in the glass blower industry is likely to lead the development of chronic respiratory disorders. PMID:1343122

  17. Glass ceramic seals to inconel

    DOEpatents

    McCollister, Howard L.; Reed, Scott T.

    1983-11-08

    A glass ceramic composition prepared by subjecting a glass composition comprising, by weight, 65-80% SiO.sub.2, 8-16%, Li.sub.2 O, 2-8% , Al.sub.2 O.sub.3, 1-8% K.sub.2 O, 1-5% P.sub.2 O.sub.5 and 1.5-7% B.sub.2 O.sub.3, to the following processing steps of heating the glass composition to a temperature sufficient to crystallize lithium metasilicate therein, holding the glass composition at a temperature and for a time period sufficient to dissolve the lithium metasilicate therein thereby creating cristobalite nucleii, cooling the glass composition and maintaining the composition at a temperature and for a time period sufficient to recrystallize lithium metasilicate therein, and thermally treating the glass composition at a temperature and for a time period sufficient to cause growth of cristobalite and further crystallization of lithium metasilicate producing a glass ceramic composition having a specific thermal expansion coefficient and products containing said composition.

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

    SciTech Connect

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

    2011-03-28

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

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

    PubMed

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

    2013-01-15

    Silicate glasses are used as containment matrices for deep geological disposal of nuclear waste arising from spent fuel reprocessing. Understanding the dissolution mechanisms of glasses in contact with iron, an element present in large amounts in the immediate environment (overpack, claystone, etc.) would be a major breakthrough toward predicting radionuclide release in the geosphere after disposal. Two different reacted glass-iron interfaces-a short-term nuclear system and a long-term archeological system-were examined using a multiscale and multianalytical approach including, for the first time on samples of this type, STXM under synchrotron radiation. Comparisons revealed remarkable similarities between the two systems and shed light on Fe-Si interactions, including migration of iron within a porous gel layer and precipitation of Fe-silicates that locally increase short-term glass alteration and are sustainable over the long-term. PMID:23237387

  20. Are gel-derived glasses different from ordinary glasses?

    NASA Technical Reports Server (NTRS)

    Weinberg, M. C.

    1986-01-01

    A review is presented of some of the previously reported differences and similarities between comparable gel glasses (and gels) and ordinary glasses. In this regard, considerations are made with respect to such factors as structure, physical and thermal properties, and phase transformation behavior. A variety of silicate glass compositions are used for illustrative purposes. The discussion is roughly divided into two sections: low and high temperature behavior. At low temperatures one anticipates that differences between gel and conventional glasses will exist, but such dissimilarities are not expected to persist to high temperatures. However, experimental evidence is presented which indicates the perpetuation of such differences to very high temperatures. A partial resolution for this anomalous behavior is offered.

  1. GLASS COMPOSITION-TCLP RESPONSE MODEL FOR WASTE GLASSES

    SciTech Connect

    Kim, Dong-Sang; Vienna, John D.

    2004-01-01

    A first-order property model for normalized Toxicity Characteristic Leaching Procedure (TCLP) release as a function of glass composition was developed using data collected from various studies. The normalized boron release is used to estimate the release of toxic elements based on the observation that the boron release represents the conservative release for those constituents of interest. The current TCLP model has two targeted application areas: (1) delisting of waste-glass product as radioactive (not mixed) waste and (2) designating the glass wastes generated from waste-glass research activities as hazardous or non-hazardous. This paper describes the data collection and model development for TCLP releases and discusses the issues related to the application of the model.

  2. Positive and Negative Mixed Glass Former Effects in Sodium Borosilicate and Borophosphate Glasses Studied by (23)Na NMR.

    PubMed

    Storek, Michael; Adjei-Acheamfour, Mischa; Christensen, Randilynn; Martin, Steve W; Böhmer, Roland

    2016-05-19

    Glasses with varying compositions of constituent network formers but constant mobile ion content can display minima or maxima in their ion transport which are known as the negative or the positive mixed glass former effect, MGFE, respectively. Various nuclear magnetic resonance (NMR) techniques are used to probe the ion hopping dynamics via the (23)Na nucleus on the microscopic level, and the results are compared with those from conductivity spectroscopy, which are more sensitive to the macroscopic charge carrier mobility. In this way, the current work examines two series of sodium borosilicate and sodium borophosphate glasses that display positive and negative MGFEs, respectively, in the composition dependence of their Na(+) ion conductivities at intermediate compositions of boron oxide substitution for silicon oxide and phosphorus oxide, respectively. A coherent theoretical analysis is performed for these glasses which jointly captures the results from measurements of spin relaxation and central-transition line shapes. On this basis and including new information from (11)B magic-angle spinning NMR regarding the speciation in the sodium borosilicate glasses, a comparison is carried out with predictions from theoretical approaches, notably from the network unit trap model. This comparison yields detailed insights into how a variation of the boron oxide content and thus of either the population of silicon or phosphorus containing network-forming units with different charge-trapping capabilities leads to nonlinear changes of the microscopic transport properties. PMID:27092392

  3. Recent developments in laser glasses

    SciTech Connect

    Weber, M.J.

