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Sample records for glass-forming aqueous mixtures

  1. Microscopic Theory of Coupled Slow Activated Dynamics in Glass-Forming Binary Mixtures.

    Science.gov (United States)

    Zhang, Rui; Schweizer, Kenneth S

    2018-04-05

    The Elastically Collective Nonlinear Langevin Equation theory for one-component viscous liquids and suspensions is generalized to treat coupled slow activated relaxation and diffusion in glass-forming binary sphere mixtures of any composition, size ratio, and interparticle interactions. A trajectory-level dynamical coupling parameter concept is introduced to construct two coupled dynamic free energy functions for the smaller penetrant and larger matrix particle. A two-step dynamical picture is proposed where the first-step process involves matrix-facilitated penetrant hopping quantified in a self-consistent manner based on a temporal coincidence condition. After penetrants dynamically equilibrate, the effectively one-component matrix particle dynamics is controlled by a new dynamic free energy (second-step process). Depending on the time scales associated with the first- and second-step processes, as well as the extent of matrix-correlated facilitation, distinct physical scenarios are predicted. The theory is implemented for purely hard-core interactions, and addresses the glass transition based on variable kinetic criteria, penetrant-matrix coupled activated relaxation, self-diffusion of both species, dynamic fragility, and shear elasticity. Testable predictions are made. Motivated by the analytic ultralocal limit idea derived for pure hard sphere fluids, we identify structure-thermodynamics-dynamics relationships. As a case study for molecule-polymer thermal mixtures, the chemically matched fully miscible polystyrene-toluene system is quantitatively studied based on a predictive mapping scheme. The resulting no-adjustable-parameter results for toluene diffusivity and the mixture glass transition temperature are in good agreement with experiment. The theory provides a foundation to treat diverse dynamical problems in glass-forming mixtures, including suspensions of colloids and nanoparticles, polymer-molecule liquids, and polymer nanocomposites.

  2. Crystal phases of a glass-forming Lennard-Jones mixture

    International Nuclear Information System (INIS)

    Fernandez, Julian R.; Harrowell, Peter

    2003-01-01

    We compare the potential energy at zero temperature of a range of crystal structures for a glass-forming binary mixture of Lennard-Jones particles. The lowest-energy ordered state consists of coexisting phases of a single component face centered cubic structure and an equimolar cesium chloride structure. An infinite number of layered crystal structures are identified with energies close to this ground state. We demonstrate that the finite size increase of the energy of the coexisting crystal with incoherent interfaces is sufficient to destabilize this ordered phase in simulations of typical size. Two specific local coordination structures are identified as of possible structural significance in the amorphous state. We observe rapid crystal growth in the equimolar mixture

  3. Do atmospheric aerosols form glasses?

    Directory of Open Access Journals (Sweden)

    D. A. Pedernera

    2008-09-01

    Full Text Available A new process is presented by which water soluble organics might influence ice nucleation, ice growth, chemical reactions and water uptake of aerosols in the upper troposphere: the formation of glassy aerosol particles. Glasses are disordered amorphous (non-crystalline solids that form when a liquid is cooled without crystallization until the viscosity increases exponentially and molecular diffusion practically ceases. The glass transition temperatures, Tg, homogeneous ice nucleation temperatures, Thom, and ice melting temperatures, Tm, of various aqueous inorganic, organic and multi-component solutions are investigated with a differential scanning calorimeter. The investigated solutes are: various polyols, glucose, raffinose, levoglucosan, an aromatic compound, sulfuric acid, ammonium bisulfate and mixtures of dicarboxylic acids (M5, of dicarboxylic acids and ammonium sulfate (M5AS, of two polyols, of glucose and ammonium nitrate, and of raffinose and M5AS. The results indicate that aqueous solutions of the investigated inorganic solutes show Tg values that are too low to be of atmospheric importance. In contrast, aqueous organic and multi-component solutions readily form glasses at low but atmospherically relevant temperatures (≤230 K. To apply the laboratory data to the atmospheric situation, the measured phase transition temperatures were transformed from a concentration to a water activity scale by extrapolating water activities determined between 252 K and 313 K to lower temperatures. The obtained state diagrams reveal that the higher the molar mass of the aqueous organic or multi-component solutes, the higher Tg of their respective solutions at a given water activity. To a lesser extent, Tg also depends on the hydrophilicity of the organic solutes. Therefore, aerosol particles containing larger (≳150 g mol−1 and

  4. Glass Transition Temperature of Saccharide Aqueous Solutions Estimated with the Free Volume/Percolation Model.

    Science.gov (United States)

    Constantin, Julian Gelman; Schneider, Matthias; Corti, Horacio R

    2016-06-09

    The glass transition temperature of trehalose, sucrose, glucose, and fructose aqueous solutions has been predicted as a function of the water content by using the free volume/percolation model (FVPM). This model only requires the molar volume of water in the liquid and supercooled regimes, the molar volumes of the hypothetical pure liquid sugars at temperatures below their pure glass transition temperatures, and the molar volumes of the mixtures at the glass transition temperature. The model is simplified by assuming that the excess thermal expansion coefficient is negligible for saccharide-water mixtures, and this ideal FVPM becomes identical to the Gordon-Taylor model. It was found that the behavior of the water molar volume in trehalose-water mixtures at low temperatures can be obtained by assuming that the FVPM holds for this mixture. The temperature dependence of the water molar volume in the supercooled region of interest seems to be compatible with the recent hypothesis on the existence of two structure of liquid water, being the high density liquid water the state of water in the sugar solutions. The idealized FVPM describes the measured glass transition temperature of sucrose, glucose, and fructose aqueous solutions, with much better accuracy than both the Gordon-Taylor model based on an empirical kGT constant dependent on the saccharide glass transition temperature and the Couchman-Karasz model using experimental heat capacity changes of the components at the glass transition temperature. Thus, FVPM seems to be an excellent tool to predict the glass transition temperature of other aqueous saccharides and polyols solutions by resorting to volumetric information easily available.

  5. Development of iodine waste forms using low-temperature sintering glass

    International Nuclear Information System (INIS)

    Krumhansl, James Lee; Nenoff, Tina Maria; Garino, Terry J.; Rademacher, David

    2010-01-01

    This presentation will describe our recent work on the use of low temperature-sintering glass powders mixed with either AgI or AgI-zeolite to produce a stable waste form. Radioactive iodine ( 129 I, half-life of 1.6 x 10 7 years) is generated in the nuclear fuel cycle and is of particular concern due to its extremely long half-life and its effects on human health. As part of the DOE/NE Advanced Fuel Cycle Initiative (AFCI), the separation of 129 I from spent fuel during fuel reprocessing is being studied. In the spent fuel reprocessing scheme under consideration, the iodine is released in gaseous form and collected using Ag-loaded zeolites, to form AgI. Although AgI has extremely low solubility in water, it has a relatively high vapor pressure at moderate temperatures (>550 C), thus limiting the thermal processing. Because of this, immobilization using borosilicate glass is not feasible. Therefore, a bismuth oxide-based glasses are being studied due to the low solubility of bismuth oxide in aqueous solution at pH > 7. These waste forms were processed at 500 C, where AgI volatility is low but the glass powder is able to first densify by viscous sintering and then crystallize. Since the glass is not melted, a more chemically stable glass can be used. The AgI-glass mixture was found to have high iodine leach resistance in these initial studies.

  6. Dynamic and thermodynamic characteristics associated with the glass transition of amorphous trehalose-water mixtures.

    Science.gov (United States)

    Weng, Lindong; Elliott, Gloria D

    2014-06-21

    The glass transition temperature Tg of biopreservative formulations is important for predicting the long-term storage of biological specimens. As a complementary tool to thermal analysis techniques, which are the mainstay for determining Tg, molecular dynamics simulations have been successfully applied to predict the Tg of several protectants and their mixtures with water. These molecular analyses, however, rarely focused on the glass transition behavior of aqueous trehalose solutions, a subject that has attracted wide scientific attention via experimental approaches. Important behavior, such as hydrogen-bonding dynamics and self-aggregation has yet to be explored in detail, particularly below, or in the vicinity of, Tg. Using molecular dynamics simulations of several dynamic and thermodynamic properties, this study reproduced the supplemented phase diagram of trehalose-water mixtures (i.e., Tg as a function of the solution composition) based on experimental data. The structure and dynamics of the hydrogen-bonding network in the trehalose-water systems were also analyzed. The hydrogen-bonding lifetime was determined to be an order of magnitude higher in the glassy state than in the liquid state, while the constitution of the hydrogen-bonding network exhibited no noticeable change through the glass transition. It was also found that trehalose molecules preferred to form small, scattered clusters above Tg, but self-aggregation was substantially increased below Tg. The average cluster size in the glassy state was observed to be dependent on the trehalose concentration. Our findings provided insights into the glass transition characteristics of aqueous trehalose solutions as they relate to biopreservation.

  7. Experimental evidence for excess entropy discontinuities in glass-forming solutions.

    Science.gov (United States)

    Lienhard, Daniel M; Zobrist, Bernhard; Zuend, Andreas; Krieger, Ulrich K; Peter, Thomas

    2012-02-21

    Glass transition temperatures T(g) are investigated in aqueous binary and multi-component solutions consisting of citric acid, calcium nitrate (Ca(NO(3))(2)), malonic acid, raffinose, and ammonium bisulfate (NH(4)HSO(4)) using a differential scanning calorimeter. Based on measured glass transition temperatures of binary aqueous mixtures and fitted binary coefficients, the T(g) of multi-component systems can be predicted using mixing rules. However, the experimentally observed T(g) in multi-component solutions show considerable deviations from two theoretical approaches considered. The deviations from these predictions are explained in terms of the molar excess mixing entropy difference between the supercooled liquid and glassy state at T(g). The multi-component mixtures involve contributions to these excess mixing entropies that the mixing rules do not take into account. © 2012 American Institute of Physics

  8. The Monte Carlo dynamics of a binary Lennard-Jones glass-forming mixture

    International Nuclear Information System (INIS)

    Berthier, L; Kob, W

    2007-01-01

    We use a standard Monte Carlo algorithm to study the slow dynamics of a binary Lennard-Jones glass-forming mixture at low temperature. We find that the Monte Carlo approach is by far the most efficient way to simulate a stochastic dynamics since the relaxation is about 10 times faster than in Brownian dynamics and about 30 times faster than in stochastic dynamics. Moreover, the average dynamical behaviour of the system is in quantitative agreement with that obtained using Newtonian dynamics, apart from at very short times where thermal vibrations are suppressed. We show, however, that dynamic fluctuations quantified by four-point dynamic susceptibilities do retain a dependence on the microscopic dynamics, as recently predicted theoretically

  9. Aqueous solutions/nuclear glasses interactions

    International Nuclear Information System (INIS)

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

    1991-01-01

    Interactions results of the borosilicate glass used in radioactive wastes confinement and aqueous solutions at various temperature and PH show that for the glass components: - the release rate evolution follows an Arrhenius law, - in acid PH, there is a selective dissolution, - in basic PH, there is a stoechiometric dissolution [fr

  10. Glass-ceramic from mixtures of bottom ash and fly ash.

    Science.gov (United States)

    Vu, Dinh Hieu; Wang, Kuen-Sheng; Chen, Jung-Hsing; Nam, Bui Xuan; Bac, Bui Hoang

    2012-12-01

    Along with the gradually increasing yield of the residues, appropriate management and treatment of the residues have become an urgent environmental protection problem. This work investigated the preparation of a glass-ceramic from a mixture of bottom ash and fly ash by petrurgic method. The nucleation and crystallization kinetics of the new glass-ceramic can be obtained by melting the mixture of 80% bottom ash and 20% fly ash at 950 °C, which was then cooled in the furnace for 1h. Major minerals forming in the glass-ceramics mainly are gehlenite (Ca(2)Al(2)SiO(7)) & akermanite (Ca(2)MgSiO(7)) and wollastonite (CaSiO(3)). In addition, regarding chemical/mechanical properties, the chemical resistance showing durability, and the leaching concentration of heavy metals confirmed the possibility of engineering and construction applications of the most superior glass-ceramic product. Finally, petrurgic method of a mixture of bottom ash and fly ash at 950 °C represents a simple, inexpensive, and energy saving method compared with the conventional heat treatment. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. Catanionic mixtures forming gemini-like amphiphiles.

    Science.gov (United States)

    Sakai, Hideki; Okabe, Yuji; Tsuchiya, Koji; Sakai, Kenichi; Abe, Masahiko

    2011-01-01

    The properties of aqueous mixtures of cationic species with alkyl dicarboxylic acid compounds have been studied. The cationic compounds used in this study were tertiary amine-type N-methyl-N-(2,3-dioxypropyl)hexadecylamine (C16amine) and quaternary ammonium-type N,N-dimethyl-N-(2,3-dioxypropyl)hexadecylammonium chloride (C16Q). The alkyl dicarboxylic acid compounds used were HOOC(CH(2))(10)COOH (C12H) and its sodium salt (C12Na). Three aqueous mixtures were examined in this study: (System I) C16amine + C12H, (System II) C16Q + C12Na, and (System III) C16Q + C12H. The solution pH was set at 12 for System III. The combination of (1)H-NMR and mass spectroscopy data has suggested that a stoichiometric complex is formed in the aqueous solutions at a mole fraction of C12H (or C12Na) = 0.33. Here, the C12H (or C12Na) molecule added to the system bridges two cationic molecules, like a spacer of gemini surfactants. In fact, the static surface tensiometry has demonstrated that the stoichiometric complex behaves as gemini-like amphiphiles in aqueous solutions. Our current study offers a possible way for easily preparing gemini surfactant systems.

  12. Aqueous corrosion of borosilicate glasses. Nature and properties of alteration layers

    International Nuclear Information System (INIS)

    Trotignon, Laurent

    1990-01-01

    This research thesis addresses physical and chemical processes which occur during aqueous corrosion of silicates, and the study of the properties of their interfaces with solutions, and thus issues related to the fate of high activity nuclear wastes which are embedded in a vitreous matrix as the potential release of radionuclides towards the environment then depends on the glass parcel behaviour submitted to chemical attacks which could alter it, notably by aqueous corrosion. The objective is then to model the dissolution of nuclear glass over long periods of time, and to predict the behaviour of radionuclides. The author compared the corrosion and alteration layers of gradually more complex borosilicate glasses, from a ternary sodium borosilicate glass to a simulated nuclear glass (the French reference glass R7T7). Complexity is increased by adding oxides. After some theoretical recalls on the structure and corrosion of borosilicate glasses, the author presents the studied materials, the corrosion experiments, and analytical techniques used to study alteration layers. The mechanism of formation of altered layers is studied based on corrosion experiments performed at 90 C on the whole set of glasses. Alteration layers formed on corroded glasses are studied and compared by using various techniques: electronic microscopy, high energy ion beams, spectroscopy, infrared, photo-electron spectroscopy. Implications for underground storage of nuclear glasses are discussed

  13. High density liquid structure enhancement in glass forming aqueous solution of LiCl

    Science.gov (United States)

    Camisasca, G.; De Marzio, M.; Rovere, M.; Gallo, P.

    2018-06-01

    We investigate using molecular dynamics simulations the dynamical and structural properties of LiCl:6H2O aqueous solution upon supercooling. This ionic solution is a glass forming liquid of relevant interest in connection with the study of the anomalies of supercooled water. The LiCl:6H2O solution is easily supercooled and the liquid state can be maintained over a large decreasing temperature range. We performed simulations from ambient to 200 K in order to investigate how the presence of the salt modifies the behavior of supercooled water. The study of the relaxation time of the self-density correlation function shows that the system follows the prediction of the mode coupling theory and behaves like a fragile liquid in all the range explored. The analysis of the changes in the water structure induced by the salt shows that while the salt preserves the water hydrogen bonds in the system, it strongly affects the tetrahedral hydrogen bond network. Following the interpretation of the anomalies of water in terms of a two-state model, the modifications of the oxygen radial distribution function and the angular distribution function of the hydrogen bonds in water indicate that LiCl has the role of enhancing the high density liquid component of water with respect to the low density component. This is in agreement with recent experiments on aqueous ionic solutions.

  14. Low melting high lithia glass compositions and methods

    Science.gov (United States)

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

    2000-01-01

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

  15. Analysis of Influence of Foaming Mixture Components on Structure and Properties of Foam Glass

    Science.gov (United States)

    Karandashova, N. S.; Goltsman, B. M.; Yatsenko, E. A.

    2017-11-01

    It is recommended to use high-quality thermal insulation materials to increase the energy efficiency of buildings. One of the best thermal insulation materials is foam glass - durable, porous material that is resistant to almost any effect of substance. Glass foaming is a complex process depending on the foaming mode and the initial mixture composition. This paper discusses the influence of all components of the mixture - glass powder, foaming agent, enveloping material and water - on the foam glass structure. It was determined that glass powder is the basis of the future material. A foaming agent forms a gas phase in the process of thermal decomposition. This aforementioned gas foams the viscous glass mass. The unreacted residue thus changes a colour of the material. The enveloping agent slows the foaming agent decomposition preventing its premature burning out and, in addition, helps to accelerate the sintering of glass particles. The introduction of water reduces the viscosity of the foaming mixture making it evenly distributed and also promotes the formation of water gas that additionally foams the glass mass. The optimal composition for producing the foam glass with the density of 150 kg/m3 is defined according to the results of the research.

  16. Talc-silicon glass-ceramic waste forms for immobilization of high- level calcined waste

    International Nuclear Information System (INIS)

    Vinjamuri, K.

    1993-06-01

    Talc-silicon glass-ceramic waste forms are being evaluated as candidates for immobilization of the high level calcined waste stored onsite at the Idaho Chemical Processing Plant. These glass-ceramic waste forms were prepared by hot isostatically pressing a mixture of simulated nonradioactive high level calcined waste, talc, silicon and aluminum metal additives. The waste forms were characterized for density, chemical durability, and glass and crystalline phase compositions. The results indicate improved density and chemical durability as the silicon content is increased

  17. Comparison of the corrosion behaviors of the glass-bonded sodalite ceramic waste form and reference HLW glasses

    International Nuclear Information System (INIS)

    Ebert, W. L.; Lewis, M. A.