    1983-01-10

    The past decade has witnessed a proliferation of new glass-forming compositions including oxides, halides, oxyhalides, and chalcogenides. Many of these glasses are applicable to lasers and have greatly expanded the range of optical properties and spectroscopic parameters available to the laser designer. Our knowledge and understanding of many properties of interest for laser action - transparency, linear and nonlinear refractive indices, and damage threshold of the host glass and the absorption spectrum, radiative and nonradiative transition probabilities, fluorescence wavelength, stimulated emission cross section, and spectroscopic inhomogeneities of the lasing ion Nd/sup 3 +/ - are reviewed.

  4. Method for manufacturing glass frit

    DOEpatents

    Budrick, Ronald G.; King, Frank T.; Nolen, Jr., Robert L.; Solomon, David E.

    1977-01-01

    A method of manufacturing a glass frit for use in the manufacture of uniform glass microspheres to serve as containers for laser fusion fuel to be exposed to laser energy which includes the formation of a glass gel which is then dried, pulverized, and very accurately sized to particles in a range of, for example, 125 to 149 micrometers. The particles contain an occluded material such as urea which expands when heated. The sized particles are washed, dried, and subjected to heat to control the moisture content prior to being introduced into a system to form microspheres.

  5. Accommodation Assisting Glasses for Presbyopia

    NASA Astrophysics Data System (ADS)

    Fujita, Toyomi; Idesawa, Masanori

    2002-10-01

    We have considered the important functions for developing accommodation-assistance glasses which can assist eye focusing for aged person with presbyopia.We focused on keys to realize small and lightweight variable focusing lens and gaze distance detection. We devised new variable focusing lenses with control and gaze distance detection with a tunnel light path device. A prototype of glasses with devised elements was manufactured experimentally. From the result of trial use of them and experiments for evaluating characteristics,it was confirmed that proposed technologies were useful for realization of accommodation-assistance glasses.

  6. Formation of Nanoporous Glass Layer

    NASA Astrophysics Data System (ADS)

    Grigoras, Kestutis; Franssila, Sami

    2004-01-01

    Porous layers have been formed in Pyrex glass by reactive ion etching (RIE). Chromium is used as an etch mask. Different etch gases (SF6, CF4/Ar) have been used, and depending on flow ratio, etch time and applied power, a dense array of high aspect ratio glass pillars with submicrometer dimensions was obtained instead of a smooth channel bottom. The pillars were about 500nm tall and 50 100nm in cross-section. The formation of porous layers is explained by the effect of mask material re-deposition during the plasma etching. Porous glass layers could have applications in chromatographic separations or microchemicalsample concentrators.

  7. Glass microspheres for medical applications

    NASA Astrophysics Data System (ADS)

    Conzone, Samuel David

    Radioactive dysprosium lithium borate glass microspheres have been developed as biodegradable radiation delivery vehicles for the radiation synovectomy treatment of rheumatoid arthritis. Once injected into a diseased joint, the microspheres deliver a potent dose of radiation to the diseased tissue, while a non-uniform chemical reaction converts the glass into an amorphous, porous, hydrated dysprosium phosphate reaction product. The non-radioactive, lithium-borate component is dissolved from the glass (up to 94% weight loss), while the radioactive 165Dy reacts with phosphate anions in the body fluids, and becomes "chemically" trapped in a solid, dysprosium phosphate reaction product that has the same size as the un-reacted glass microsphere. Ethylene diamine tetraacetate (EDTA) chelation therapy can be used to dissolve the dysprosium phosphate reaction product after the radiation delivery has subsided. The dysprosium phosphate reaction product, which formed in vivo in the joint of a Sprague-Dawley rat, was dissolved by EDTA chelation therapy in <1 week, without causing any detectable joint damage. The combination of dysprosium lithium borate glass microspheres and EDTA chelation therapy provides an unique "tool" for the medical community, which can deliver a large dose (>100 Gy) of localized beta radiation to a treatment site within the body, followed by complete biodegradability. The non-uniform reaction process is a desirable characteristic for a biodegradable radiation delivery vehicle, but it is also a novel material synthesis technique that can convert a glass to a highly porous materials with widely varying chemical composition by simple, low-temperature, glass/solution reaction. The reaction product formed by nonuniform reaction occupies the same volume as the un-reacted glass, and after drying for 1 h at 300°C, has a specific surface area of ≈200 m2/g, a pore size of ≈30 nm, and a nominal crushing strength of ≈10 MPa. Finally, rhenium glass

  8. Thermo-physical and structural studies of sodium zinc borovanadate glasses in the region of high concentration of modifier oxides

    SciTech Connect

    Chethana, B.K.; Reddy, C. Narayana; Rao, K.J.

    2012-07-15

    Highlights: ► Highly modified sodium zinc borovanadate glasses. ► Structural model for borovanadate glasses. ► Network forming tendency of ZnO in borovanadate glasses. ► Fragility can be limited to NBO concentration in borovanadate glasses. -- Abstract: This paper reports investigation of Na{sub 2}O and ZnO modified borovanadate glasses in the highly modified regime of compositions. These glasses have been prepared by microwave route. Ultraviolet (UV) and visible, infrared (IR), Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies have been used to characterize the speciation in the glasses. Together with the variation of properties such as molar volume and glass transition temperatures, spectroscopic data indicate that at high levels of modification, ZnO tends to behave like network former. It is proposed that the observed variation of all the properties can be reasonably well understood with a structural model. The model considers that the modification and speciation in glasses are strongly determined by the hierarchy of group electronegativities. Further, it is proposed that the width of the transitions of glasses obtained under same condition reflects the fragility of the glasses. An empirical expression has been suggested to quantify fragility on the basis of width of the transition regions.

  9. Glass corrosion in the presence of iron-bearing materials and potential corrosion suppressors

    SciTech Connect

    Reiser, Joelle T.; Neill, Lindsay; Weaver, Jamie L.; Parruzot, Benjamin; Musa, Christopher; Neeway, James J.; Ryan, Joseph V.; Qafoku, Nikolla; Gin, Stephane; Wall, Nathalie

    2015-07-16

    A complete understanding of radioactive waste glass interactions with near-field materials is essential for appropriate nuclear waste repository performance assessment. In many geologic repository designs, Fe is present in both the natural environment and in the containers that will hold the waste glasses. In this paper we discuss investigations into the alteration of International Simple Glass (ISG) in the presence of Fe0 foil and hematite (Fe2O3). ISG alteration is more pronounced in the presence of Fe0 than with hematite. Additionally, minimal glass corrosion is observed for distances equal to 5 mm between Fe materials and ISG, but substantial glass corrosion is observed for systems exhibiting full contact between Fe0 material and ISG. Diatomaceous earth appears to be a better corrosion suppressant than silica when present with iron and ISG.

  10. Simulation of cooling and solidification of three-dimensional bulk borosilicate glass. Effect of structural relaxations

    SciTech Connect

    Barth, N.; George, D.; Ahzi, Said; Remond, Y.; Joulaee, N.; Khaleel, Mohammad A.; Bouyer, F.

    2013-04-20

    The modeling of the viscoelastic stress evolution and specific volume relaxation of a bulky glass cast is presented in this article and is applied to the experimental cooling process of an inactive nuclear waste vitrification process. The concerned borosilicate glass is solidified and cooled down to ambient temperature in a stainless steel canister, and the thermomechanical response of the package is simulated. There exists a deviant compression of the liquid core due to the large glass package compared to standard tempered glass plates. The stress load development of the glass cast is finally studied for different thermal load scenarios, where the cooling process parameters or the final cooldown rates were changed, and we found a great influence of the studied cooldown rates on the maximum stress buildup at ambient temperature.

  11. Simulation of cooling and solidification of three-dimensional bulk borosilicate glass: effect of structural relaxations

    NASA Astrophysics Data System (ADS)

    Barth, N.; George, D.; Ahzi, S.; Rémond, Y.; Joulaee, N.; Khaleel, M. A.; Bouyer, F.

    2014-02-01

    The modeling of the viscoelastic stress evolution and specific volume relaxation of a bulky glass cast is presented in this article and is applied to the experimental cooling process of an inactive nuclear waste vitrification process. The concerned borosilicate glass is solidified and cooled down to ambient temperature in a stainless steel canister, and the thermomechanical response of the package is simulated. There exists a deviant compression of the liquid core due to the large glass package compared to standard tempered glass plates. The stress load development of the glass cast is finally studied for different thermal load scenarios, where the cooling process parameters or the final cooldown rates were changed, and we found a great influence of the studied cooldown rates on the maximum stress build-up at ambient temperature.