    1999-01-01

    A glass-bonded sodalite ceramic waste form is being developed for the long-term immobilization of salt wastes that are generated during spent nuclear fuel conditioning activities. A durable waste form is prepared by hot isostatic pressing (HIP) a mixture of salt-loaded zeolite powders and glass frit. A mechanistic description of the corrosion processes is being developed to support qualification of the CWF for disposal. The initial set of characterization tests included two standard tests that have been used extensively to study the corrosion behavior of high level waste (HLW) glasses: the Material Characterization Center-1 (MCC-1) Test and the Product Consistency Test (PCT). Direct comparison of the results of tests with the reference CWF and HLW glasses indicate that the corrosion behaviors of the CWF and HLW glasses are very similar

  18. Glass transition behavior of octyl β-D-glucoside and octyl β-D-thioglucoside/water binary mixtures.

    Science.gov (United States)

    Ogawa, Shigesaburo; Asakura, Kouichi; Osanai, Shuichi

    2010-11-22

    The lyotropic behavior and glass-forming properties of octyl β-D-glucoside (C8Glu) and octyl β-D-thioglucoside (C8SGlu)/water binary mixtures were evaluated using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The results clearly indicate that the mixture forms a glass in the supercooling state of liquid crystalline phases such as cubic, lamellar, and smectic. The glass transition temperature (T(g)) of the mixture was strongly dependent on solute concentration, with a higher concentration correlating with a higher T(g). The experimental T(g) was consistent with the predicted value calculated using the Couchman-Karasz equation in both the C8Glu and C8SGlu/water mixtures. The change of heat capacity at T(g) showed the two bending points under variation of concentrations. And the highest temperature of phase transition from lamellar to isotropic solution was observed at around 50% molar concentration. It was expected that non-percolated state of water existed in extremely higher concentration ranges. Copyright © 2010 Elsevier Ltd. All rights reserved.

  19. Methods of vitrifying waste with low melting high lithia glass compositions

    Science.gov (United States)

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

    2001-01-01

    The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.

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

    Science.gov (United States)

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

    2010-01-01

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

  1. Glass polymorphism in glycerol-water mixtures: I. A computer simulation study.

    Science.gov (United States)

    Jahn, David A; Wong, Jessina; Bachler, Johannes; Loerting, Thomas; Giovambattista, Nicolas

    2016-04-28

    We perform out-of-equilibrium molecular dynamics (MD) simulations of water-glycerol mixtures in the glass state. Specifically, we study the transformations between low-density (LDA) and high-density amorphous (HDA) forms of these mixtures induced by compression/decompression at constant temperature. Our MD simulations reproduce qualitatively the density changes observed in experiments. Specifically, the LDA-HDA transformation becomes (i) smoother and (ii) the hysteresis in a compression/decompression cycle decreases as T and/or glycerol content increase. This is surprising given the fast compression/decompression rates (relative to experiments) accessible in MD simulations. We study mixtures with glycerol molar concentration χ(g) = 0-13% and find that, for the present mixture models and rates, the LDA-HDA transformation is detectable up to χ(g) ≈ 5%. As the concentration increases, the density of the starting glass (i.e., LDA at approximately χ(g) ≤ 5%) rapidly increases while, instead, the density of HDA remains practically constant. Accordingly, the LDA state and hence glass polymorphism become inaccessible for glassy mixtures with approximately χ(g) > 5%. We present an analysis of the molecular-level changes underlying the LDA-HDA transformation. As observed in pure glassy water, during the LDA-to-HDA transformation, water molecules within the mixture approach each other, moving from the second to the first hydration shell and filling the first interstitial shell of water molecules. Interestingly, similar changes also occur around glycerol OH groups. It follows that glycerol OH groups contribute to the density increase during the LDA-HDA transformation. An analysis of the hydrogen bond (HB)-network of the mixtures shows that the LDA-HDA transformation is accompanied by minor changes in the number of HBs of water and glycerol. Instead, large changes in glycerol and water coordination numbers occur. We also perform a detailed analysis of the effects that

  2. Copper oxide content dependence of crystallization behavior, glass forming ability, glass stability and fragility of lithium borate glasses

    International Nuclear Information System (INIS)

    Soliman, A.A.; Kashif, I.

    2010-01-01

    Differential thermal analysis (DTA) and X-ray diffraction (XRD) have been employed to investigate the copper oxide content dependence of the glass transition temperatures data, activation energy for the glass transition E t , glass stability GS, fragility index Fi, the glass-forming ability (GFA) and crystallization behavior of {(100-x) mol% Li 2 B 4 O 7 -x mol% CuO} glass samples, where x=0-40 mol% CuO. From the dependence of the glass transition temperature T g on the heating rate β, the fragility, F i , and the activation energy, E t , have been calculated. It is seen that F i and E t are attained their minimum values at 0 x -T g , SCL region and the GS. The GFA has been investigated on the basis of Hruby parameter K H , which is a strong indicator of GFA, and the relaxation time. Results of GFA are in good agreement with the fragility index, F i , calculations indicating that {90Li 2 B 4 O 7 .10CuO} is the best glass former. The stronger glass forming ability has decreasing the fragility index. XRD result indicates that no fully amorphous samples but a mixture of crystalline and amorphous phases are formed in the samples containing x>25 mol% CuO and below it composed of glassy phase. Increasing the CuO content above 25 mol% helps the crystallization process, and thus promotes a distinct SCL region. XRD suggests the presence of micro-crystallites of remaining residual amorphous matrix by increasing the CuO content.

  3. Radiation effects in glass and glass-ceramic waste forms for the immobilization of CANDU UO2 fuel reprocessing waste

    International Nuclear Information System (INIS)

    Tait, J.C.

    1993-05-01

    AECL has investigated three waste forms for the immobilization of high-level liquid wastes that would arise if used CANDU fuels were reprocessed at some time in the future to remove fissile materials for the fabrication of new power reactor fuel. These waste forms are borosilicate glasses, aluminosilicate glasses and titanosilicate glass-ceramics. This report discusses the potential effects of alpha, beta and gamma radiation on the releases of radionuclides from these waste forms as a result of aqueous corrosion by groundwaters that would be present in an underground waste disposal vault. The report discusses solid-state damage caused by radiation-induced atomic displacements in the waste forms as well as irradiation of groundwater solutions (radiolysis), and their potential effects on waste-form corrosion and radionuclide release. The current literature on radiation effects on borosilicate glasses and in ceramics is briefly reviewed, as are potential radiation effects on specialized waste forms for the immobilization of 129 I, 85 Kr and 14 C. (author). 104 refs., 9 tabs., 5 figs

  4. Glycine phases formed from frozen aqueous solutions: Revisited

    Energy Technology Data Exchange (ETDEWEB)

    Surovtsev, N. V. [Institute of Automation and Electrometry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Adichtchev, S. V.; Malinovsky, V. K. [Institute of Automation and Electrometry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Ogienko, A. G.; Manakov, A. Yu. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Drebushchak, V. A. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Institute of Geology and Mineralogy, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Ancharov, A. I.; Boldyreva, E. V. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Institute of Solid Chemistry and Mechanochemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Yunoshev, A. S. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Lavrentiev Institute of Hydrodynamics, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation)

    2012-08-14

    Glycine phases formed when aqueous solutions were frozen and subsequently heated under different conditions were studied by Raman scattering, x-ray diffraction, and differential scanning calorimetry (DSC) techniques. Crystallization of ice I{sub h} was observed in all the cases. On cooling at the rates of 0.5 K/min and 5 K/min, glassy glycine was formed as an intermediate phase which lived about 1 min or less only, and then transformed into {beta}-polymorph of glycine. Quench cooling of glycine solutions (15% w/w) in liquid nitrogen resulted in the formation of a mixture of crystalline water ice I{sub h} and a glassy glycine, which could be preserved at cryogenic temperatures (80 K) for an indefinitely long time. This mixture remained also quite stable for some time after heating above the cryogenic temperature. Subsequent heating under various conditions resulted in the transformation of the glycine glass into an unknown crystalline phase (glycine 'X-phase') at 209-216 K, which at 218-226 K transformed into {beta}-polymorph of glycine. The 'X-phase' was characterized by Raman spectroscopy; it could be obtained in noticeable amounts using a special preparation technique and tentatively characterized by x-ray powder diffraction (P2, a= 6.648 A, b= 25.867 A, c= 5.610 A, {beta}= 113.12 Masculine-Ordinal-Indicator ); the formation of 'X-phase' from the glycine glassy phase and its transformation into {beta}-polymorph were followed by DSC. Raman scattering technique with its power for unambiguous identification of the crystalline and glassy polymorphs without limitation on the crystallite size helped us to follow the phase transformations during quenching, heating, and annealing. The experimental findings are considered in relation to the problem of control of glycine polymorphism on crystallization.

  5. Glycine phases formed from frozen aqueous solutions: Revisited

    Science.gov (United States)

    Surovtsev, N. V.; Adichtchev, S. V.; Malinovsky, V. K.; Ogienko, A. G.; Drebushchak, V. A.; Manakov, A. Yu.; Ancharov, A. I.; Yunoshev, A. S.; Boldyreva, E. V.

    2012-08-01

    Glycine phases formed when aqueous solutions were frozen and subsequently heated under different conditions were studied by Raman scattering, x-ray diffraction, and differential scanning calorimetry (DSC) techniques. Crystallization of ice Ih was observed in all the cases. On cooling at the rates of 0.5 K/min and 5 K/min, glassy glycine was formed as an intermediate phase which lived about 1 min or less only, and then transformed into β-polymorph of glycine. Quench cooling of glycine solutions (15% w/w) in liquid nitrogen resulted in the formation of a mixture of crystalline water ice Ih and a glassy glycine, which could be preserved at cryogenic temperatures (80 K) for an indefinitely long time. This mixture remained also quite stable for some time after heating above the cryogenic temperature. Subsequent heating under various conditions resulted in the transformation of the glycine glass into an unknown crystalline phase (glycine "X-phase") at 209-216 K, which at 218-226 K transformed into β-polymorph of glycine. The "X-phase" was characterized by Raman spectroscopy; it could be obtained in noticeable amounts using a special preparation technique and tentatively characterized by x-ray powder diffraction (P2, a = 6.648 Å, b = 25.867 Å, c = 5.610 Å, β = 113.12°); the formation of "X-phase" from the glycine glassy phase and its transformation into β-polymorph were followed by DSC. Raman scattering technique with its power for unambiguous identification of the crystalline and glassy polymorphs without limitation on the crystallite size helped us to follow the phase transformations during quenching, heating, and annealing. The experimental findings are considered in relation to the problem of control of glycine polymorphism on crystallization.

  6. Radiation effects in glass and glass-ceramic waste forms for the immobilization of CANDU UO{sub 2} fuel reprocessing waste

    Energy Technology Data Exchange (ETDEWEB)

    Tait, J C

    1993-05-01

    AECL has investigated three waste forms for the immobilization of high-level liquid wastes that would arise if used CANDU fuels were reprocessed at some time in the future to remove fissile materials for the fabrication of new power reactor fuel. These waste forms are borosilicate glasses, aluminosilicate glasses and titanosilicate glass-ceramics. This report discusses the potential effects of alpha, beta and gamma radiation on the releases of radionuclides from these waste forms as a result of aqueous corrosion by groundwaters that would be present in an underground waste disposal vault. The report discusses solid-state damage caused by radiation-induced atomic displacements in the waste forms as well as irradiation of groundwater solutions (radiolysis), and their potential effects on waste-form corrosion and radionuclide release. The current literature on radiation effects on borosilicate glasses and in ceramics is briefly reviewed, as are potential radiation effects on specialized waste forms for the immobilization of {sup 129}I, {sup 85}Kr and {sup 14}C. (author). 104 refs., 9 tabs., 5 figs.

  7. Modelling aqueous corrosion of nuclear waste phosphate glass

    Energy Technology Data Exchange (ETDEWEB)

    Poluektov, Pavel P.; Schmidt, Olga V.; Kascheev, Vladimir A. [Bochvar All-Russian Scientific Research Institute for Inorganic Materials (VNIINM), Moscow (Russian Federation); Ojovan, Michael I., E-mail: m.ojovan@sheffield.ac.uk [Immobilisation Science Laboratory, Department of Materials Science and Engineering, University of Sheffield, Mappin Street, Sheffield, S1 3JD (United Kingdom)

    2017-02-15

    A model is presented on nuclear sodium alumina phosphate (NAP) glass aqueous corrosion accounting for dissolution of radioactive glass and formation of corrosion products surface layer on the glass contacting ground water of a disposal environment. Modelling is used to process available experimental data demonstrating the generic inhibiting role of corrosion products on the NAP glass surface. - Highlights: • The radionuclides yield is determined by the transport from the glass through the surface corrosion layer. • Formation of the surface layer is due to the dissolution of the glass network and the formation of insoluble compounds. • The model proposed accounts for glass dissolution, formation of corrosion layer, specie diffusion and chemical reactions. • Analytical solutions are found for corrosion layer growth rate and glass components component leaching rates.

  8. Glass polymorphism in glycerol–water mixtures: I. A computer simulation study

    Science.gov (United States)

    Jahn, David A.; Wong, Jessina; Bachler, Johannes; Loerting, Thomas

    2016-01-01

    We perform out-of-equilibrium molecular dynamics (MD) simulations of water–glycerol mixtures in the glass state. Specifically, we study the transformations between low-density (LDA) and high-density amorphous (HDA) forms of these mixtures induced by compression/decompression at constant temperature. Our MD simulations reproduce qualitatively the density changes observed in experiments. Specifically, the LDA–HDA transformation becomes (i) smoother and (ii) the hysteresis in a compression/decompression cycle decreases as T and/or glycerol content increase. This is surprising given the fast compression/decompression rates (relative to experiments) accessible in MD simulations. We study mixtures with glycerol molar concentration χ g = 0–13% and find that, for the present mixture models and rates, the LDA–HDA transformation is detectable up to χ g ≈ 5%. As the concentration increases, the density of the starting glass (i.e., LDA at approximately χ g ≤ 5%) rapidly increases while, instead, the density of HDA remains practically constant. Accordingly, the LDA state and hence glass polymorphism become inaccessible for glassy mixtures with approximately χ g > 5%. We present an analysis of the molecular-level changes underlying the LDA–HDA transformation. As observed in pure glassy water, during the LDA-to-HDA transformation, water molecules within the mixture approach each other, moving from the second to the first hydration shell and filling the first interstitial shell of water molecules. Interestingly, similar changes also occur around glycerol OH groups. It follows that glycerol OH groups contribute to the density increase during the LDA–HDA transformation. An analysis of the hydrogen bond (HB)-network of the mixtures shows that the LDA–HDA transformation is accompanied by minor changes in the number of HBs of water and glycerol. Instead, large changes in glycerol and water coordination numbers occur. We also perform a detailed analysis of the

  9. Aqueous corrosion of silicate glasses. Analogy between volcanic glasses and the French nuclear waste glass R7T7

    International Nuclear Information System (INIS)

    Goldschmidt, F.

    1991-01-01

    The behaviour of borosilicate glasses upon aqueous corrosion is controlled for long periods of time (>10,000 years) by processes which are not directly accessible by means of laboratory experiments. The analogical approach consists here to compare leaching performances between the french nuclear waste glass R7T7 and natural volcanic glasses, basaltic and rhyolitic ones. The three glasses were leached in the same conditions; open system, 90 deg C, initial pH of 9.7. Basaltic and R7T7 glasses having the same kinetic of dissolution, the basaltic glass was chosen as the best analogue. (author). refs., figs., tabs

  10. Interaction of cadmium and indium nitrate mixture with sodium tungstate in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Belousova, E E; Krivobok, V I; Gruba, A I [Donetskij Gosudarstvennyj Univ. (Ukrainian SSR)

    1982-01-01

    The interaction of the mixture of cadmium and indium nitrates with sodium tungstate in aqueous solution is studied using the methods of ''residual concentrations'', pH potentiometry and conductometry. Independent of the ratio of components in the initial solution a mixture of coprecipitated normal tungstates of cadmium and indium is formed in the system. Heat treatment of the precipitates at 800 deg C for 50 hrs with subsequent hardening results in the formation of solid solutions on the basis of normal cadmium and indium tungstates.

  11. Effect of geologic repository parameters on aqueous corrosion of nuclear glass

    International Nuclear Information System (INIS)

    Tovena, I.; Advocat, T.; Jollivet, P.; Godon, N.; Vernaz, E.

    1995-01-01

    Twenty alumino-borosilicate glass compositions containing simulated fission product oxides were defined using the experimentation plan methodology. Three additional glass compositions were also tested. Monolithic glass corrosion tests in a dilute aqueous medium at 90 deg C indicated the variation range for the initial corrosion rates. Significant but only qualitative correlations were established between the initial corrosion rate and the molar fraction of glass network forming oxides (SiO 2 + Al 2 O 3 ), and between the initial rate and the (Na 2 O + Li 2 O + B 2 O 3 ) / (SiO 2 + Al 2 O 3 ) molar ratio in the glass. The experimentation plan allowed a polynomial model to be defined relating the initial corrosion rate at 90 deg C to the oxide concentrations in the glass. Although the model is theoretically capable of predicting the corrosion rates, it does not always account for the actual data measured during other experiments; this discrepancy may be attributable either to the presence of other chemical elements (MgO) or to CaO concentrations differing from the fixed value adopted for the experimentation plan. Glass powder corrosion tests designed to simulate advanced corrosion reaction progress, account for the wide variations in the dissolved glass quantities, although no correlation exists with the glass chemical composition. (authors). 49 refs., 4 figs., 34 tabs

  12. Effect of geologic repository parameters on aqueous corrosion of nuclear glass

    Energy Technology Data Exchange (ETDEWEB)

    Tovena, I; Advocat, T; Jollivet, P; Godon, N; Vernaz, E

    1996-12-31

    Twenty alumino-borosilicate glass compositions containing simulated fission product oxides were defined using the experimentation plan methodology. Three additional glass compositions were also tested. Monolithic glass corrosion tests in a dilute aqueous medium at 90 deg C indicated the variation range for the initial corrosion rates. Significant but only qualitative correlations were established between the initial corrosion rate and the molar fraction of glass network forming oxides (SiO{sub 2} + Al{sub 2}O{sub 3}), and between the initial rate and the (Na{sub 2}O + Li{sub 2}O + B{sub 2}O{sub 3}) / (SiO{sub 2} + Al{sub 2}O{sub 3}) molar ratio in the glass. The experimentation plan allowed a polynomial model to be defined relating the initial corrosion rate at 90 deg C to the oxide concentrations in the glass. Although the model is theoretically capable of predicting the corrosion rates, it does not always account for the actual data measured during other experiments; this discrepancy may be attributable either to the presence of other chemical elements (MgO) or to CaO concentrations differing from the fixed value adopted for the experimentation plan. Glass powder corrosion tests designed to simulate advanced corrosion reaction progress, account for the wide variations in the dissolved glass quantities, although no correlation exists with the glass chemical composition. (authors). 49 refs., 4 figs., 34 tabs.

  13. Corrosion behaviors of a glass-bonded sodalite ceramic waste form and its constituents

    International Nuclear Information System (INIS)

    Lewis, M. A.; Ebert, W. L.; Morss, L.

    1999-01-01

    A ceramic waste form (CWF) of glass bonded sodalite is being developed as a waste form for the long-term immobilization of fission products and transuranic elements from the U.S. Department of Energy's activities on spent nuclear fuel conditioning. A durable waste form was prepared by hot isostatic pressing (HIP) a mixture of salt-loaded zeolite powders and glass frit. During HIP the zeolite is converted to sodalite, and the resultant CWF is been completed for durations of up to 182 days. Four dissolution modes were identified: dissolution of free salt, dissolution of the aluminosilicate matrix of sodalite and the accompanying dissolution of occluded salt, dissolution of the boroaluminosilicate matrix of the glass, and ion exchange. Synergies inherent to the CWF were identified by comparing the results of the tests with pure glass and sodalite with those of the composite CWF

  14. Characterization of glass and glass ceramic nuclear waste forms

    International Nuclear Information System (INIS)

    Lutze, W.; Borchardt, J.; De, A.K.

    1979-01-01

    Characteristics of solidified nuclear waste forms, glass and glass ceramic compositions and the properties (composition, thermal stability, crystallization, phase behavior, chemical stability, mechanical stability, and radiation effects) of glasses and glass ceramics are discussed. The preparation of glass ceramics may be an optional step for proposed vitrification plants if tailored glasses are used. Glass ceramics exhibit some improved properties with respect to glasses. The overall leach resistance is similar to that of glasses. An increased leach resistance may become effective for single radionuclides being hosted in highly insoluble crystal phases mainly when higher melting temperatures are applicable in order to get more leach resistant residual glass phases. The development of glass ceramic is going on. The technological feasibility is still to be demonstrated. The potential gain of stability when using glass ceramics qualifies the material as an alternative nuclear waste form

  15. The glass-forming ability of model metal-metalloid alloys

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai; Liu, Yanhui; Schroers, Jan [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Center for Research on Interface Structures and Phenomena, Yale University, New Haven, Connecticut 06520 (United States); Shattuck, Mark D. [Department of Physics and Benjamin Levich Institute, The City College of the City University of New York, New York, New York 10031 (United States); Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); O’Hern, Corey S. [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Center for Research on Interface Structures and Phenomena, Yale University, New Haven, Connecticut 06520 (United States); Department of Physics, Yale University, New Haven, Connecticut 06520 (United States); Department of Applied Physics, Yale University, New Haven, Connecticut 06520 (United States)

    2015-03-14

    Bulk metallic glasses (BMGs) are amorphous alloys with desirable mechanical properties and processing capabilities. To date, the design of new BMGs has largely employed empirical rules and trial-and-error experimental approaches. Ab initio computational methods are currently prohibitively slow to be practically used in searching the vast space of possible atomic combinations for bulk glass formers. Here, we perform molecular dynamics simulations of a coarse-grained, anisotropic potential, which mimics interatomic covalent bonding, to measure the critical cooling rates for metal-metalloid alloys as a function of the atomic size ratio σ{sub S}/σ{sub L} and number fraction x{sub S} of the metalloid species. We show that the regime in the space of σ{sub S}/σ{sub L} and x{sub S} where well-mixed, optimal glass formers occur for patchy and LJ particle mixtures, coincides with that for experimentally observed metal-metalloid glass formers. Thus, our simple computational model provides the capability to perform combinatorial searches to identify novel glass-forming alloys.

  16. A new correlation for nucleate pool boiling of aqueous mixtures

    International Nuclear Information System (INIS)

    Thome, J.R.; Shakir, S.

    1987-01-01

    A new mixture boiling correlation was developed for nucleate pool boiling of aqueous mixtures on plain, smooth tubes. The semi-empirical correlation models the rise in the local bubble point temperature in a mixture caused by the preferential evaporation of the more volatile component during bubble growth. This rise varies from zero at low heat fluxes (where only single-phase natural convection is present) up to nearly the entire boiling range at the peak heat flux (where latent heat transport is dominant). The boiling range, which is the temperature difference between the dew point and bubble point of a mixture, is used to characterize phase equilibrium effects. An exponential term models the rise in the local bubble point temperature as a function of heat flux. The correlation was compared against binary mixture boiling data for ethanol-water, methanol-water, n-propanol-water, and acetone-water. The majority of the data was predicted to within 20%. Further experimental research is currently underway to obtain multicomponent boiling data for aqueous mixtures with up to five components and for wider boiling ranges

  17. Glass binder development for a glass-bonded sodalite ceramic waste form

    International Nuclear Information System (INIS)

    Riley, Brian J.; Vienna, John D.; Frank, Steven M.; Kroll, Jared O.; Peterson, Jacob A.

    2017-01-01

    This paper discusses work to develop Na_2O-B_2O_3-SiO_2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. In this paper, five new glasses with ~20 mass% Na_2O were designed to generate waste forms with high sodalite. The glasses were then used to produce ceramic waste forms with a surrogate salt waste. The waste forms made using these new glasses were formulated to generate more sodalite than those made with previous baseline glasses for this type of waste. The coefficients of thermal expansion for the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature than previous binder glasses used. Finally, these improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability.

  18. Cold crucible induction melter studies for making glass ceramic waste forms: A feasibility assessment

    International Nuclear Information System (INIS)

    Crum, Jarrod; Maio, Vince; McCloy, John; Scott, Clark; Riley, Brian; Benefiel, Brad; Vienna, John; Archibald, Kip; Rodriguez, Carmen; Rutledge, Veronica; Zhu, Zihua; Ryan, Joe; Olszta, Matthew

    2014-01-01

    Glass ceramics are being developed to immobilize fission products, separated from used nuclear fuel by aqueous reprocessing, into a stable waste form suitable for disposal in a geological repository. This work documents the glass ceramic formulation at bench scale and for a scaled melter test performed in a pilot-scale (∼1/4 scale) cold crucible induction melter (CCIM). Melt viscosity, electrical conductivity, and crystallization behavior upon cooling were measured on a small set of compositions to select a formulation for melter testing. Property measurements also identified a temperature range for melter operation and cooling profiles necessary to crystallize the targeted phases in the waste form. Bench scale and melter run results successfully demonstrate the processability of the glass ceramic using the CCIM melter technology

  19. Production of sodalite waste forms by addition of glass

    International Nuclear Information System (INIS)

    Pereira, C.

    1995-01-01

    Spent nuclear fuel can be treated in a molten salt electrorefiner for conversion into metal and mineral waste forms for geologic disposal. Sodalite is one of the mineral waste forms under study. Fission products in the molten salt are ion-exchanged into zeolite A, which is converted to sodalite and consolidated. Sodalite can be formed directly from mixtures of salt and zeolite A at temperatures above 975 K; however, nepheline is usually produced as a secondary phase. Addition of small amounts of glass frit to the mixture reduced nepheline formation significantly. Loss of fission products was not observed for reaction below 1000 K. Hot-pressing of the sodalite powders yielded dense pellets (∼2.3 g/cm 3 ) without any loss of fission product species. Normalized release rates were below 1 g/m 2 ·day for pre-washed samples in 28-day leach tests based on standard MCC-1 tests but increased with the presence of free salt on the sodalite

  20. Dynamic viscosity versus probe-reported microviscosity of aqueous mixtures of poly(ethylene glycol)

    International Nuclear Information System (INIS)

    Bhanot, Chhavi; Trivedi, Shruti; Gupta, Arti; Pandey, Shubha; Pandey, Siddharth

    2012-01-01

    Highlights: ► Aqueous polymer mixtures, non-toxic media of huge industrial importance, are investigated. ► Bulk viscosity of aqueous. PEG mixtures is shown to vary widely with composition and temperature. ► T-dependent viscosity follows Arrhenius behavior suggesting aqueous PEGs to be Newtonian fluids. ► Microviscosity sensed by a fluorescence ratiometric probe is estimated and correlated with viscosity. ► Microviscosity correlates well with bulk viscosity at higher PEG concentrations. - Abstract: Correlation between the dynamic viscosity (η) and the microviscosity of a hybrid green medium constituted of water and poly(ethylene glycol) (PEG) of average molar mass (200, 400, and 600) g · mol −1 , respectively, is explored over the temperatures range (10 to 90) °C across the complete composition regime. The microviscosity is obtained using a fluorescence probe 1,3-bis-(1-pyrenyl)propane (BPP), which is manifested through the ratio of the monomer-to-intramolecular excimer intensities (I M /I E ). Aqueous PEG mixtures are observed to behave similar to Newtonian fluids as the temperature dependence of dynamic viscosity follows Arrhenius-type behavior. Surprisingly, a simple and convenient linear dependence of ln η with wt% PEG of the mixture is established. The BPP I M /I E is observed, in general, to increase with the bulk dynamic viscosity of the mixture having >10 wt% PEG suggesting a good correlation between the bulk dynamic viscosity and BPP-reported microviscosity when the viscosity of the aqueous PEG mixture is relatively high.

  1. Candidate Low-Temperature Glass Waste Forms for Technetium-99 Recovered from Hanford Effluent Management Facility Evaporator Concentrate

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Mei [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Tang, Ming [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Rim, Jung Ho [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chamberlin, Rebecca M. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-07-24

    Alternative treatment and disposition options may exist for technetium-99 (99Tc) in secondary liquid waste from the Hanford Direct-Feed Low-Activity Waste (DFLAW) process. One approach includes development of an alternate glass waste form that is suitable for on-site disposition of technetium, including salts and other species recovered by ion exchange or precipitation from the EMF evaporator concentrate. By recovering the Tc content from the stream, and not recycling the treated concentrate, the DFLAW process can potentially be operated in a more efficient manner that lowers the cost to the Department of Energy. This report provides a survey of candidate glass formulations and glass-making processes that can potentially incorporate technetium at temperatures <700 °C to avoid volatilization. Three candidate technetium feed streams are considered: (1) dilute sodium pertechnetate loaded on a non-elutable ion exchange resin; (2) dilute sodium-bearing aqueous eluent from ion exchange recovery of pertechnetate, or (3) technetium(IV) oxide precipitate containing Sn and Cr solids in an aqueous slurry. From the technical literature, promising candidate glasses are identified based on their processing temperatures and chemical durability data. The suitability and technical risk of three low-temperature glass processing routes (vitrification, encapsulation by sintering into a glass composite material, and sol-gel chemical condensation) for the three waste streams was assessed, based on available low-temperature glass data. For a subset of candidate glasses, their long-term thermodynamic behavior with exposure to water and oxygen was modeled using Geochemist’s Workbench, with and without addition of reducing stannous ion. For further evaluation and development, encapsulation of precipitated TcO2/Sn/Cr in a glass composite material based on lead-free sealing glasses is recommended as a high priority. Vitrification of pertechnetate in aqueous anion exchange eluent solution

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

    International Nuclear Information System (INIS)

    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. Stability indicating HPLC-DAD method for analysis of Ketorolac binary and ternary mixtures in eye drops: Quantitative analysis in rabbit aqueous humor.

    Science.gov (United States)

    El Yazbi, Fawzy A; Hassan, Ekram M; Khamis, Essam F; Ragab, Marwa A A; Hamdy, Mohamed M A

    2017-11-15

    Ketorolac tromethamine (KTC) with phenylephrine hydrochloride (PHE) binary mixture (mixture 1) and their ternary mixture with chlorpheniramine maleate (CPM) (mixture 2) were analyzed using a validated HPLC-DAD method. The developed method was suitable for the in vitro as well as quantitative analysis of the targeted mixtures in rabbit aqueous humor. The analysis in dosage form (eye drops) was a stability indicating one at which drugs were separated from possible degradation products arising from different stress conditions (in vitro analysis). For analysis in aqueous humor, Guaifenesin (GUF) was used as internal standard and the method was validated according to FDA regulation for analysis in biological fluids. Agilent 5 HC-C18(2) 150×4.6mm was used as stationary phase with a gradient eluting solvent of 20mM phosphate buffer pH 4.6 containing 0.2% triethylamine and acetonitrile. The drugs were resolved with retention times of 2.41, 5.26, 7.92 and 9.64min for PHE, GUF, KTC and CPM, respectively. The method was sensitive and selective to analyze simultaneously the three drugs in presence of possible forced degradation products and dosage form excipients (in vitro analysis) and also with the internal standard, in presence of aqueous humor interferences (analysis in biological fluid), at a single wavelength (261nm). No extraction procedure was required for analysis in aqueous humor. The simplicity of the method emphasizes its capability to analyze the drugs in vivo (in rabbit aqueous humor) and in vitro (in pharmaceutical formulations). Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Electrochemical characterization of Zr-based thin film metallic glass in hydrochloric aqueous solution

    International Nuclear Information System (INIS)

    Chuang, Ching-Yen; Liao, Yi-Chia; Lee, Jyh-Wei; Li, Chia-Lin; Chu, Jinn P.; Duh, Jenq-Gong

    2013-01-01

    Recently thin film metallic glass represents a class of promising engineering materials for structural applications. In this work, the Zr-based thin film metallic glass (TFMG) was fabricated on the Si and AISI 420 substrates using a Zr–Cu–Ni–Al alloy and pure Zr metal targets by a pulsed DC magnetron sputtering system. The chemical compositions, crystalline structures, microstructures and corrosion behavior in hydrochloric (HCl) aqueous solutions of Zr-based TFMGs were investigated. The results showed that the surface morphologies of Zr-based TFMG were very smooth. A compact and dense structure without columnar structure was observed. The amorphous structure of Zr-based TFMG was characterized by the X-ray diffractometer and transmission electron microscopy analyses. After the potentiodynamic polarization test, the better corrosion resistance was achieved for the Zr-based TFMG coated AISI 420 in 1 mM HCl aqueous solution. Based on the surface morphologies and chemical analysis results of the corroded surfaces, the pitting, crevice corrosion and filiform corrosion were found. The corrosion mechanisms of the Zr-based TFMG were discussed in this work. - Highlights: ► Zr-based thin film metallic glass with amorphous structure. ► Better corrosion resistance of Zr-based thin film metallic glass observed. ► Pitting, crevice and filiform corrosion reactions revealed. ► The Cu-rich corrosion products found in the pit. ► Nanowire and flaky corrosion products formed adjacent to the filiform corrosion path

  5. Performance Characteristics of Waste Glass Powder Substituting Portland Cement in Mortar Mixtures

    Science.gov (United States)

    Kara, P.; Csetényi, L. J.; Borosnyói, A.

    2016-04-01

    In the present work, soda-lime glass cullet (flint, amber, green) and special glass cullet (soda-alkaline earth-silicate glass coming from low pressure mercury-discharge lamp cullet and incandescent light bulb borosilicate glass waste cullet) were ground into fine powders in a laboratory planetary ball mill for 30 minutes. CEM I 42.5N Portland cement was applied in mortar mixtures, substituted with waste glass powder at levels of 20% and 30%. Characterisation and testing of waste glass powders included fineness by laser diffraction particle size analysis, specific surface area by nitrogen adsorption technique, particle density by pycnometry and chemical analysis by X-ray fluorescence spectrophotometry. Compressive strength, early age shrinkage cracking and drying shrinkage tests, heat of hydration of mortars, temperature of hydration, X-ray diffraction analysis and volume stability tests were performed to observe the influence of waste glass powder substitution for Portland cement on physical and engineering properties of mortar mixtures.

  6. Comparison of analysis techniques by liquid scintillation and Cerenkov Effect for 40K quantification in aqueous samples

    International Nuclear Information System (INIS)

    Miranda C, L.; Davila R, J. I.; Lopez del R, H.; Mireles G, F.