  12. The Effect of Foaming and Silica Dissolution on Melter Feed Rheology during Conversion to Glass

    SciTech Connect

    Marcial, Jose; Chun, Jaehun; Hrma, Pavel R.; Schweiger, Michael J.

    2014-11-23

    As the nuclear waste glass melter feed is converted to molten glass, the feed eventually becomes a continuous glass-forming melt in which dissolving refractory constituents are suspended together with numerous gas bubbles. Knowledge of mechanical properties of the melter feed is crucial for understanding the feed-to-glass conversion as it occurs in the cold cap. We measured the viscosity during heating of the feed and correlated it with the independently determined volume fractions of dissolving quartz particles and the gas phase. The measurement was performed with a rotating spindle rheometer on the melter feed heated at 5 K/min starting at several different temperatures. The effect of quartz particles, gas bubbles, and compositional inhomogeneity on the glass-forming melt viscosity was determined by fitting a linear relationship between log viscosity and volume fractions of suspended phases to data.

  13. Conversion of radioactive ferrocyanide compounds to immobile glasses

    DOEpatents

    Schulz, Wallace W.; Dressen, A. Louise

    1977-04-26

    Complex radioactive ferrocyanide compounds result from the scavenging of cesium from waste products produced in the chemical reprocessing of nuclear fuel. These ferrocyanides, in accordance with this process, are converted to an immobile glass, resistant to leaching by water, by fusion together with sodium carbonate and a mixture of (a) basalt and boron trioxide (B.sub.2 O.sub.3) or (b) silica (SiO.sub.2) and lime (CaO).

  14. Radiation Effects in Nuclear Waste Materials

    SciTech Connect

    William j. Weber; Lumin Wang; Jonathan Icenhower

    2004-07-09

    The objective of this project is to develop a fundamental understanding of radiation effects in glasses and ceramics, as well as the influence of solid-state radiation effects on aqueous dissolution kinetics, which may impact the performance of nuclear waste forms and stabilized nuclear materials.

  15. Turning geothermal waste into glasses and glass ceramics

    SciTech Connect

    Diaz, C. ); Torres-Martinez, L.M.; Garza, L. ); Avalos-Borja, M. ); Rincon, J.M. )

    1993-10-01

    Researchers investigating the waste on the pipes at the Cerro Prieto geothermal plant in Mexico found that it contained high amounts of silica. Initial tests showed that this waste silica had a high specific surface area, contained salts that could easily be eliminated, and resisted high temperatures effectively. Further research was done to see if this waste material could be used as silica sand in the production of glass. Testing of the waste material included the following: X-ray diffraction with nickel filters; EDX spectroscopy with ultrathin window; Differential thermal analysis; IR spectroscopy analysis; Electron microscope analysis. The tests were done on the raw material itself and on four sets of glass formulated from the raw material. Two sets of glass were formulated from untreated waste material, and two sets were formulated from treated waste material. The raw material was tested for purity, and the glass was tested for hardness, toughness, and transparency. As the tests show, the silica material from the Cerro Prieto plant steam pipes is not merely useless industrial waste. It is a reproducible source of silica sand that producers can use in ceramic and glass production. The initial tests show that the properties of the raw material, and those of the glass formulated from the raw material, will meet industry requirements.

  16. Galactic Hearts of Glass

    NASA Technical Reports Server (NTRS)

    2006-01-01

    [figure removed for brevity, see original site] Click on image for larger graph

    This artist's concept shows delicate greenish crystals sprinkled throughout the violent core of a pair of colliding galaxies. The white spots represent a thriving population of stars of all sizes and ages. NASA's Spitzer Space Telescope detected more than 20 bright and dusty galactic mergers like the one depicted here, all teeming with the tiny gem-like crystals.

    When galaxies collide, they trigger the birth of large numbers of massive stars. Astronomers believe these blazing hot stars act like furnaces to produce silicate crystals in the same way that glass is made from sand. The stars probably shed the crystals as they age, and as they blow apart in supernovae explosions.

    At the same time the crystals are being churned out, they are also being destroyed. Fast-moving particles from supernova blasts easily convert silicates crystals back to their amorphous, or shapeless, form.

    How is Spitzer seeing the crystals if they are rapidly disappearing? Astronomers say that, for a short period of time at the beginning of galactic mergers, massive stars might be producing silicate crystals faster than they are eliminating them. When our own galaxy merges with the Andromeda galaxy in a few billion years, a similar burst of massive stars and silicate crystals might occur.

    Crystal Storm in Distant Galaxy The graph (see inset above) of infrared data from NASA's Spitzer Space Telescope tells astronomers that a distant galaxy called IRAS 08752+3915 is experiencing a storm of tiny crystals made up of silicates. The crystals are similar to the glass-like grains of sand found on Earth's many beaches.

    The data were taken by Spitzer's infrared spectrograph, which splits light open to reveal its rainbow-like components. The resulting spectrum shown here reveals the signatures of both crystalline (green) and non-crystalline (brown) silicates.

    Spitzer detected the same

  17. Potential and challenges of interdisciplinary research on historical window glass, stained glass and reverse glass paintings

    NASA Astrophysics Data System (ADS)

    Trümpler, Stefan; Wolf, Sophie; Kessler, Cordula; Goll, Jürg

    The interdisciplinary study of ancient materials has become an increasingly common strategy, mainly because it has proved to be a highly rewarding approach to studying the age, provenance and production of archaeological objects. The results of such an approach sometimes also provide answers to questions relating not only to socio-cultural, economic or technological developments in a particular region or period (trade, innovation, production etc.), but also the conservation of the materials or artefacts in question. A number of analytical methods, ranging from microscopic to elementary analyses, have been successfully applied to determine the nature of materials and technologies used in the production, as well as to identify the provenance of ancient glass. As far as window glass and stained glass is concerned, the study of architectural context and art history - as well as the technological characteristics of materials - has proved to be most helpful in determining history, production and artistic importance of the objects under study. This paper discusses some of the multidisciplinary studies that the Vitrocentre Romont has conducted on early medieval window glass, stained glass and reverse glass paintings and illustrates the potential of a holistic approach in solving questions about materials, techniques, window design and conservation. It also addresses the limitations of the approach, which are often related to finding appropriate (i.e. non-destructive and possibly portable) methods for the analysis of sometimes extremely fragile stained glass windows.

  18. The role of test parameters on the kinetics and thermodynamics of glass leaching. [None

    SciTech Connect

    Jantzen, C M

    1988-01-01

    The relative durabilities of nuclear waste, natural, and ancient glasses have been assessed by standard laboratory leach tests. Different test conditions result in different glass surface areas (SA), leachant volumes (V), and test durations (t). Leachate concentrations are known to be a parabolic function of the kinetic test parameter SAV/center dot/t. Based on durability experiments of glass monoliths at low (SAV)/center dot/ glass durability has been shown to be a logarithmic function of the thermodynamic hydration free energy, ..delta..G/sub hyd/. The thermodynamic hydration free energy, ..delta..G/sub hyd/, can be calculated from glass composition and solution pH. In the repository environment high effective glass surface areas to solution volume ratios may occur as a result of slow groundwater flow rates. The application of hydration thermodynamics to crushed glass, high (SAV)/center dot/t, durability tests has been demonstrated. The relative contributions of the kinetic test parameters, (SAV)/center dot/t, and the thermodynamic parameter, ..delta..G/sub hyd/, have been shown to define a plane in ..delta..G/sub hyd/-concentration-(SAV)/center dot/t space. At constant test conditions, e.g. constant (SAV/center dot/t, the intersection with this surface indicates that all /delta G//sub hyd/-concentration plots should have similar slopes and predict the same relative durabilities for various glasses as a function of glass composition. Using this approach, the durability of nuclear waste glasses has been interpolated to be -- 10/sup 6/ years and no less than 10/sup 3/ years. 28 refs., 24 figs.

  19. Combined Experimental and Computational Approach to Predict the Glass-Water Reaction

    SciTech Connect

    Pierce, Eric M; Bacon, Diana

    2011-01-01

    The use of mineral and glass dissolution rates measured in laboratory experiments to predict the weathering of primary minerals and volcanic and nuclear waste glasses in field studies requires the construction of rate models that accurately describe the weathering process over geologic time-scales. Additionally, the need to model the long-term behavior of nuclear waste glass for the purpose of estimating radionuclide release rates requires that rate models are validated with long-term experiments. Several long-term test methods have been developed to accelerate the glass-water reaction [drip test, vapor hydration test, product consistency test-B, and pressurized unsaturated flow (PUF)], thereby reducing the duration required to evaluate long-term performance. Currently, the PUF test is the only method that mimics the unsaturated hydraulic properties expected in a subsurface disposal facility and simultaneously monitors the glass-water reaction. PUF tests are being conducted to accelerate the weathering of glass and validate the model parameters being used to predict long-term glass behavior. A one-dimensional reactive chemical transport simulation of glass dissolution and secondary phase formation during a 1.5-year long PUF experiment was conducted with the subsurface transport over reactive multi-phases code. Results show that parameterization of the computer model by combining direct bench-scale laboratory measurements and thermodynamic data provides an integrated approach to predicting glass behavior over the length of the experiment. Over the 1.5-year long test duration, the rate decreased from 0.2 to 0.01 g/(m2 d) base on B release. The observed decrease is approximately two orders of magnitude higher than the decrease observed under static conditions with the SON68 glass (estimated to be a decrease by 4 orders of magnitude) and suggest the gel-layer properties are less protective under these dynamic conditions.