    2015-09-01

    In this work the counting by liquid scintillation and Cerenkov Effect to quantify 40 K in aqueous samples was used. The performance of both techniques was studied by comparing the response of three commercial liquid scintillation OptiPhase HiSafe 3, Ultima Gold Ab and OptiPhase TriSafe, the vial type and presentation conditions of the sample for counting. In liquid scintillation, the ability to form homogeneous mixtures depended on the ionic strength of the aqueous solutions. The scintillator OptiPhase HiSafe 3 showed a greater charge capacity for solutions with high ionic strength (<3.4), while the scintillator OptiSafe TriSafe no form homogeneous mixtures for solutions of ionic strength higher than 0.3. Counting efficiencies for different proportions of sample and scintillator near 100% for the scintillators OptiSafe HiSafe 3 and Ultima Gold Ab were obtained. In the counting by Cerenkov Effect, the efficiency and sensitivity depended of the vial type; polyethylene vials were more suitable for counting that the glass vials. The sample volume had not significant effect on counting efficiency, obtaining an average value of 44.8% for polyethylene vials and 37.3% for glass vials. Therefore, the liquid scintillation was more efficient and sensitive for the measurement of 40 K in aqueous solutions. (Author)

  7. Glass Ceramic Waste Forms for Combined CS+LN+TM Fission Products Waste Streams

    International Nuclear Information System (INIS)

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

    2010-01-01

    In this study, glass ceramics were explored as an alternative waste form for glass, the current baseline, to be used for immobilizing alkaline/alkaline earth + lanthanide (CS+LN) or CS+LN+transition metal (TM) fission-product waste streams generated by a uranium extraction (UREX+) aqueous separations type process. Results from past work on a glass waste form for the combined CS+LN waste streams showed that as waste loading increased, large fractions of crystalline phases precipitated upon slow cooling.(1) The crystalline phases had no noticeable impact on the waste form performance by the 7-day product consistency test (PCT). These results point towards the development of a glass ceramic waste form for treating CS+LN or CS+LN+TM combined waste streams. Three main benefits for exploring glass ceramics are: (1) Glass ceramics offer increased solubility of troublesome components in crystalline phases as compared to glass, leading to increased waste loading; (2) The crystalline network formed in the glass ceramic results in higher heat tolerance than glass; and (3) These glass ceramics are designed to be processed by the same melter technology as the current baseline glass waste form. It will only require adding controlled canister cooling for crystallization into a glass ceramic waste form. Highly annealed waste form (essentially crack free) with up to 50X lower surface area than a typical High-Level Waste (HLW) glass canister. Lower surface area translates directly into increased durability. This was the first full year of exploring glass ceramics for the Option 1 and 2 combined waste stream options. This work has shown that dramatic increases in waste loading are achievable by designing a glass ceramic waste form as an alternative to glass. Table S1 shows the upper limits for heat, waste loading (based on solubility), and the decay time needed before treatment can occur for glass and glass ceramic waste forms. The improvements are significant for both combined waste

  8. Glass Ceramic Waste Forms for Combined CS+LN+TM Fission Products Waste Streams

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-09-23

    In this study, glass ceramics were explored as an alternative waste form for glass, the current baseline, to be used for immobilizing alkaline/alkaline earth + lanthanide (CS+LN) or CS+LN+transition metal (TM) fission-product waste streams generated by a uranium extraction (UREX+) aqueous separations type process. Results from past work on a glass waste form for the combined CS+LN waste streams showed that as waste loading increased, large fractions of crystalline phases precipitated upon slow cooling.[1] The crystalline phases had no noticeable impact on the waste form performance by the 7-day product consistency test (PCT). These results point towards the development of a glass ceramic waste form for treating CS+LN or CS+LN+TM combined waste streams. Three main benefits for exploring glass ceramics are: (1) Glass ceramics offer increased solubility of troublesome components in crystalline phases as compared to glass, leading to increased waste loading; (2) The crystalline network formed in the glass ceramic results in higher heat tolerance than glass; and (3) These glass ceramics are designed to be processed by the same melter technology as the current baseline glass waste form. It will only require adding controlled canister cooling for crystallization into a glass ceramic waste form. Highly annealed waste form (essentially crack free) with up to 50X lower surface area than a typical High-Level Waste (HLW) glass canister. Lower surface area translates directly into increased durability. This was the first full year of exploring glass ceramics for the Option 1 and 2 combined waste stream options. This work has shown that dramatic increases in waste loading are achievable by designing a glass ceramic waste form as an alternative to glass. Table S1 shows the upper limits for heat, waste loading (based on solubility), and the decay time needed before treatment can occur for glass and glass ceramic waste forms. The improvements are significant for both combined waste

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

    International Nuclear Information System (INIS)

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

    2003-01-01

    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)

  10. Binary eutectic clusters and glass formation in ideal glass-forming liquids

    International Nuclear Information System (INIS)

    Lu, Z. P.; Shen, J.; Xing, D. W.; Sun, J. F.; Liu, C. T.

    2006-01-01

    In this letter, a physical concept of binary eutectic clusters in 'ideal' glass-forming liquids is proposed based on the characteristics of most well-known bulk metallic glasses (BMGs). The authors approach also includes the treatment of binary eutectic clusters as basic units, which leads to the development of a simple but reliable method for designing BMGs more efficiently and effectively in these unique glass-forming liquids. As an example, bulk glass formers with superior glass-forming ability in the Zr-Ni-Cu-Al and Zr-Fe-Cu-Al systems were identified with the use of the strategy

  11. Glass Ceramic Formulation Data Package

    International Nuclear Information System (INIS)

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

    2012-01-01

    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

  12. Immobilization of radwastes in glass containers and products formed thereby

    International Nuclear Information System (INIS)

    Macedo, P.B.; Litovitz, T.A.; Simmons, C.J.; Simmons, J.H.; Lagakos, N.; Tran, D.C.

    1982-01-01

    A mixture of glass packing and radioactive or other toxic material is placed in a solid glass container, and the container is heated to drive off volatile components and collapse and seal the container

  13. Method of denitrification and stabilization of radioactive aqueous solutions of radioisotope nitrates

    International Nuclear Information System (INIS)

    Pecak, V.; Matous, V.

    1983-01-01

    The method is solved of denitrification and of the stabilization of aqueous solutions of radioactive isotopes produced during the reprocessing of nuclear fuel. The aqueous solution is first mixed with the vitreous component, most frequently phosphoric acid, ammonium phosphate or boric acid and if needed with the addition of alkalis, possibly with clarifying or anti-foam components, e.g., arsenic trioxide, antimony or cerium oxide. The mixture is further adjusted with ammonia to pH 5 - 9. The liquid mixture is then thermally and pyrolytically processed, e.g., by calcinator or fluid-bed reactor or by pot melting at temperatures of 3O0 to 900 degC while of a powder product or glass melt is formed in the presence of gaseous emissions composed of nitrous oxide - nitrogen. The resulting product is further processed by containerization or is sealed in a metal matrix. (B.S.)

  14. PHASE-TRANSITIONS IN THE BILAYERS OF VESICLES FORMED FROM BINARY-MIXTURES OF SYMMETRICAL DI-N-ALKYLPHOSPHATES IN AQUEOUS-SOLUTIONS

    NARCIS (Netherlands)

    BLANDAMER, MJ; BRIGGS, B; CULLIS, PM; ENGBERTS, JBFN; WAGENAAR, A; SMITS, E; HOEKSTRA, D; KACPERSKA, A

    1994-01-01

    Vesicles in aqueous solutions were prepared from binary equimolar mixtures of di-n-alkyl-phosphates (sodium and potassium), (R(1)O)(2)PO(2)(-)M(+) and (R(2)O)(2)PO(2)(-)M(+). When the number of carbon atoms in R(1) and R(2) differs by two and when R(1) or R(2) = C12H25, C14H29, C16H33 and C18H37 the

  15. Effect of water content on the glass transition temperature of mixtures of sugars, polymers, and penetrating cryoprotectants in physiological buffer.

    Science.gov (United States)

    Drake, Andrew C; Lee, Youngjoo; Burgess, Emma M; Karlsson, Jens O M; Eroglu, Ali; Higgins, Adam Z

    2018-01-01

    Long-term storage of viable mammalian cells is important for applications ranging from in vitro fertilization to cell therapy. Cryopreservation is currently the most common approach, but storage in liquid nitrogen is relatively costly and the requirement for low temperatures during shipping is inconvenient. Desiccation is an alternative strategy with the potential to enable viable cell preservation at more convenient storage temperatures without the need for liquid nitrogen. To achieve stability during storage in the dried state it is necessary to remove enough water that the remaining matrix forms a non-crystalline glassy solid. Thus, the glass transition temperature is a key parameter for design of cell desiccation procedures. In this study, we have investigated the effects of moisture content on the glass transition temperature (Tg) of mixtures of sugars (trehalose or raffinose), polymers (polyvinylpyrrolidone or Ficoll), penetrating cryoprotectants (ethylene glycol, propylene glycol, or dimethyl sulfoxide), and phosphate buffered saline (PBS) solutes. Aqueous solutions were dried to different moisture contents by equilibration with saturated salt solutions, or by baking at 95°C. The glass transition temperatures of the dehydrated samples were then measured by differential scanning calorimetry. As expected, Tg increased with decreasing moisture content. For example, in a desiccation medium containing 0.1 M trehalose in PBS, Tg ranged from about 360 K for a completely dry sample to about 220 K at a water mass fraction of 0.4. Addition of polymers to the solutions increased Tg, while addition of penetrating cryoprotectants decreased Tg. Our results provide insight into the relationship between relative humidity, moisture content and glass transition temperature for cell desiccation solutions containing sugars, polymers and penetrating cryoprotectants.

  16. Flash-Point prediction for binary partially miscible aqueous-organic mixtures

    OpenAIRE

    Liaw, Horng-Jang; Chen, Chien Tsun; Gerbaud, Vincent

    2008-01-01

    Flash point is the most important variable used to characterize fire and explosion hazard of liquids. Herein, partially miscible mixtures are presented within the context of liquid-liquid extraction processes and heterogeneous distillation processes. This paper describes development of a model for predicting the flash point of binary partially miscible mixtures of aqueous-organic system. To confirm the predictive efficiency of the derived flash points, the model was verified by comparing the ...

  17. Absorption of Carbon Dioxide in Aqueous Solutions of N-methyldiethanolamine Mixtures

    Science.gov (United States)

    Ma’mun, S.; Svendsen, H. F.

    2018-05-01

    Carbon dioxide (CO2) is one of the greenhouse gases (GHG) that has contributed to the global warming problem. Carbon dioxide is produced in large quantity from coal-fired power plants, iron and steel production, cement production, chemical and petrochemical industries, natural gas purification, and transportation. Some efforts to reduce the CO2 emissions to the atmosphere are then required. Amine-based absorption may be an option for post-combustion capture. The objective of this study is to measure the effect of promoter addition as well as MDEA concentration for the CO2 absorption into the aqueous solutions of MDEA to improve its performances, i.e. increasing the absorption rate and the absorption capacity. Absorption of CO2 in aqueous solutions of MDEA mixtures were measured at 40 °C in a bubble tank reactor. The systems tested were the mixtures of 30 wt% MDEA with 5 and 10 wt% BEA and the mixtures of 40 and 50 wt% MDEA with 6 wt% AEEA. It was found that for MDEA-BEA-H2O mixtures, the higher the promoter concentraation the higher the CO2 absorption rate, while for the MDEA-AEEA-H2O mixtures, the higher the MDEA concentration the lower the CO2 absorption rate.

  18. Evolution of the spectrum of the solvated electron in BeF2 aqueous glasses at 76 K

    International Nuclear Information System (INIS)

    Nguyen, T.Q.; Walker, D.C.; Gillis, H.A.

    1978-01-01

    Evidence is presented for a spontaneous shift from infrared-to- red-to-green in the overall spectrum of the electron trapped in an aqueous glass at 76 K following nanosecond pulse radiolysis. As with the alcohols, after the pulse the infrared absorption decays, there is a growth-then-decay of absorbance at intermediate wavelengths and net growth of absorption due to the equilibrated trapped electron state, e - /sub vis/. This progressive transition was not characterised by a single-step process and was discernible in aqueous glasses containing 7.5 or 10.7M BeF 2 in D 2 O. At higher BeF 2 concentrations, or with LiBr as glass-forming electrolyte, no growth of e - /sub vis/ was observed, probably because of concurrent loss of e - /sub vis/ in those glasses, as in LiCl and other glasses. BeF 2 glasses of trapped electrons showed several other features of interest: (i) wavelength- selective bleaching of the e - /sub vis/ band indicates that it is composed of a broad ''green'' band (lambda/sub max/, 530--590 nm) which bleaches homogeneously, and a broad ''red'' region which bleaches inhomogeneously. (ii) lambda/sub max/ for e - /sub vis/ changes with BeF 2 concentration, being blue shifted with increasing concentration , with both green and red underlying structures shifting slightly. (iii) No absorption due to F - 2 was found following pulse radiolysis in these glasses at 76 K. (iv) Several recent findings with LiCl are mimicked by F - 2 glasses. For instance, G (e - /sub vis/) increases and G (e - /sub ir/) decreases as the electrolyte concentration is increased, while the combined yield remains constant at 1.8 +- 0.1

  19. Reactive oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in the Anthropocene.

    Science.gov (United States)

    Tong, Haijie; Lakey, Pascale S J; Arangio, Andrea M; Socorro, Joanna; Kampf, Christopher J; Berkemeier, Thomas; Brune, William H; Pöschl, Ulrich; Shiraiwa, Manabu

    2017-08-24

    Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (formation can be explained by the decomposition of organic hydroperoxides, which are a prominent fraction of SOA, through interactions with water and Fenton-like reactions with dissolved transition metal ions. Our findings imply that the chemical reactivity and aging of SOA particles can be enhanced upon interaction with mineral dust in deliquesced particles or cloud/fog droplets. SOA decomposition could be comparably important to the classical Fenton reaction of H 2 O 2 with Fe 2+ and that SOA can be the main source of OH radicals in aqueous droplets at low concentrations of H 2 O 2 and Fe 2+ . In the human respiratory tract, the inhalation and deposition of SOA and mineral dust can also lead to the release of ROS, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols in the Anthropocene.

  20. Interfacial energies of aqueous mixtures and porous coverings for enhancing pool boiling heat transfer

    Energy Technology Data Exchange (ETDEWEB)

    Melendez, Elva [CIICAp, Universidad Autonoma del Estado de Morelos, 62210 (Mexico); Reyes, Rene [Departamento de Ingenieria Quimica y Alimentos, Universidad de las Americas Puebla, Santa Catarina Martir Cholula, Puebla 72820 (Mexico)

    2006-08-15

    The interfacial energies effects on pool boiling were measured for combinations of aqueous ethanol mixtures and cationic surfactants. The mixture with 16% ethanol by weight had the lowest contact angle (associated to the highest wettability) and produced the highest convective heat transfer coefficient, h, among the aqueous ethanol mixtures. The surfactant sodium-lauryl-sulfate added at 100 ppm (its calculated critical micelle concentration CMC) to the 16% ethanol aqueous mixture produced an additional increment of the wettability of the mixture and of the h values; other concentrations of the surfactant reduced de contact angle and h values. The effect of these interfacial energies represents a mass-transfer contribution to pool boiling and the proposal of mixture effects both as increased spreadability and as micelle states. Several randomly constructed porous coverings, contributing to the breakage of vapor slugs around the heater, were tested; produced the highest h values for average pore diameters of 0.5 mm, and covering thickness of 0.972 mm. The synergistic effect on h of the interfacial energies of mixtures at their critical micelle concentration, and porous coverings was measured. Therefore, the independent driving forces combined in this study for increasing pool boiling heat transfer are (a) spreadability of the liquid on the solid; (b) the bubble's size reduction, achieved by micelle states; and (c) the bubble's breakage, induced by the porous coverings, for vapor flow not under pressure drop control. (author)

  1. Glass transition behaviour of the quaternary ammonium type ionic liquid, {[DEME][I] + H2O} mixtures

    International Nuclear Information System (INIS)

    Imai, Yusuke; Abe, Hiroshi; Matsumoto, Hitoshi; Shimada, Osamu; Hanasaki, Tomonori; Yoshimura, Yukihiro

    2011-01-01

    By a simple DTA system, the glass transition temperatures of the quaternary ammonium type ionic liquid, {N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium iodide, [DEME][I] + H 2 O} mixtures after quick pre-cooling were measured as a function of water concentration (x mol% H 2 O). Results were compared with the previous results of {[DEME][BF 4 ] + H 2 O} mixtures in which double glass transitions were observed in the water concentration region of (16.5 to 30.0) mol% H 2 O. Remarkably, we observed the double glass transition phenomenon in {[DEME][I] + H 2 O} mixtures too, but the two-T g s regions lie towards the water-rich side of (77.5 to 85.0) mol% H 2 O. These clearly reflect the difference in the anionic effect between BF 4 - and I - on the water structure. The end of the glass-formation region of {[DEME][I] + H 2 O} mixtures is around x = 95.0 mol% H 2 O, and this is comparable to that of {[DEME][BF 4 ] + H 2 O} mixtures (x = 96.0 mol% H 2 O).

  2. Review of glass ceramic waste forms

    International Nuclear Information System (INIS)

    Rusin, J.M.

    1981-01-01

    Glass ceramics are being considered for the immobilization of nuclear wastes to obtain a waste form with improved properties relative to glasses. Improved impact resistance, decreased thermal expansion, and increased leach resistance are possible. In addition to improved properties, the spontaneous devitrification exhibited in some waste-containing glasses can be avoided by the controlled crystallization after melting in the glass-ceramic process. The majority of the glass-ceramic development for nuclear wastes has been conducted at the Hahn-Meitner Institute (HMI) in Germany. Two of their products, a celsian-based (BaAl 3 Si 2 O 8 ) and a fresnoite-based (Ba 2 TiSi 2 O 8 ) glass ceramic, have been studied at Pacific Northwest Laboratory (PNL). A basalt-based glass ceramic primarily containing diopsidic augite (CaMgSi 2 O 6 ) has been developed at PNL. This glass ceramic is of interest since it would be in near equilibrium with a basalt repository. Studies at the Power Reactor and Nuclear Fuel Development Corporation (PNC) in Japan have favored a glass-ceramic product based upon diopside (CaMgSi 2 O 6 ). Compositions, processing conditions, and product characterization of typical commercial and nuclear waste glass ceramics are discussed. In general, glass-ceramic waste forms can offer improved strength and decreased thermal expansion. Due to typcially large residual glass phases of up to 50%, there may be little improvement in leach resistance

  3. Multiple Glass Transitions and Freezing Events of Aqueous Citric Acid

    Science.gov (United States)

    2014-01-01

    Calorimetric and optical cryo-microscope measurements of 10–64 wt % citric acid (CA) solutions subjected to moderate (3 K/min) and slow (0.5 and 0.1 K/min) cooling/warming rates and also to quenching/moderate warming between 320 and 133 K are presented. Depending on solution concentration and cooling rate, the obtained thermograms show one freezing event and from one to three liquid–glass transitions upon cooling and from one to six liquid–glass and reverse glass–liquid transitions, one or two freezing events, and one melting event upon warming of frozen/glassy CA/H2O. The multiple freezing events and glass transitions pertain to the mother CA/H2O solution itself and two freeze-concentrated solution regions, FCS1 and FCS2, of different concentrations. The FCS1 and FCS2 (or FCS22) are formed during the freezing of CA/H2O upon cooling and/or during the freezing upon warming of partly glassy or entirely glassy mother CA/H2O. The formation of two FCS1 and FCS22 regions during the freezing upon warming to our best knowledge has never been reported before. Using an optical cryo-microscope, we are able to observe the formation of a continuous ice framework (IF) and its morphology and reciprocal distribution of IF/(FCS1 + FCS2). Our results provide a new look at the freezing and glass transition behavior of aqueous solutions and can be used for the optimization of lyophilization and freezing of foods and biopharmaceutical formulations, among many other applications where freezing plays a crucial role. PMID:25482069

  4. The effect of aqueous media on the mechanical properties of fluorapatite-mullite glass-ceramics.

    Science.gov (United States)

    Mollazadeh, S; Ajalli, Siamak; Kashi, Tahereh S Jafarzadeh; Yekta, Bijan Eftekhai; Javadpour, Jafar; Jafari, S; Youssefi, Abbas; Fazel, Akbar

    2015-11-01

    To verify the effects of alternating thermal changes in aqueous media and chemical composition on mechanical properties of apatite-mullite glass-ceramics and to investigate concentration of ions eluted from glass-ceramics in aqueous media. The glass compositions were from SiO2Al2O3P2O5CaOTiO2BaOZrO2CaF2 system. Glass-ceramics were prepared by heat-treating at 1100°C for 3h samples alternately immersed in water at 5 and 60°C. The 3-point bending strength (n=10) were determined using 3×4×25mm/bar and a universal testing machine, at a cross-head speed of 0.1mm/min. Vickers micro hardness were evaluated by applying a total of 15-20 indentations under a 100g load for 30s. Concentrations of ions eluted from glass-ceramics immersed in 60±5°C double distilled water were determined by ion chromatography. The toxicity of glass-ceramics was assessed by seeding the osteosarcoma cells (MG63) on powder for different days and their cell proliferation assessment was investigated by MTT assay. The data were analyzed using one way analysis of variance and the means were compared by Tukey's test (5% significance level). The highest flexural strength and hardness values after thermal changes belonged to TiO2 and ZrO2 containing glass-ceramics which contained lower amount of released ions. BaO containing glass-ceramic and sample with extra amount of silica showed the highest amount of reduction in their mechanical strength values. These additives enhanced the concentration of eluted ions in aqueous media. MTT results showed that glass-ceramics were almost equivalent concerning their in-vitro biological behavior. Thermal changes and chemical compositions had significant effects on flexural strength and Vickers micro-hardness values. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  5. Excess Properties of Aqueous Mixtures of Methanol: Simple Models Versus Experiment

    Czech Academy of Sciences Publication Activity Database

    Vlček, Lukáš; Nezbeda, Ivo

    roč. 131-132, - (2007), s. 158-162 ISSN 0167-7322. [International Conference on Solution Chemistry /29./. Portorož, 21.08.2005-25.08.2005] R&D Projects: GA AV ČR(CZ) IAA4072303; GA AV ČR(CZ) 1ET400720409 Institutional research plan: CEZ:AV0Z40720504 Keywords : aqueous mixtures * primitive models * water-alcohol mixtures Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.982, year: 2007

  6. Ceramic and glass radioactive waste forms

    Energy Technology Data Exchange (ETDEWEB)

    Readey, D.W.; Cooley, C.R. (comps.)

    1977-01-01

    This report contains 14 individual presentations and 6 group reports on the subject of glass and polycrystalline ceramic radioactive waste forms. It was the general consensus that the information available on glass as a waste form provided a good basis for planning on the use of glass as an initial waste form, that crystalline ceramic forms could also be good waste forms if much more development work were completed, and that prediction of the chemical and physical stability of the waste form far into the future would be much improved if the basic synergistic effects of low temperature, radiation and long times were better understood. Continuing development of the polycrystalline ceramic forms was recommended. It was concluded that the leach rate of radioactive species from the waste form is an important criterion for evaluating its suitability, particularly for the time period before solidified waste is permanently placed in the geologic isolation of a Federal repository. Separate abstracts were prepared for 12 of the individual papers; the remaining two were previously abstracted.

  7. Glass Forming Ability in Systems with Competing Orderings

    Science.gov (United States)

    Russo, John; Romano, Flavio; Tanaka, Hajime

    2018-04-01

    Some liquids, if cooled rapidly enough to avoid crystallization, can be frozen into a nonergodic glassy state. The tendency for a material to form a glass when quenched is called "glass-forming ability," and it is of key significance both fundamentally and for materials science applications. Here, we consider liquids with competing orderings, where an increase in the glass-forming ability is signaled by a depression of the melting temperature towards its minimum at triple or eutectic points. With simulations of two model systems where glass-forming ability can be tuned by an external parameter, we are able to interpolate between crystal-forming and glass-forming behavior. We find that the enhancement of the glass-forming ability is caused by an increase in the structural difference between liquid and crystal: stronger competition in orderings towards the melting point minimum makes a liquid structure more disordered (more complex). This increase in the liquid-crystal structure difference can be described by a single adimensional parameter, i.e., the interface energy cost scaled by the thermal energy, which we call the "thermodynamic interface penalty." Our finding may provide a general physical principle for not only controlling the glass-forming ability but also the emergence of glassy behavior of various systems with competing orderings, including orderings of structural, magnetic, electronic, charge, and dipolar origin.

  8. Crystallization In Multicomponent Glasses

    International Nuclear Information System (INIS)

    Kruger, A.A.; Hrma, P.R.

    2009-01-01

    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.

  9. CRYSTALLIZATION IN MULTICOMPONENT GLASSES

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. The role of nuclear analytical techniques in the study of aqueous corrosion of glasses

    International Nuclear Information System (INIS)

    Trocellier, P.

    1984-01-01

    Direct observation of resonant nuclear reactions, backscattering spectrometry and X ray microanalysis with a nuclear microprobe were used to determine elementary depth profiles in the near surface region of leached glasses. Some computing programs required to interpretate the analytical information detected were built. Experimental conditions to characterize glass samples without secondary effects were defined; and the influence of some leaching parameters was studied to describe the first stages of aqueous corrosion of borosilicate glasses [fr

  11. Physicochemical analysis of cryocrystallization processes of aqueous solutions of yttrium, barium, copper nitrates and their mixtures

    International Nuclear Information System (INIS)

    Kulakov, A.B.; Mozhaev, A.P.; Tesker, A.M.; Churagulov, B.R.

    1992-01-01

    Products of fast hardening of aqueous solutions of different concentration of yttrium, barium copper nitrates and their mixtures including mixture of three nitrates with molar ratio equal to 1:2:3 used for synthesis of YBa 2 Cu 3 O 7-x HTSC by cryochemical technique, in liquid nitrogen, are studied using low-temperature, differential thermal and X-ray phase analyses. Aqueous solutions of barium, copper, yttrium nitrates are shown to belong to three different classes which differ in behaviour at fast cooling and subsequent slow heating. Cryogranulate at YBa 2 Cu 2 O 7-x synthesis using cryochemical technique represents mixture of X-ray amorphous Ba(NO 3 ) 2 , crystalline Cu(NO 3 ) 2 ·6H 2 O and ice, as well as, supercooled aqueous solution of yttrium and copper nitrates

  12. Study of thermodynamic and acoustic behaviour of nicotinic acid in binary aqueous mixtures of D-lactose

    Science.gov (United States)

    Sharma, Ravi; Thakur, R. C.

    2017-07-01

    In the present study, the thermodynamic properties such as partial molar volumes, partial molar expansibilities, partial molar compressibilities, partial molar heat capacities and isobaric thermal expansion coefficient of different solutions of nicotinic acid in binary aqueous mixtures of D-lactose have been determined at different temperatures (298.15, 303.15, 308.15, 313.15) K. Masson's equation is used to interpret the data in terms of solute-solute and solute-solvent interactions. In the present study it has been found that nicotinic acid behaves as structure maker in aqueous and binary aqueous mixtures of D-lactose.

  13. Sonochemical degradation of perfluorooctanesulfonate in aqueous film-forming foams.

    Science.gov (United States)

    Vecitis, Chad D; Wang, Yajuan; Cheng, Jie; Park, Hyunwoong; Mader, Brian T; Hoffmann, Michael R

    2010-01-01

    Aqueous film-forming foams (AFFFs) are fire extinguishing agents developed by the Navy to quickly and effectively combat fires occurring close to explosive materials and are utilized today at car races, airports, oil refineries, and military locations. Fluorochemical (FC) surfactants represent 1-5% of the AFFF composition, which impart properties such as high spreadability, negligible fuel diffusion, and thermal stability to the foam. FC's are oxidatively recalcitrant, persistent in the environment, and have been detected in groundwater at AFFF training sites. Ultrasonic irradiation of aqueous FCs has been reported to degrade and subsequently mineralize the FC surfactants perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS). Here we present results of the sonochemical degradation of aqueous dilutions of FC-600, a mixture of hydrocarbon (HC) and fluorochemical components including cosolvents, anionic hydrocarbon surfactants, fluorinated amphiphilic surfactants, anionic fluorinated surfactants, and thickeners such as starch. The primary FC surfactant in FC-600, PFOS, was sonolytically degraded over a range of FC-600 aqueous dilutions, 65 ppb or = 1, indicating that bubble-water interfacial pyrolytic cleavage of the C-S bond in PFOS is the initial degradation step, in agreement with previous studies done in Milli-Q water. Sonochemical fluoride production is significantly below quantitative expectations, delta[F-]/delta[PFOS] 4 vs 17, suggesting that in the AFFF matrix, PFOS' fluorochemical tail is not completely degraded, whereas Milli-Q studies yielded quantitative F- production. Measurements of time-dependent methylene blue active substances and total organic carbon indicate that the other FC-600 components were also sonolytically decomposed.

  14. Analysis of form deviation in non-isothermal glass molding

    Science.gov (United States)

    Kreilkamp, H.; Grunwald, T.; Dambon, O.; Klocke, F.

    2018-02-01

    Especially in the market of sensors, LED lighting and medical technologies, there is a growing demand for precise yet low-cost glass optics. This demand poses a major challenge for glass manufacturers who are confronted with the challenge arising from the trend towards ever-higher levels of precision combined with immense pressure on market prices. Since current manufacturing technologies especially grinding and polishing as well as Precision Glass Molding (PGM) are not able to achieve the desired production costs, glass manufacturers are looking for alternative technologies. Non-isothermal Glass Molding (NGM) has been shown to have a big potential for low-cost mass manufacturing of complex glass optics. However, the biggest drawback of this technology at the moment is the limited accuracy of the manufactured glass optics. This research is addressing the specific challenges of non-isothermal glass molding with respect to form deviation of molded glass optics. Based on empirical models, the influencing factors on form deviation in particular form accuracy, waviness and surface roughness will be discussed. A comparison with traditional isothermal glass molding processes (PGM) will point out the specific challenges of non-isothermal process conditions. Furthermore, the underlying physical principle leading to the formation of form deviations will be analyzed in detail with the help of numerical simulation. In this way, this research contributes to a better understanding of form deviations in non-isothermal glass molding and is an important step towards new applications demanding precise yet low-cost glass optics.

  15. Atomic Fermi-Bose mixtures in inhomogeneous and random lattices: From Fermi glass to quantum spin glass and quantum percolation

    International Nuclear Information System (INIS)

    Sanpera, A.; Lewenstein, M.; Kantian, A.; Sanchez-Palencia, L.; Zakrzewski, J.

    2004-01-01

    We investigate strongly interacting atomic Fermi-Bose mixtures in inhomogeneous and random optical lattices. We derive an effective Hamiltonian for the system and discuss its low temperature physics. We demonstrate the possibility of controlling the interactions at local level in inhomogeneous but regular lattices. Such a control leads to the achievement of Fermi glass, quantum Fermi spin-glass, and quantum percolation regimes involving bare and/or composite fermions in random lattices

  16. Effect of different glass and zeolite A compositions on the leach resistance of ceramic waste forms

    International Nuclear Information System (INIS)

    Lewis, M.A.; Hash, M.; Glandorf, D.

    1996-01-01

    A ceramic waste form is being developed for waste generated during electrometallurgical treatment of spent nuclear fuel. The waste is generated when fission products are removed from the electrolyte, LiCl-KCl eutectic. The waste form is a composite fabricated by hot isostatic pressing a mixture of glass frit and zeolite occluded with fission products and salt. Normalized release rate is less than 1 g/m 2 d for all elements in MCC-1 leach test run for 28 days in deionized water at 90 C. This leach resistance is comparable to that of early Savannah River glasses. We are investigating how leach resistance is affected by changes in cationic form of zeolite and in glass composition. Composites were made with 3 forms of zeolite A and 6 glasses. We used 3-day ASTM C1220-92 (formerly MCC-1) leach tests to screen samples for development purposes only. The leach test results show that the glass composites of zeolites 5A and 4A retain fission products equally well. Loss of Cs is small (0.1-0.5 wt%), while the loss of divalent and trivalent fission products is one or more orders of magnitude smaller. Composites of 5A retain chloride ion better in these short-term screens than 4A and 3A. The more leach resistant composites were made with durable glasses rich in silica and poor in alkaline earth oxides. XRD show that a salt phase was absent in the leach resistant composites of 5A and the better glasses but was present in the other composites with poorer leach performance. Thus, absence of salt phase corresponds to improved leach resistance. Interactions between zeolite and glass depend on composition of both

  17. Excess Properties of Aqueous Mixtures of Methanol: Simulation Versus Experiment

    Czech Academy of Sciences Publication Activity Database

    González-Salgado, D.; Nezbeda, Ivo

    2006-01-01

    Roč. 240, č. 2 (2006), s. 161-166 ISSN 0378-3812 R&D Projects: GA AV ČR(CZ) IAA4072303 Grant - others:BEMUSAC(XE) G1MA/CT/2002/04019 Institutional research plan: CEZ:AV0Z40720504 Keywords : aqueous mixtures * excess properties * partial molar properties Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.680, year: 2006

  18. Solvation of hydrocarbons in aqueous-organic mixtures

    International Nuclear Information System (INIS)

    Sedov, I.A.; Magsumov, T.I.; Solomonov, B.N.

    2016-01-01

    Highlights: • Thermodynamic functions of solvation in mixtures of water with acetone and acetonitrile are measured at T = 298.15 K. • Solvation of n-octane and toluene in aqueous-organic mixtures is studied. • When increasing water content, Gibbs free energies grow up steadily, while enthalpies have a maximum. • Hydrocarbons are preferentially solvated with organic cosolvent even in mixtures with rather high water content. • Acetonitrile suppresses the hydrophobic effect less than acetone. - Abstract: We study the solvation of two hydrocarbons, n-octane and toluene, in binary mixtures of water with organic cosolvents. Two polar aprotic cosolvents that are miscible with water in any proportions, acetonitrile and acetone, were considered. We determine the magnitudes of thermodynamic functions of dissolution and solvation at T = 298.15 K in the mixtures with various compositions. Solution calorimetry was used to measure the enthalpies of solution, and GC headspace analysis was applied to obtain limiting activity coefficients of solutes in the studied systems. For the first time, the enthalpies of solution of alkane in the mixtures with high water content were measured directly. We observed well-pronounced maxima of the dependencies of enthalpies of solvation from the composition of solvent and no maxima for the Gibbs free energies of solvation. Two factors are concluded to be important to explain the observed tendencies: high energy cost of reorganization of binary solvent upon insertion of solute molecules and preferential surrounding of hydrocarbons with the molecules of organic cosolvent. Enthalpy-entropy compensation leads to a steady growth of the Gibbs free energies with increasing water content. On the other hand, consideration of the plots of the Gibbs free energy against enthalpy of solvation clearly shows that the solvation properties are changed dramatically after addition of a rather small amount of organic cosolvents. It is shown that they

  19. A new method locating good glass-forming compositions

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Dechuan [Department of Materials Physics and Chemistry, Northeastern University, No.3-11, Wenhua Road, Shenyang, 110819 (China); Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016 (China); Geng, Yan [Department of Materials Physics and Chemistry, Northeastern University, No.3-11, Wenhua Road, Shenyang, 110819 (China); Li, Zhengkun [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016 (China); Liu, Dingming [Department of Materials Physics and Chemistry, Northeastern University, No.3-11, Wenhua Road, Shenyang, 110819 (China); Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016 (China); Fu, Huameng; Zhu, Zhengwang [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016 (China); Qi, Yang, E-mail: qiyang@imp.neu.edu.cn [Department of Materials Physics and Chemistry, Northeastern University, No.3-11, Wenhua Road, Shenyang, 110819 (China); Zhang, Haifeng, E-mail: hfzhang@imr.ac.cn [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016 (China)

    2015-10-15

    A new method was proposed to pinpoint the compositions with good glass forming ability (GFA) by combining atomic clusters and mixing entropy. The clusters were confirmed by analyzing competing crystalline phases. The method was applied to the Zr–Al–Ni–Cu–Ag alloy system. A series of glass formers with diameter up to 20 mm were quickly detected in this system. The good glass formers were located only after trying 5 compositions around the calculated composition. The method was also effective in other multi-component systems. This method might provide a new way to understand glass formation and to quickly pinpoint compositions with high GFA. - Highlights: • A new method was proposed to quickly design glass formers with high glass forming ability. • The method of designing pentabasic Zr–Al–Ni–Cu–Ag alloys was applied. • A series of new Zr-based bulk metallic glasses with critical diameter of 20 mm were discovered.