  20. 7 CFR 2902.30 - Glass cleaners.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 15 2011-01-01 2011-01-01 false Glass cleaners. 2902.30 Section 2902.30 Agriculture... Glass cleaners. (a) Definition. Cleaning products designed specifically for use in cleaning glass... qualifying biobased glass cleaners. By that date, Federal agencies that have the responsibility for...

  1. 7 CFR 2902.30 - Glass cleaners.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 15 2010-01-01 2010-01-01 false Glass cleaners. 2902.30 Section 2902.30 Agriculture... Glass cleaners. (a) Definition. Cleaning products designed specifically for use in cleaning glass... qualifying biobased glass cleaners. By that date, Federal agencies that have the responsibility for...

  2. EVA-glass interface bond stability

    NASA Technical Reports Server (NTRS)

    Koenig, J. L.

    1984-01-01

    The ethylene vinyl acetate/glass interface bond stability was investigated. Special methods to determine the structure of polymer/glass interface were developed. Structural changes related to hydrothermal degradation of polymer/glass interface are examined. Methods to inhibit the degradation reaction which occur at polymer/glass interface are developed.

  3. Properties Of Soda/Yttria/Silica Glasses

    NASA Technical Reports Server (NTRS)

    Angel, Paul W.; Hann, Raiford E.

    1994-01-01

    Experimental study of glass-formation compositional region of soda/ yttria/silicate system and of selected physical properties of glasses within compositional region part of continuing effort to identify glasses with high coefficients of thermal expansion and high softening temperatures, for use as coatings on superalloys and as glass-to-metal seals.

  4. Apollo applications of beta fiber glass

    NASA Technical Reports Server (NTRS)

    Naimer, J.

    1971-01-01

    The physical characteristics of Beta fiber glass are discussed. The application of Beta fiber glass for fireproofing the interior of spacecraft compartments is described. Tests to determine the flammability of Beta fiber glass are presented. The application of Beta fiber glass for commercial purposes is examined.

  5. Containerless Manufacture of Glass Optical Fibers

    NASA Technical Reports Server (NTRS)

    Naumann, R. J.; Ethridge, E. C.

    1985-01-01

    Contamination and crystallization reduced in proposed process. Solid optical fiber drawn from an acoustically levitated lump of molten glass. New material added in solid form, melted and then moved into main body of molten glass. Single axis acoustic levitation furnances levitate glass melts at temperature up to about 700 degrees C. Processing in unit limited to low-melting temperature glasses.

  6. Taylor impact of glass bars

    NASA Astrophysics Data System (ADS)

    Murray, Natalie; Bourne, Neil; Field, John

    1997-07-01

    Brar and Bless pioneeered the use of plate impact upon bars as a technique for investigating the 1D stress loading of glass. We wish to extend this technique by applying VISAR and embedded stress gauge measurements to a symmetrical version of the test. In this configuration two rods impact one upon the other in a symmetrical version of the Taylor test geometry in which the impact is perfectly rigid in the centre of mass frame. Previous work in the laboratory has characterised the three glass types (float, borosilicate and a high density lead glass). These experiments will identify the 1D stress failure mechanisms from high-speed photography and the stress and particle velocity histories will be interpreted in the light of these results. The differences in response of the three glasses will be highlighted.

  7. 2012 Problem 13: Misty Glass

    NASA Astrophysics Data System (ADS)

    Huang, Shan; Li, Xiao; Gao, Wenli; Zhou, Huijun

    2015-10-01

    Based on diffraction theory, we propose a model to explain the formation of colorful rings created by a misty glass. The model is verified by examining the relation between the size of the ring and size of the droplets.

  8. Inorganic glass ceramic slip rings

    NASA Technical Reports Server (NTRS)

    Glossbrenner, E. W.; Cole, S. R.