  20. A new method locating good glass-forming compositions

    International Nuclear Information System (INIS)

    Yu, Dechuan; Geng, Yan; Li, Zhengkun; Liu, Dingming; Fu, Huameng; Zhu, Zhengwang; Qi, Yang; Zhang, Haifeng

    2015-01-01

    A new method was proposed to pinpoint the compositions with good glass forming ability (GFA) by combining atomic clusters and mixing entropy. The clusters were confirmed by analyzing competing crystalline phases. The method was applied to the Zr–Al–Ni–Cu–Ag alloy system. A series of glass formers with diameter up to 20 mm were quickly detected in this system. The good glass formers were located only after trying 5 compositions around the calculated composition. The method was also effective in other multi-component systems. This method might provide a new way to understand glass formation and to quickly pinpoint compositions with high GFA. - Highlights: • A new method was proposed to quickly design glass formers with high glass forming ability. • The method of designing pentabasic Zr–Al–Ni–Cu–Ag alloys was applied. • A series of new Zr-based bulk metallic glasses with critical diameter of 20 mm were discovered

  1. Cosolvent effect on the dynamics of water in aqueous binary mixtures

    Science.gov (United States)

    Zhang, Xia; Zhang, Lu; Jin, Tan; Zhang, Qiang; Zhuang, Wei

    2018-04-01

    Water rotational dynamics in the mixtures of water and amphiphilic molecules, such as acetone and dimethyl sulfoxide (DMSO), measured by femtosecond infrared, often vary non-monotonically as the amphiphilic molecule's molar fraction changes from 0 to 1. Recent study has attributed the non-ideal water rotation with concentration in DMSO-water mixtures to different microscopic hydrophilic-hydrophobic segregation structure in water-rich and water-poor mixtures. Interestingly, the acetone molecule has very similar molecular structure to DMSO, but the extremum of the water rotational time in the DMSO-water mixtures significantly shifts to lower concentration and the rotation of water is much faster than those in acetone-water mixtures. The simulation results here shows that the non-ideal rotational dynamics of water in both mixtures are due to the frame rotation during the interval of hydrogen bond (HB) switchings. A turnover of the frame rotation with concentration takes place as the structure transition of mixture from the hydrogen bond percolation structure to the hydrophobic percolation structure. The weak acetone-water hydrogen bond strengthens the hydrophobic aggregation and accelerates the relaxation of the hydrogen bond, so that the structure transition takes places at lower concentration and the rotation of water is faster in acetone-water mixture than in DMSO-water mixture. A generally microscopic picture on the mixing effect on the water dynamics in binary aqueous mixtures is presented here.

  2. Shear viscosity of glass-forming melts in the liquid-glass transition region

    International Nuclear Information System (INIS)

    Sanditov, D. S.

    2010-01-01

    A new approach to interpreting the hole-activation model of a viscous flow of glass-forming liquids is proposed. This model underlies the development of the concept on the exponential temperature dependence of the free energy of activation of a flow within the range of the liquid-glass transition in complete agreement with available experimental data. The 'formation of a fluctuation hole' in high-heat glass-forming melts is considered as a small-scale low-activation local deformation of a structural network, i.e., the quasi-lattice necessary for the switching of the valence bond, which is the main elementary event of viscous flow of glasses and their melts. In this sense, the hole formation is a conditioned process. A drastic increase in the activation free energy of viscous flow in the liquid-glass transition region is explained by a structural transformation that is reduced to a limiting local elastic deformation of the structural network, which, in turn, originates from the excitation (critical displacement) of a bridging atom like the oxygen atom in the Si-O-Si bridge. At elevated temperatures, as a rule, a necessary amount of excited bridging atoms (locally deformed regions of the structural network) always exists, and the activation free energy of viscous flow is almost independent of temperature. The hole-activation model is closely connected with a number of well-known models describing the viscous flow of glass-forming liquids (the Avramov-Milchev, Nemilov, Ojovan, and other models).

  3. Forming Glasses from Se and Te

    Directory of Open Access Journals (Sweden)

    Pierre Lucas

    2009-10-01

    Full Text Available Despite being close neighbors on the Periodic Table, selenium and tellurium present a totally different abilities to form glasses. Se is a very good glass former, and gives rise to numerous glass compositions which are popular for their transparency in the infrared range and their stability against crystallization. These glasses can be shaped into sophisticated optical devices such as optical fibers, planar guides or lenses. Nevertheless, their transparencies are limited at about 12 μm (depending on the thickness of the optical systems due to the relatively small mass of the Se element. On the other hand, tellurium is heavier and its use in substitution for Se permits to shift the IR cutoff beyond 20 μm. However, the semimetallic nature of Te limits its glass formation ability and this glass family is known to be unstable and consequently has found application as phase change material in the Digital Versatile Disk (DVD technology. In this paper, after a review of selenide glasses and their applications, it will be shown how, in a recent past, it has been possible to stabilize tellurium glasses by introducing new elements like Ga or I in their compositions.

  4. DEHYDRATION AND REHYDRATION OF AN ION-LEACHABLE GLASS USED IN GLASS-IONOMER CEMENTS

    Directory of Open Access Journals (Sweden)

    Jacek Klos

    2017-03-01

    Full Text Available Samples of the ionomer glass known as G338 have been heated at 240°C for 24 hours, after which they lost 1.19 % (Standard deviation 0.16% of their original mass. This loss was attributed to removal of water, as both molecular water and the product of reaction of silanol groups to form siloxane bridges. Exposing samples of glass either to air at ambient humidity or to air at 95% relative humidity showed a degree of rehydration, but mass uptake did not approach the original mass loss in either case. It is suggested that this is because of the relatively difficulty in forming new silanol groups from the siloxane bridges. Glass-ionomer cements prepared from these glass samples with aqueous poly(acrylic acid solution had different properties, depending on the glass used. Dehydrated glass gave cements which set faster but were weaker than those formed by as-received glass. The role of silanol groups in influencing reaction rate and promoting strength development is discussed.

  5. Quantification of Protein Hydration, Glass Transitions, and Structural Relaxations of Aqueous Protein and Carbohydrate-Protein Systems.

    Science.gov (United States)

    Roos, Yrjö H; Potes, Naritchaya

    2015-06-11

    Water distribution and miscibility of carbohydrate and protein components in biological materials and their structural contributions in concentrated solids are poorly understood. In the present study, structural relaxations and a glass transition of protein hydration water and antiplasticization of the hydration water at low temperatures were measured using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) for bovine whey protein (BWP), aqueous glucose-fructose (GF), and their mixture. Thermal transitions of α-lactalbumin and β-lactoglobulin components of BWP included water-content-dependent endothermic but reversible dehydration and denaturation, and exothermic and irreversible aggregation. An α-relaxation assigned to hydration water in BWP appeared at water-content-dependent temperatures and increased to over the range of 150-200 K at decreasing water content and in the presence of GF. Two separate glass transitions and individual fractions of unfrozen water of ternary GF-BWP-water systems contributed to uncoupled α-relaxations, suggesting different roles of protein hydration water and carbohydrate vitrification in concentrated solids during freezing and dehydration. Hydration water in the BWP fraction of GF-BWP systems was derived from equilibrium water sorption and glass transition data of the GF fraction, which gave a significant universal method to quantify (i) protein hydration water and (ii) the unfrozen water in protein-carbohydrate systems for such applications as cryopreservation, freezing, lyophilization, and dehydration of biological materials. A ternary supplemented phase diagram (state diagram) established for the GF-BWP-water system can be used for the analysis of the water distribution across carbohydrate and protein components in such applications.

  6. Characterization of the bioactive and mechanical behavior of dental ceramic/sol-gel derived bioactive glass mixtures.

    Science.gov (United States)

    Abbasi, Zahra; Bahrololoum, Mohammad E; Bagheri, Rafat; Shariat, Mohammad H

    2016-02-01

    Dental ceramics can be modified by bioactive glasses in order to develop apatite layer on their surface. One of the benefits of such modification is to prolong the lifetime of the fixed dental prosthesis by preventing the formation of secondary caries. Dental ceramic/sol-gel derived bioactive glass mixture is one of the options for this modification. In the current study, mixtures of dental ceramic/bioactive glass with different compositions were successfully produced. To evaluate their bioactive behavior, prepared samples were immersed in a simulated body fluid at various time intervals. The prepared and soaked specimens were characterized using Fourier transform infrared spectroscopy, X-ray diffractometry and scanning electron microscopy. Since bioactive glasses have deleterious effects on the mechanical properties of dental ceramics, 3-point bending tests were used to evaluate the flexural strength, flexural strain, tangent modulus of elasticity and Weibull modulus of the specimens in order to find the optimal relationship between mechanical and bioactive properties. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Silicate glasses. Chapter 1

    International Nuclear Information System (INIS)

    Lutze, W.

    1988-01-01

    This chapter is a survey of world-wide research and development efforts in nuclear waste glasses and its production technology. The principal glasses considered are silicate glasses which contain boron, i.e. borosilicate glass. A historical overview of waste form development programs in nine countries is followed by a summary of the design criteria for borosilicate glass compositions glass compositions. In the sections on glass properties the waste form is characterized in terms of potential alterations under the influence of heat, thermal gradients, radiation, aqueous solutions and combinations thereof. The topics are phase transformations, mechanical properties, radiation effects and chemical durability. The results from studies of volcanic glasses, as natural analogues for borosilicate nuclear waste glasses in order to verify predictions obtained from short-term tests in the laboratory, have been compiled in a special section on natural analogues. A special section on advanced vitrification techniques summarizes the various actual and potential processing schemes and describes the facilities. The literature has been considered until 1985. (author). 430 refs.; 68 figs.; 29 tabs

  8. Aqueous alteration of Japanese simulated waste glass P0798: Effects of alteration-phase formation on alteration rate and cesium retention

    International Nuclear Information System (INIS)

    Inagaki, Y.; Shinkai, A.; Idemistu, K.; Arima, T.; Yoshikawa, H.; Yui, M.

    2006-01-01

    Aqueous alteration tests were performed with a Japanese simulated waste glass P0798 in alkaline solutions as a function of pH or species/concentration of alkaline metals in the solution in order to evaluate the alteration conditions determining whether smectite (2:1 clay mineral) or analcime (zeolite) forms as the major alteration-phase. XRD analysis of the alteration-phases showed that smectite forms at any pH between 9.5 and 12, and analcime forms at pH above 11, though the formation also depends on species and concentrations of alkaline metals in the solution. These results cannot agree with the thermodynamically predicted phase stability, e.g., smectite is more stable than the thermodynamic prediction shows. On the basis of the results of alteration conditions, the alteration tests were performed under smectite forming conditions, where only smectite forms or no crystalline phases form, in order to evaluate the alteration rate and the mechanism of cesium release/retention. The results showed that the glass alteration proceeds slowly in proportion to square root of time under smectite forming conditions, which indicates that the alteration rate can be controlled by a diffusion process. It was suggested that the alteration rate under smectite forming conditions is independent of the pH, alkaline metal species/concentration in the solution and whether smectite actually forms or not. The results also indicated that most of cesium dissolved from the glass can be retained in the alteration-phases by reversible sorption onto smectite or irreversible incorporation into analcime, pollucite or solid solutions of them

  9. Glass forming ability of calcium aluminosilicate melts

    DEFF Research Database (Denmark)

    Moesgaard, Mette; Yue, Yuanzheng

    2011-01-01

    The glass forming ability (GFA) of two series of calcium aluminosilicate melts is studied by measuring their viscous behavior and crystallization tendency. The first series consists of five compositions on the joining line between the eutectic point of anorthite-wollastonite-tridymite and that of......The glass forming ability (GFA) of two series of calcium aluminosilicate melts is studied by measuring their viscous behavior and crystallization tendency. The first series consists of five compositions on the joining line between the eutectic point of anorthite......-wollastonite-tridymite and that of anorthite-wollastonite-gehlenite. The series includes the eutectic compositions as end members. The second series consists of five compositions on a line parallel to the joining line on the alumina rich side. In the present work, GFA is described in terms of glass stability, i.e., the ability of a glass...... to resist crystallization during reheating. In addition, the fragility index (m) is derived by fitting the viscosity data with the Avramov-Milchev equation. The results show that m is inversely proportional to the glass stability for the two series of melts, implying that m is an indirect measure of GFA...

  10. Lead and copper removal from aqueous solutions by porous glass derived calcium hydroxyapatite

    International Nuclear Information System (INIS)

    Liang Wen; Zhan Lei; Piao Longhua; Ruessel, Christian

    2011-01-01

    Graphical abstract: . Adsorption of Pb 2+ increases with the increase in NaCl volume percentage (1:0%, 2:30%, 3:40%, 4:40%) of the Glass Derived Hydroxyapatite and reaches equilibrium after 24 h. Highlights: → Novel porous glass derived hydroxyapatite matrix is prepared. → Glass derived hydroxyapatite matrix adsorbs lead and copper ions in solutions effectively. → Two adsorption mechanisms including ion exchange theory and the dissolution and precipitation theory are involved in removal of the heavy metal ions from the solutions. - Abstract: A porous glass was prepared by sintering Na 2 O-CaO-B 2 O 3 glass powder with powdered sodium chloride. Subsequently, the sodium chloride was dissolved in water resulting in a highly porous material. A sample was prepared consisting of 60 vol% glass and 40 vol% salt which both had particle sizes 2 HPO 4 solutions at room temperature for 1 day. The porous glass derived hydroxyapatite matrix was then processed for removing lead and copper ions from aqueous solutions. The results showed that the glass derived calcium hydroxyapatite matrix effectively immobilizes lead and copper ions in solution. The adsorption mechanism was investigated by the X-ray Diffraction (XRD) and Scanning Electron Microscopy including Energy Dispersive X-Ray Spectrometry (SEM-EDX).

  11. Experimental investigation of the effects of aqueous species on the dissolution kinetics of R7T7 glass; Etude experimentale de l`influence d`especes aqueuses sur la cinetique de dissolution du verre nucleaire R7T7

    Energy Technology Data Exchange (ETDEWEB)

    Gin, S

    1994-10-01

    This contribution to the study of aqueous corrosion of the French ``R7T7`` reference nuclear containment glass includes a bibliographic survey of prior investigations, highlighting the problems encountered in interpreting the interactions in systems containing clay materials in contact with the glass. An experimental methodology is proposed to investigate the effects of inorganic aqueous species separately from those of a few organic acids on the dissolution mechanisms and kinetics of R7T7 glass at 90 deg. C. The experimental results discussed support the idea that several glass network forming elements may have a kinetically limiting role. The most likely hypothesis to account for the absence of saturation conditions with respect to the glass in certain clay media involves the formation of complexes with kinetically limiting metallic elements such as aluminum released by glass corrosion. This work contributes to a better understanding of the basic mechanisms of nuclear glass dissolution in a geological repository environment. It facilitates the interpretation of glass alteration studies in realistic or actual solutions and may contribute to specifying near field chemical barriers in the form of additives (amorphous silica, aluminum hydroxides or phosphates) around the glass disposal package to enhance the stability of the glass matrix. (author). 148 refs., 40 figs., 32 tabs., 1 append.

  12. Size-controlled synthesis of gold bipyramids using an aqueous mixture of CTAC and salicylate anions as the soft template.

    Science.gov (United States)

    Yoo, Hyojong; Jang, Min Hoon

    2013-08-07

    One-dimensional (1D) gold (Au) bipyramids are successfully synthesized through a facile seed-mediated method using cetyltrimethylammonium chloride (CTAC), Au seed nanoparticles, Ag(+) ions, and ascorbic acid. The length and optical properties of the synthesized Au bipyramids are controlled with precision by varying the amount of salicylate anions (Sal(-)) added during the synthesis. The micelles formed from CTA(+)-Sal(-) mixtures in aqueous solutions act as effective templates for the size-controlled synthesis of 1D nanocrystals.

  13. Simulation of an Aspheric Glass Lens Forming Behavior in Progressive GMP Process

    International Nuclear Information System (INIS)

    Chang, Sung Ho; Lee, Young Min; Kang, Jeong Jin; Hong, Seok Kwan; Shin, Gwang Ho; Heo, Young Moo; Jung, Tae Sung

    2007-01-01

    Recently, GMP(Glass Molding Press) process is mainly used to produce aspheric glass lenses. Because glass lens is heated at high temperature above Tg (Transformation Temperature) for forming the glass, the quality of aspheric glass lens is deteriorated by residual stresses which are generated in a aspheric glass lens after forming. In this study, as a fundamental study to develop the mold for progressive GMP process, we conducted a aspheric glass lens forming simulation. Prior to a aspheric glass lens forming simulation, compression and thermal conductivity tests were carried out to obtain mechanical and thermal properties of K-PBK40 which is newly developed material for precision molding, and flow characteristics of K-PBK40 were obtained at high temperature. Then, using the flow characteristics obtained, compression simulation was carried out and compared with the experimental result for the purpose of verifying the obtained flow characteristics. Finally, a glass lens press simulation in progressive GMP process was carried out and we could forecast the shape of deformed glass lenses and residual stresses contribution in the structure of deformed glass lenses after forming

  14. Anomalies in the Thermophysical Properties of Undercooled Glass-Forming Alloys

    Science.gov (United States)

    Hyers, Robert W.; Rogers, Jan R.; Kelton, Kenneth F.; Gangopadhyay, Anup

    2008-01-01

    The surface tension, viscosity, and density of several bulk metallic glass-forming alloys have been measured using noncontact techniques in the electrostatic levitation facility (ESL) at NASA Marshall Space Flight Center. All three properties show unexpected behavior in the undercooled regime. Similar deviations were previously observed in titanium-based quasicrystal-forming alloys,but the deviations in the properties of the glass-forming alloys are much more pronounced. New results for anomalous thermophysical properties in undercooled glass-forming alloys will be presented and discussed.

  15. PROCESSING OF CONCENTRATED AQUEOUS ZIRCONIA-BIOGLASS SLIPS BY SLIP CASTING

    Directory of Open Access Journals (Sweden)

    Beltina Leon

    2017-03-01

    Full Text Available 3 mol% yttria-partially stabilized zirconia (Y-TZP powder and a sol-gel derived CaO- P₂O₅- SiO₂ (64S bioglass, were used to produce Y-TZP- bioglass slip cast compacts. The rheological properties of concentrated aqueous Y-TZP- 64S suspensions prepared with two different glass contents: 10.5 vol% and 19.9 vol%, and ammonium polyacrylate (NH₄PA as dispersant, were investigated and compared with those of Y-TZP. The density of green cast samples was related to the degree of slip dispersion. The substitution of Y-TZP by 64S glass in the mixtures resulted in greater adsorption of NH₄PA; however, the viscosity and yield stress values of Y-TZP-64S slips were higher than those of Y-TZP ones for the solid loadings studied. The increase in the glass content from 10.5 to 19.9 vol% increased the viscosity and yield stress values. The presence of 64S glass in the mixtures resulted in a less dense packing of cast samples.

  16. Are the dynamics of silicate glasses and glass-forming liquids embedded in their elastic properties?

    DEFF Research Database (Denmark)

    Smedskjær, Morten Mattrup; Mauro, John C.

    According to the elastic theory of the glass transition, the dynamics of glasses and glass-forming liquids are controlled by the evolution of shear modulus. In particular, the elastic shoving model expresses dynamics in terms of an activation energy required to shove aside the surrounding atoms......, which is determined by the shear modulus. First, we here present an in situ high-temperature Brillouin spectroscopy test of the shoving model near the glass transition of eight aluminosilicate glass-forming systems. We find that the measured viscosity data agree qualitatively with the measured...... temperature dependence of shear moduli, as predicted by the shoving model. However, the model systematically underpredicts the values of fragility. Second, we also present a thorough test of the shoving model for predicting the low temperature dynamics of an aluminosilicate glass system. This is done...

  17. Measuring the Thermophysical and Structural Properties of Glass-Forming and Quasicrystal-Forming Liquids

    Science.gov (United States)

    Hyers, Robert W.; Bradshaw, Richard C.; Rogers, Jan R.; Gangopadhyay, Anup K.; Kelton, Ken F.

    2006-01-01

    The thermophysical properties of glass-forming and quasicrystal-forming alloys show many interesting features in the undercooled liquid range. Some of the features in the thermophysical property curves are expected to reflect changes in the structure and coordination of the liquid. These measurements require containerless processing such as electrostatic levitation to access the undercooled liquid regime. An overview of the state of the art in measuring the thermophysical properties and structure of undercooled liquid glass-forming and quasicrystal-forming alloys will be presented, along with the status of current measurements.

  18. Formation and composition of adsorbates on hydrophobic carbon surfaces from aqueous laccase-maltodextrin mixture suspension

    Energy Technology Data Exchange (ETDEWEB)

    Corrales Ureña, Yendry Regina, E-mail: yendry386@hotmail.com [UNESP São Paulo State University, Av. Eng. Luiz Edmundo Carrijo Coube, 14-01, Bauru, São Paulo (Brazil); Fraunhofer Institute for Manufacturing Technology and Advanced Materials IFAM, Wiener Strasse 12, 28359 Bremen (Germany); Lisboa-Filho, Paulo Noronha [UNESP São Paulo State University, Av. Eng. Luiz Edmundo Carrijo Coube, 14-01, Bauru, São Paulo (Brazil); Szardenings, Michael [Fraunhofer Institute for Cell Therapy and Immunology IZI, Perlickstrasse 1, 04103 Leipzig (Germany); Gätjen, Linda; Noeske, Paul-Ludwig Michael; Rischka, Klaus [Fraunhofer Institute for Manufacturing Technology and Advanced Materials IFAM, Wiener Strasse 12, 28359 Bremen (Germany)

    2016-11-01

    Highlights: • Less than 10 nm layer formed on carbon based materials composed by laccase and maltodextrin. • Improvement of the wettability of carbon based materials. • A protein-polysaccharide biofilm layer formation at solid liquid interface. • Stable layers formed under buffer and water rinsing. - Abstract: A robust procedure for the surface bio-functionalization of carbon surfaces was developed. It consists on the modification of carbon materials in contact with an aqueous suspension of the enzyme laccase from Trametes versicolor and the lyophilization agent maltodextrin, with the pH value adjusted close to the isoelectric point of the enzyme. We report in-situ investigations applying Quartz Crystal Microbalance with Dissipation (QCM-D) for carbon-coated sensor surfaces and, moreover, ex-situ measurements with static contact angle measurements, X-ray Photoelectron Spectroscopy (XPS) and Scanning Force Microscopy (SFM) for smooth Highly Oriented Pyrolytic Graphite (HOPG) substrates, for contact times between the enzyme formulation and the carbon material surface ranging from 20 s to 24 h. QCM-D studies reveals the formation of rigid layer of biomaterial, a few nanometers thin, which shows a strongly improved wettability of the substrate surface upon contact angle measurements. Following spectroscopic characterization, these layers are composed of mixtures of laccase and maltodextrin. The formation of these adsorbates is attributed to attractive interactions between laccase, the maltodextrin-based lyophilization agent and the hydrophobic carbon surfaces; a short-term contact between the aqueous laccase mixture suspension and HOPG surfaces is shown to merely result in de-wetting patterns influencing the results of contact angle measurements. The new enzyme-based surface modification of carbon-based materials is suggested to be applicable for the improvement of not only the wettability of low energy substrate surfaces with fluid formulations like coatings

  19. Crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics for immobilization of simulated sulfate bearing high-level liquid waste

    Science.gov (United States)

    Wu, Lang; Xiao, Jizong; Wang, Xin; Teng, Yuancheng; Li, Yuxiang; Liao, Qilong

    2018-01-01

    The crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics with different content (0-30 wt %) of simulated sulfate bearing high-level liquid waste (HLLW) were evaluated. The sulfate phase segregation in vitrification process was also investigated. The results show that the glass-ceramics with 0-20 wt% of HLLW possess mainly zirconolite phase along with a small amount baddeleyite phase. The amount of perovskite crystals increases while the amount of zirconolite crystals decreases when the HLLW content increases from 20 to 30 wt%. For the samples with 20-30 wt% HLLW, yellow phase was observed during the vitrification process and it disappeared after melting at 1150 °C for 2 h. The viscosity of the sample with 16 wt% HLLW (HLLW-16) is about 27 dPa·s at 1150 °C. The addition of a certain amount (≤20 wt %) of HLLW has no significant change on the aqueous stability of glass-ceramic waste forms. After 28 days, the 90 °C PCT-type normalized leaching rates of Na, B, Si, and La of the sample HLLW-16 are 7.23 × 10-3, 1.57 × 10-3, 8.06 × 10-4, and 1.23 × 10-4 g·m-2·d-1, respectively.

  20. New insight on glass-forming ability and designing Cu-based bulk metallic glasses: The solidification range perspective

    International Nuclear Information System (INIS)

    Wu, Jili; Pan, Ye; Li, Xingzhou; Wang, Xianfei

    2014-01-01

    Highlights: • The equation, T rg = T g /T l , was rotationally modified to T rg = κ(T m /T l ) + C/T l . • The newly generalized equation suggests a way for describing glass-forming ability. • Several new Cu-based bulk metallic glasses were discovered by solidification range. - Abstract: In this paper, a new equation was rationally generalized from the reduced glass transition temperature. This equation indicates that solidification range can be used for describing glass-forming ability, which can be calculated with the aid of computational thermodynamic approach. Based on this scenario, several new Cu-based bulk metallic glasses in the ternary Cu–Zr–Ti alloy system were discovered. The as-cast samples were characterized by X-ray diffraction and transmission electronic microscopy. The results indicate that as-cast samples have monolithic amorphous nature. Thermal analysis validates that the smaller solidification range is closely related to the higher glass-forming ability, which is contributed to the effect of solidification time on the formation of bulk metallic glasses. This work also suggests that solidus can influence glass formation

  1. Fluorescence quenching of polycyclic aromatic hydrocarbons within deep eutectic solvents and their aqueous mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Ashish; Yadav, Anita; Bhawna; Pandey, Siddharth, E-mail: sipandey@chemistry.iitd.ac.in

    2017-03-15

    Two common and popular deep eutectic solvents (DESs) composed of the salt choline chloride and H-bond donors glycerol and urea in 1:2 mol ratio named glyceline and reline, respectively, are investigated for the analysis of polycyclic aromatic hydrocarbons (PAHs) using quenching of both steady-state and time-resolved fluorescence of ten different PAHs by nitromethane at 30 °C. Based on their quenching efficiencies, the PAHs are divided into two groups – group 1 is constituted of the five PAHs whose fluorescence are quenched less effectively by nitromethane whereas the other five exhibiting high quenching efficiency are associated to group 2. Quenching of steady-state fluorescence of group 1 PAHs by nitromethane, albeit not very significant, follow a simple Stern-Volmer behavior. The excited-state emission intensity decay of these PAHs, in both absence and presence of nitromethane, fit best to a single exponential model with small but monotonic decrease in lifetimes. The decrease in lifetime also follows Stern-Volmer behavior, however, the quenching constants (K{sub D}) are lower than those obtained from steady-state fluorescence (K{sub SV}). This is ascribed to the possible formation of charge-transfer complex between the PAH and the nitromethane. Steady-state fluorescence quenching of group 2 PAHs exhibit distinct upward curvature from linear Stern-Volmer behavior implying highly efficient quenching. The intensity decay fits best to a double exponential decay model with longer of the decay times following simple Stern-Volmer behavior. Formation of a complex or the presence of nitromethane within the quenching sphere of action of the PAH having short decay time is proposed. Quenching behavior was found to be similar irrespective of the identity of the DES. A representative group 2 PAH, pyrene, is employed to investigate diffusion dynamics within aqueous mixtures of the two DESs. The bimolecular quenching rate constant (k{sub q}) is found to increase linearly with

  2. Zr-Cu-Ni-Al bulk metallic glasses with superhigh glass-forming ability

    International Nuclear Information System (INIS)

    Sun, Y.J.; Qu, D.D.; Huang, Y.J.; Liss, K.-D.; Wei, X.S.; Xing, D.W.; Shen, J.

    2009-01-01

    Zr-Cu-Ni-Al quaternary amorphous alloy compositions with varying glass-forming ability are developed by an efficient method of proportional mixing of binary eutectics. The critical diameter of the glassy sample is improved from 6 mm for Zr 53 Cu 18.7 Ni 12 Al 16.3 to 14 mm for Zr 50.7 Cu 28 Ni 9 Al 12.3 by straightforwardly adjusting the eutectic unit's coefficients. The drastic improvement in GFA is attributed to balancing the chemical affinities of the Zr, Cu, Ni and Al components in the melt prior to solidification which makes the precipitation of competing crystalline phases more difficult. As the glass-forming ability increases, the concentration of Cu in the alloys exhibits a same trend. Based on synchrotron radiation high-energy X-ray diffraction analysis and Miracle's structural model, it is envisioned that the substitution of additional Cu atoms for Zr atoms in the investigated alloys stabilizes the efficient cluster packing structure of the amorphous alloys, leading to the pronounced increase in their glass-forming ability

  3. Direct conversion of plutonium metal, scrap, residue, and transuranic waste to glass

    International Nuclear Information System (INIS)

    Forsberg, C.W.; Beahm, E.C.; Parker, G.W.; Malling, J.F.; Rudolph, J.

    1995-01-01

    A method for the direct conversion of metals, ceramics, organics, and amorphous solids to borosilicate glass has been invented. The process is called the Glass Material Oxidation and Dissolution System (GMODS). Traditional glass-making processes can convert only oxide materials to glass. However, many wastes contain complex mixtures of metals, ceramics, organics, and amorphous solids. Conversion of such mixtures to oxides followed by their conversion to glass is often impractical. GMODS may create a practical method to convert such mixtures to glass. Plutonium-containing materials (PCMS) exist in many forms, including metals, ceramics, organics, amorphous solids, and mixtures thereof. These PCMs vary from plutonium metal to filters made of metal, organic binders, and glass fibers. For storage and/or disposal of PCMS, it is desirable to convert PCMs to borosilicate glass. Borosilicate glass is the preferred repository waste form for high-level waste (HLW) because of its properties. PCMs converted to a transuranic borosilicate homogeneous glass would easily pass all waste acceptance and storage criteria. Conversion of PCMs to a glass would also simplify safeguards by conversion of heterogeneous PCMs to homogeneous glass. Thermodynamic calculations and proof-of-principle experiments on the GMODS process with cerium (plutonium surrogate), uranium, stainless steel, aluminum, Zircaloy-2, and carbon were successfully conducted. Initial analysis has identified potential flowsheets and equipment. Major unknowns remain, but the preliminary data suggests that GMODS may be a major new treatment option for PCMs

  4. Recirculation within a glass mixture subjected to external and resistive heating

    International Nuclear Information System (INIS)

    Pepper, D.W.

    1985-01-01

    Convective motion within a glass mixture undergoing external and resistive (joule) heating is numerically simulated. A time-split finite element technique and a pseudo-pressure formulation are used to solve the two- and three-dimensional primitive equations of motion. The viscosity, thermal diffusivity, and electrical conductivity vary as a function of temperature; the temperature varies from ambient to 1150 0 C. 15 refs., 4 figs

  5. Direct conversion of plutonium-containing materials to borosilicate glass for storage or disposal

    International Nuclear Information System (INIS)

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

    1995-01-01

    A new process, the Glass Material Oxidation and Dissolution System (GMODS), has been invented for the direct conversion of plutonium metal, scrap, and residue into borosilicate glass. The glass should be acceptable for either the long-term storage or disposition of plutonium. Conversion of plutonium from complex chemical mixtures and variable geometries into homogeneous glass (1) simplifies safeguards and security; (2) creates a stable chemical form that meets health, safety, and environmental concerns; (3) provides an easy storage form; (4) may lower storage costs; and (5) allows for future disposition options. In the GMODS process, mixtures of metals, ceramics, organics, and amorphous solids containing plutonium are fed directly into a glass melter where they are directly converted to glass. Conventional glass melters can accept materials only in oxide form; thus, it is its ability to accept materials in multiple chemical forms that makes GMODS a unique glass making process. Initial proof-of-principle experiments have converted cerium (plutonium surrogate), uranium, stainless steel, aluminum, and other materials to glass. Significant technical uncertainties remain because of the early nature of process development

  6. Leaching behavior of glass ceramic nuclear waste forms

    International Nuclear Information System (INIS)

    Lokken, R.O.

    1981-11-01

    Glass ceramic waste forms have been investigated as alternatives to borosilicate glasses for the immobilization of high-level radioactive waste at Pacific Northwest Laboratory (PNL). Three glass ceramic systems were investigated, including basalt, celsian, and fresnoite, each containing 20 wt % 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 0 C for 3 to 28 days in deionized water and silicate water. The results, expressed in normalized elemental mass loss, (g/m 2 ), 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 g/m 2 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

  7. Surface properties of aqueous amino acid solutions II. Leucine-leucine hydrochloride and leucine-sodium leucinate mixtures.

    Science.gov (United States)

    Matubayasi, Norihiro; Matsuyama, Shohei; Akizuki, Ryosuke

    2005-08-15

    To understand the distinction between the effects of zwitterionic, anionic, and cationic l-leucine upon adsorption and lateral interactions at air/water surface, the surface tensions of aqueous solutions of l-leucine-l-leucine hydrochloride and l-leucine-sodium l-leucinate mixtures were measured as a function of concentration and composition at 25 degrees C. The surface activity decreases in the order l-leucine >l-leucine hydrochloride > sodium l-leucinate. Both l-leucine hydrochloride and sodium l-leucinate form gaseous adsorbed films through the experimentally accessible concentration range, while the adsorbed film of zwitterionic l-leucine shows a transition between gaseous and expanded film.

  8. Femtosecond Laser-Induced Formation of Gold-Rich Nanoalloys from the Aqueous Mixture of Gold-Silver Ions

    Directory of Open Access Journals (Sweden)

    Yuliati Herbani

    2010-01-01

    Full Text Available The synthesis of gold-silver (AuAg nanoalloys of various compositions has been performed by direct irradiation of highly intense femtosecond laser pulse in the presence of polyvinylpyrrolidone (PVP. The mixture of Au and Ag ions of low concentration was simply introduced into a glass vial and subjected to femtosecond laser pulses for several minutes. The AuAg nanoalloys of 2-3 nm with reasonably narrow size distribution were formed, and the position of the surface plasmon resonance (SPR increased monotonically with an increase in the gold molar fraction in the ion solutions. The high resolution transmission electron microscope (HRTEM images exhibited the absence of core-shell structures, and the energy dispersive X-ray spectroscopy (EDX analysis confirmed that the particles were Au-rich alloys even for the samples with large fraction of Ag+ ions fed in the solution mixture. The formation mechanism of the alloy nanoparticles in the high intensity optical field was also discussed.

  9. A systematic investigation and insight into the formation mechanism of bilayers of fatty acid/soap mixtures in aqueous solutions.

    Science.gov (United States)

    Xu, Wenlong; Song, Aixin; Dong, Shuli; Chen, Jingfei; Hao, Jingcheng

    2013-10-08

    Vesicles are the most common form of bilayer structures in fatty acid/soap mixtures in aqueous solutions; however, a peculiar bilayer structure called a "planar sheet" was found for the first time in the mixtures. In the past few decades, considerable research has focused on the formation theory of bilayers in fatty acid/soap mixtures. The hydrogen bond theory has been widely accepted by scientists to explain the formation of bilayers. However, except for the hydrogen bond, no other driving forces were proposed systematically. In this work, three kinds of weak interactions were investigated in detail, which could perfectly demonstrate the formation mechanism of bilayer structures in the fatty acid/soap mixtures in aqueous solutions. (i) The influence of hydrophobic interaction was detected by changing the chain length of fatty acid (C(n)H(2n+1)COOH), in which n = 10 to 18, the phase behavior was investigated, and the phase region was presented. With the help of cryogenic transmission electron microscopy (cryo-TEM) observations, deuterium nuclear magnetic resonance ((2)H NMR), and X-ray diffraction (XRD) measurements, the vesicles and planar sheets were determined. The chain length of C(n)H(2n+1)COOH has an important effect on the physical state of the hydrophobic chain, resulting in an obvious difference in the viscoelasticity of the solution samples. (ii) The existence of hydrogen bonds between fatty acids and their soaps in aqueous solutions was demonstrated by Fourier transform infrared (FT-IR) spectroscopy and molecule dynamical simulation. From the pH measurements, the pH ranges of the bilayer formation were at the pKa values of fatty acids, respectively. (iii) Counterions can be embedded in the stern layer of the bilayers and screen the electrostatic repulsion between the COO(-) anionic headgroups. FT-IR characterization demonstrated a bidentate bridging coordination mode between counterions and carboxylates. The conductivity measurements provided the degree

  10. Preparation of concrete mixtures with electric arc furnace slag and recycled ground glass

    Science.gov (United States)

    Pérez Rojas, Y.; López, E. Vera; López Rodríguez, M.; Díaz Pita, J.