    1972-01-01

    Prototypes of slip rings have been fabricated from ceramic glass, a material which is highly resistant to deterioration due to high temperature. Slip ring assemblies were not structurally damaged by mechanical tests and performed statisfactorily for 200 hours.

  9. Ion implantation in silicate glasses

    SciTech Connect

    Arnold, G.W.

    1993-12-01

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

  10. High Tech Art: Chameleon Glass

    NASA Technical Reports Server (NTRS)

    1993-01-01

    Dichroic Glass is a technology wherein extremely thin films of metal are vacuum deposited on a glass surface. The coated glass shields spacecraft instruments from cosmic radiation and protects human vision from unfiltered sunlight in space. Because the coating process allows some wavelengths of light and color to reflect and others to pass through, a chameleon effect is produced. Murray Schwartz, a former aerospace engineer, has based his business KROMA on this NASA optical technology. He produces dichroic stained glass windows, mobiles and jewelry. The technique involves deposition of super thin layers of metal oxides applied one layer at a time in a specific order and thickness for the desired effect. His product line is unique and has been very successful.

  11. Porous glasses for optical sensors

    NASA Astrophysics Data System (ADS)

    Dorosz, Dominik; Procyk, Bernadeta

    2006-03-01

    Microporous glasses from the Na II0-B II0 3-Si0 II system can be obtained by appropriate thermal and chemical treatment. During the thermal treatment the separation of the borate phase from the silicon skeleton has been occurred. The borates are in the form small drops joined to each other. In the course of chemical treatment the borates become leached in water, water solutions of acids or basis and the glass becomes porous. Microporous glasses may find application in many branches of science and engineering. The applications depend on the internal arrangement, size and shape of pores. These parameters may be in a wide range modified by a change of the chemical composition. The received porous glass was used as an element in optical fibre NO II sensor. The specific coloration reaction between organic reagents and NO II in the pores was occurred. It is possible to detection of 10-50 ppm NO II level.

  12. Fast Crystals and Strong Glasses

    SciTech Connect

    Weitz, David

    2009-11-04

    This talk describes new results on model colloid systems that provide insight into the behavior of fundamental problems in colloid physics, and more generally, for other materials as well. By visualizing the nucleation and growth of colloid crystals, we find that the incipient crystallites are much more disordered than expected, leading to a larger diversity of crystal morphologies. When the entropic contribution of these diverse morphologies is included in the free energy, we are able to describe the behavior very well, and can predict the nucleation rate surprisingly accurately. The talk also describes the glass transition in deformable colloidal particles, and will show that when the internal elasticity of the particles is included, the colloidal glass transition mimics that of molecular glass formers much more completely. These results also suggest that the elasticity at the scale of the fundamental unit, either colloid particle or molecule, determines the nature of the glass transition, as described by the "fragility."

  13. Dispersion of barium gallogermanate glass.

    PubMed

    Zelmon, David E; Bayya, Shyam S; Sanghera, Jasbinder S; Aggarwal, Ishwar D

    2002-03-01

    Gallogermanate glasses are the subject of intense study as a result of their unique combination of physical and optical properties, including transmission from 0.4 to beyond 5.0 microm. These glasses can be easily made into large optics with high-index homogeneity for numerous U.S. Department of Defense and commercial visible-IR window applications such as reconnaissance, missile domes, IR countermeasures, avionics, and collision avoidance on automobiles. These applications require a knowledge of the refractive index of glass throughout the region of transmission. Consequently, we have measured the refractive index of BaO-Ga2O3-GeO2 glass from 0.4 to 5.0 microm and calculated the Sellmeier coefficients required for optical device design. PMID:11900015

  14. Glass Furnace Model Version 2

    Energy Science and Technology Software Center (ESTSC)

    2003-05-06

    GFM2.0 is a derivative of the GFM code with substantially altered and enhanced capabilities. Like its predecessor, it is a fully three-dimensional, furnace simulation model that provides a more accurate representation of the entire furnace, and specifically, the glass melting process, by coupling the combustion space directly to the glass batch and glass melt via rigorous radiation heat transport models for both the combustion space and the glass melt. No assumptions are made with regardmore » to interfacial parameters of heat, flux, temperature distribution, and batch coverage as must be done using other applicable codes available. These critical parameters are calculated. GFM2.0 contains a processor structured to facilitate use of the code, including the entry of teh furnace geometry and operating conditions, the execution of the program, and display of the computational results. Furnace simulations can therefore be created in a straightforward manner.« less

  15. Fiber glass pulling. [in space

    NASA Technical Reports Server (NTRS)

    Workman, Gary L.

    1987-01-01

    Experiments were conducted to determine the viability of performing containerless glass fiber pulling in space. The optical transmission properties and glass-forming capabilities of the heavy metal fluorides are reviewed and the acoustic characteristics required for a molten glass levitation system are examined. The design limitations of, and necessary modifications to the acoustic levitation furnace used in the experiments are discussed in detail. Acoustic levitator force measurements were performed and a thermal map of the furnace was generated from thermocouple data. It was determined that the thermal capability of the furnace was inadequate to melt a glass sample in the center. The substitution of a 10 KW carbon monoxide laser for the original furnace heating elements resulted in improved melt heating.

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

    SciTech Connect

    Epstein, S.; Stolper, E.

    1992-03-01

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

  17. Product consistency testing of three reference glasses in stainless steel and perfluoroalkoxy resin vessels

    SciTech Connect

    Olson, K.M.; Smith, G.L.; Marschman, S.C.

    1995-03-01

    Because of their chemical durability, silicate glasses have been proposed and researched since the mid-1950s as a medium for incorporating high-level radioactive waste (HLW) generated from processing of nuclear materials. A number of different waste forms were evaluated and ranked in the early 1980s; durability (leach resistance) was the highest weighted factor. Borosilicate glass was rated the best waste form available for incorporation of HLW. Four different types of vessels and three different glasses were used to study the possible effect of vessel composition on durability test results from the Production Consistency Test (PCT). The vessels were 45-m 304 stainless steel vessels, 150-m 304 L stainless steel vessels, and 60-m perfluoroalkoxy (PFA) fluoropolymer resin vessels. The three glasses were the Environmental Assessment glass manufactured by Corning Incorporated and supplied by Westinghouse Savannah River company, and West Valley Nuclear Services reference glasses 5 and 6, manufactured and supplied by Catholic University of America. Within experimental error, no differences were found in durability test results using the 3 different glasses in the 304L stainless steel or PFA fluoropolymer resin vessels over the seven-day test period.

  18. Metallic Glass Cooling

    NASA Technical Reports Server (NTRS)

    2003-01-01

    A sample of advanced metallic glass alloy cools down during an experiment with the TEMPUS furnace on STS-94, July 7, 1997, MET:5/23:35 (approximate). The sequence shows the sample glowing, then fading to black as scientists began the process of preserving the liquid state, but lowering the temperature below the normal solidification temperature of the alloy. This process is known as undercooling. (10 second clip covering approximately 50 seconds.) TEMPUS (stands for Tiegelfreies Elektromagnetisches Prozessiere unter Schwerelosigkeit (containerless electromagnetic processing under weightlessness). It was developed by the German Space Agency (DARA) for flight aboard Spacelab. The DARA project scientist was Igon Egry. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1R mission (STS-94, July 1-17 1997). DARA and NASA are exploring the possibility of flying an advanced version of TEMPUS on the International Space Station. (354KB JPEG, 2700 x 2038 pixels; downlinked video, higher quality not available) The MPG from which this composite was made is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300189.html.

  19. Tailoring Silicon Oxycarbide Glasses for Oxidative Stability

    NASA Technical Reports Server (NTRS)

    Hurwitz, F. I.; Meador, M. A. B.

    1997-01-01

    Blackglas(Trademark) polysiloxane systems produce silicon oxycarbide glasses by pyrolysis in inert atmosphere. The silicon oxycarbides evidence oxidative degradation that limits their lifetime as composite matrices. The present study characterizes bonding rearrangements in the oxycarbide network accompanying increases in pyrolysis temperature. It also addresses the changes in susceptibility to oxidation due to variations in the distribution of Si bonded species obtained under different processing conditions. The study is carried out using Si-29 nuclear magnetic resonance (NMR) spectroscopy and a design of experiments approach to model the oxidation behavior. The NMR results are compared with those obtained by thermogravimetric analysis (TGA). Samples pyrolyzed under inert conditions are compared to those pyrolyzed in reactive ammonia environments.

  20. Luminescence of powdered uranium glasses

    NASA Technical Reports Server (NTRS)

    Eubanks, A. G.; Mcgarrity, J. M.; Silverman, J.

    1974-01-01

    Measurement of cathodoluminescence and photoluminescence efficiencies in powdered borosilicate glasses having different particle size and different uranium content. Excitation with 100 to 350 keV electrons and with 253.7 nm light was found to produce identical absolute radiant exitance spectra in powdered samples. The most efficient glass was one containing 29.4 wt% B2O3, 58.8 wt% SiO2, 9.8 wt% Na2O and 2.0 wt% UO2.