    2017-12-01

    The present work includes the first advances in the development of investigations that seek to include Ground Grinding Glass (GRR) and the Electric Arc Furnace Slag (EAFS) in the production of mixtures of hydraulic concrete mixing them simultaneously, so that it satisfies the specifications techniques to be used in the construction of rigid pavements. Firstly, we cite the tests carried out on the different materials to obtain their physical, chemical and mechanical characterization and determine their compliance, as well as the measurement of certain characteristics that may be somewhat empirical to standardize their control. Technique such as X-Ray Diffraction (XRD), X-ray Fluorescence Spectrometry (XFR) and Scanning Electron Microscopy (SEM) have been used. Once the results of the characterization tests and their correspondence with the Colombian technical standards have been obtained, it has become possible to select the use of the Transparent Recycled Ground Glass (TRGG) as the most suitable for the replacement of the sand in the dosage of new mixtures modified concrete.

  11. Evaluation of final waste forms and recommendations for baseline alternatives to group and glass

    Energy Technology Data Exchange (ETDEWEB)

    Bleier, A.

    1997-09-01

    An assessment of final waste forms was made as part of the Federal Facilities Compliance Agreement/Development, Demonstration, Testing, and Evaluation (FFCA/DDT&E) Program because supplemental waste-form technologies are needed for the hazardous, radioactive, and mixed wastes of concern to the Department of Energy and the problematic wastes on the Oak Ridge Reservation. The principal objective was to identify a primary waste-form candidate as an alternative to grout (cement) and glass. The effort principally comprised a literature search, the goal of which was to establish a knowledge base regarding four areas: (1) the waste-form technologies based on grout and glass, (2) candidate alternatives, (3) the wastes that need to be immobilized, and (4) the technical and regulatory constraints on the waste-from technologies. This report serves, in part, to meet this goal. Six families of materials emerged as relevant; inorganic, organic, vitrified, devitrified, ceramic, and metallic matrices. Multiple members of each family were assessed, emphasizing the materials-oriented factors and accounting for the fact that the two most prevalent types of wastes for the FFCA/DDT&E Program are aqueous liquids and inorganic sludges and solids. Presently, no individual matrix is sufficiently developed to permit its immediate implementation as a baseline alternative. Three thermoplastic materials, sulfur-polymer cement (inorganic), bitumen (organic), and polyethylene (organic), are the most technologically developed candidates. Each warrants further study, emphasizing the engineering and economic factors, but each also has limitations that regulate it to a status of short-term alternative. The crystallinity and flexible processing of sulfur provide sulfur-polymer cement with the highest potential for short-term success via encapsulation. Long-term immobilization demands chemical stabilization, which the thermoplastic matrices do not offer. Among the properties of the remaining

  12. Comparison of analysis techniques by liquid scintillation and Cerenkov Effect for {sup 40}K quantification in aqueous samples; Comparacion de las tecnicas de analisis por centelleo liquido y efecto Cerenkov para la cuantificacion {sup 40}K en muestras acuosas

    Energy Technology Data Exchange (ETDEWEB)

    Miranda C, L.; Davila R, J. I.; Lopez del R, H.; Mireles G, F., E-mail: lilimica20@hotmail.com [Universidad Autonoma de Zacatecas, Unidad Academica de Estudios Nucleares, Cipres No. 10, Fracc. La Penuela, 98068 Zacatecas, Zac. (Mexico)

    2015-09-15

    In this work the counting by liquid scintillation and Cerenkov Effect to quantify {sup 40}K in aqueous samples was used. The performance of both techniques was studied by comparing the response of three commercial liquid scintillation OptiPhase HiSafe 3, Ultima Gold Ab and OptiPhase TriSafe, the vial type and presentation conditions of the sample for counting. In liquid scintillation, the ability to form homogeneous mixtures depended on the ionic strength of the aqueous solutions. The scintillator OptiPhase HiSafe 3 showed a greater charge capacity for solutions with high ionic strength (<3.4), while the scintillator OptiSafe TriSafe no form homogeneous mixtures for solutions of ionic strength higher than 0.3. Counting efficiencies for different proportions of sample and scintillator near 100% for the scintillators OptiSafe HiSafe 3 and Ultima Gold Ab were obtained. In the counting by Cerenkov Effect, the efficiency and sensitivity depended of the vial type; polyethylene vials were more suitable for counting that the glass vials. The sample volume had not significant effect on counting efficiency, obtaining an average value of 44.8% for polyethylene vials and 37.3% for glass vials. Therefore, the liquid scintillation was more efficient and sensitive for the measurement of {sup 40}K in aqueous solutions. (Author)

  13. Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing.

    Science.gov (United States)

    Kim, Chae Un; Tate, Mark W; Gruner, Sol M

    2015-09-22

    Observation of theorized glass-to-liquid transitions between low-density amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-to-liquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-to-liquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water.

  14. Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing

    Science.gov (United States)

    Kim, Chae Un; Tate, Mark W.; Gruner, Sol M.

    2015-01-01

    Observation of theorized glass-to-liquid transitions between low-density amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-to-liquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-to-liquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water. PMID:26351671

  15. Separation of Th and U using borosilicate glasses

    International Nuclear Information System (INIS)

    Chandramouleeswaran, S.; Ramkumar, Jayshree; Singhal, R.K.; Reddy, A.V.R.; Sudarsan, V.

    2010-01-01

    Boroaluminosilicate glasses having B 2 O 3 to Na 2 O ratio 0.23 and 9.8 were prepared by conventional melt-quench method and used as room temperature ion exchanger for the sorption of thorium from aqueous solutions. Various experimental conditions were optimized to achieve selective and maximum uptake of thorium. The studies were extended to synthetic mixtures of thorium and uranium, wherein thorium could be selectively removed in presence of 10 fold excess of uranium. Structural elucidation studies were carried out to understand the ion exchange property of glasses. It is seen that presence of linkages like Si-O - and B-O - in the glasses was responsible for the uptake of metal ions. It is seen that the uptake depends on pH of the solution, composition of glass and the initial concentration of thorium ion in solution. (author)

  16. Applications of High Energy Ion Beam Techniques in Environmental Science: Investigation Associated with Glass and Ceramic Waste Forms

    Energy Technology Data Exchange (ETDEWEB)

    Thevuthasan, Suntharampillai; Shutthanandan, V; Zhang, Yanwen

    2006-02-01

    High energy ion beam capabilities including Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA) have been very effectively used in environmental science to investigate the ion exchange mechanisms in glass waste forms and the effects of irradiation in glass and ceramic waste forms in the past. In this study, RBS and NRA along with SIMNRA simulations were used to monitor the Na depletion and D and 18O uptake in alumina silicate glasses, respectively, after the glass coupons were exposed to aqueous solution. These results show that the formation of a reaction layer and an establishment of a region where diffusion limited ion exchange occur in these glasses during exposure to silica-saturated solutions. Different regions including reaction and diffusion regions were identified on the basis of the depth distributions of these elements. In the case of ceramics, damage accumulation was studied as a function of ion dose at different irradiation temperatures. A sigmoidal dependence of relative disorder on the ion dose was observed. The defect dechanneling factors were calculated for two irradiated regions in SrTiO? using the critical angles determined from the angular yield curves. The dependence of defect dechanneling parameter on the incident energy was investigated and it was observed that the generated defects are mostly interstitial atoms and amorphous clusters. Thermal recovery experiments were performed to study the damage recovery processes up to a maximum temperature of 870 K.

  17. Immobilisation of radwastes in glass containers and products formed thereby

    International Nuclear Information System (INIS)

    Macedo, P.B.; Simmons, C.J.; Lagakos, N.; Simmons, J.H.; Tran, D.C.

    1980-01-01

    A method of preventing the dissemination of toxic material to the environment comprises forming an admixture of toxic material and glass packing in a hollow doped glass container of high silica content, or forming the admixture in a first container and then depositing at least a portion of the admixture in a hollow doped glass container of high silica content. The glass container is then heated to collapse its walls and to seal the container so that the toxic material is entrapped and sealed within the collapsed doped glass container. The thermal expansion coefficient of the container may be decreased prior to use by exchanging hydrogen ion in pores thereof with other cations followed by collapsing the pores. (author)

  18. A Two-Stage Layered Mixture Experiment Design for a Nuclear Waste Glass Application-Part 2

    International Nuclear Information System (INIS)

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

    2003-01-01

    Part 1 (Cooley and Piepel, 2003a) describes the first stage of a two-stage experimental design to support property-composition modeling for high-level waste (HLW) glass to be produced at the Hanford Site in Washington state. Each stage used a layered design having an outer layer, an inner layer, a center point, and some replicates. However, the design variables and constraints defining the layers of the experimental glass composition region (EGCR) were defined differently for the second stage than for the first. The first-stage initial design involved 15 components, all treated as mixture variables. The second-stage augmentation design involved 19 components, with 14 treated as mixture variables and 5 treated as non-mixture variables. For each second-stage layer, vertices were generated and optimal design software was used to select alternative subsets of vertices for the design and calculate design optimality measures. A model containing 29 partial quadratic mixture terms plus 5 linear terms for the non-mixture variables was the basis for the optimal design calculations. Predicted property values were plotted for the alternative subsets of second-stage vertices and the first-stage design points. Based on the optimality measures and the predicted property distributions, a ''best'' subset of vertices was selected for each layer of the second-stage to augment the first-stage design

  19. Determination of the Structure of Vitrified Hydroceramic/CBC Waste Form Glasses Manufactured from DOE Reprocessing Waste

    International Nuclear Information System (INIS)

    Scheetz, B.E.; White, W. B.; Chesleigh, M.; Portanova, A.; Olanrewaju, J.

    2005-01-01

    The selection of a glass-making option for the solidification of nuclear waste has dominated DOE waste form programs since the early 1980's. Both West Valley and Savannah River are routinely manufacturing glass logs from the high level waste inventory in tank sludges. However, for some wastes, direct conversion to glass is clearly not the optimum strategy for immobilization. INEEL, for example, has approximately 4400 m 3 of calcined high level waste with an activity that produces approximately 45 watts/m 3 , a rather low concentration of radioactive constituents. For these wastes, there is value in seeking alternatives to glass. An alternative approach has been developed and the efficacy of the process demonstrated that offers a significant savings in both human health and safety exposures and also a lower cost relative to the vitrification option. The alternative approach utilizes the intrinsic chemical reactivity of the highly alkaline waste with the addition of aluminosilicate admixtures in the appropriate proportions to form zeolites. The process is one in which a chemically bonded ceramic is produced. The driving force for reaction is derived from the chemical system itself at very modest temperatures and yet forms predominantly crystalline phases. Because the chemically bonded ceramic requires an aqueous medium to serve as a vehicle for the chemical reaction, the proposed zeolite-containing waste form can more adequately be described as a hydroceramic. The hydrated crystalline materials are then subject to hot isostatic pressing (HIP) which partially melts the material to form a glass ceramic. The scientific advantages of the hydroceramic/CBC approach are: (1) Low temperature processing; (2) High waste loading and thus only modest volumetric bulking from the addition of admixtures; (3) Ability to immobilize sodium; (4) Ability to handle low levels of nitrate (2-3% NO 3 - ); (5) The flexibility of a vitrifiable waste; and (6) A process that is based on an

  20. Effects of partitioned enthalpy of mixing on glass-forming ability

    Energy Technology Data Exchange (ETDEWEB)

    Song, Wen-Xiong; Zhao, Shi-Jin, E-mail: shijin.zhao@shu.edu.cn [Institute of Materials Science, Shanghai University, Shanghai 200072 (China)

    2015-04-14

    We explore the inherent reason at atomic level for the glass-forming ability of alloys by molecular simulation, in which the effect of partitioned enthalpy of mixing is studied. Based on Morse potential, we divide the enthalpy of mixing into three parts: the chemical part (Δ E{sub nn}), strain part (Δ E{sub strain}), and non-bond part (Δ E{sub nnn}). We find that a large negative Δ E{sub nn} value represents strong AB chemical bonding in AB alloy and is the driving force to form a local ordered structure, meanwhile the transformed local ordered structure needs to satisfy the condition (Δ E{sub nn}/2 + Δ E{sub strain}) < 0 to be stabilized. Understanding the chemical and strain parts of enthalpy of mixing is helpful to design a new metallic glass with a good glass forming ability. Moreover, two types of metallic glasses (i.e., “strain dominant” and “chemical dominant”) are classified according to the relative importance between chemical effect and strain effect, which enriches our knowledge of the forming mechanism of metallic glass. Finally, a soft sphere model is established, different from the common hard sphere model.

  1. How Solid-Electrolyte Interphase Forms in Aqueous Electrolytes.

    Science.gov (United States)

    Suo, Liumin; Oh, Dahyun; Lin, Yuxiao; Zhuo, Zengqing; Borodin, Oleg; Gao, Tao; Wang, Fei; Kushima, Akihiro; Wang, Ziqiang; Kim, Ho-Cheol; Qi, Yue; Yang, Wanli; Pan, Feng; Li, Ju; Xu, Kang; Wang, Chunsheng

    2017-12-27

    Solid-electrolyte interphase (SEI) is the key component that enables all advanced electrochemical devices, the best representative of which is Li-ion battery (LIB). It kinetically stabilizes electrolytes at potentials far beyond their thermodynamic stability limits, so that cell reactions could proceed reversibly. Its ad hoc chemistry and formation mechanism has been a topic under intensive investigation since the first commercialization of LIB 25 years ago. Traditionally SEI can only be formed in nonaqueous electrolytes. However, recent efforts successfully transplanted this concept into aqueous media, leading to significant expansion in the electrochemical stability window of aqueous electrolytes from 1.23 V to beyond 4.0 V. This not only made it possible to construct a series of high voltage/energy density aqueous LIBs with unprecedented safety, but also brought high flexibility and even "open configurations" that have been hitherto unavailable for any LIB chemistries. While this new class of aqueous electrolytes has been successfully demonstrated to support diversified battery chemistries, the chemistry and formation mechanism of the key component, an aqueous SEI, has remained virtually unknown. In this work, combining various spectroscopic, electrochemical and computational techniques, we rigorously examined this new interphase, and comprehensively characterized its chemical composition, microstructure and stability in battery environment. A dynamic picture obtained reveals how a dense and protective interphase forms on anode surface under competitive decompositions of salt anion, dissolved ambient gases and water molecule. By establishing basic laws governing the successful formation of an aqueous SEI, the in-depth understanding presented in this work will assist the efforts in tailor-designing better interphases that enable more energetic chemistries operating farther away from equilibria in aqueous media.

  2. Structural origin of fractional Stokes-Einstein relation in glass-forming liquids.

    Science.gov (United States)

    Pan, Shaopeng; Wu, Z W; Wang, W H; Li, M Z; Xu, Limei

    2017-01-06

    In many glass-forming liquids, fractional Stokes-Einstein relation (SER) is observed above the glass transition temperature. However, the origin of such phenomenon remains elusive. Using molecular dynamics simulations, we investigate the break- down of SER and the onset of fractional SER in a model of metallic glass-forming liquid. We find that SER breaks down when the size of the largest cluster consisting of trapped atoms starts to increase sharply at which the largest cluster spans half of the simulations box along one direction, and the fractional SER starts to follows when the largest cluster percolates the entire system and forms 3-dimentional network structures. Further analysis based on the percolation theory also confirms that percolation occurs at the onset of the fractional SER. Our results directly link the breakdown of the SER with structure inhomogeneity and onset of the fraction SER with percolation of largest clusters, thus provide a possible picture for the break- down of SER and onset of fractional SER in glass-forming liquids, which is is important for the understanding of the dynamic properties in glass-forming liquids.

  3. Simulation of Glass Fiber Forming Processes

    DEFF Research Database (Denmark)

    Von der Ohe, Renate

    Two glass fiber forming processes have been simulated using FEM, which are the drawing of continuous glass fibers for reinforcement purposes and the spinning of discontinuous glass fibers - stone wool for insulation. The aim of this work was to set up a numerical model for each process, and to use...... this model in finding relationships between the production conditions and the resulting fiber properties. For both processes, a free surface with large deformation and radiative and convective heat transfer must be taken into account. The continuous fiber drawing has been simulated successfully......, and parametric studies have been made. Several properties that characterize the process have been calculated, and the relationship between the fictive temperature and the cooling rate of the fibers has been found. The model for the discontinuous fiber spinning was brought to the limits of the commercial code...

  4. Sorption of a mixture of phenols in aqueous solution with activated carbon

    International Nuclear Information System (INIS)

    Mejia M, D.; Lopez M, B.E.; Iturbe G, J.L.

    2003-01-01

    The main objective of this work is the sorption of an aqueous mixture of phenol-4 chloro phenol of different concentrations in a molar relationship 1:1 in activated carbon of mineral origin of different nets (10, 20 and 30) and to diminish with it its presence in water. The experimental results show that the removal capacity depends so much of the surface properties of the sorbent like of the physical and chemical properties of the sorbate. In all the cases it was observed that in the aqueous systems of low concentration the 4-chloro phenol are removed in an approximate proportion of 1.2-4 times greater to than phenol, however to concentrations but high both they are removed approximately in the same proportion. (Author)

  5. Glass-forming liquids: one or more "order" parameters"

    DEFF Research Database (Denmark)

    Bailey, Nicholas; Christensen, Tage Emil; Jakobsen, Bo

    2008-01-01

    We first summarize the classical arguments that the vast majority of glass-forming liquids require more than one ‘order' parameter for their description. Critiques against this conventional wisdom are then presented, and it is argued that the matter deserves to be reconsidered in the light...... that a description with a single "order" parameter applies to a good approximation whenever thermal equilibrium fluctuations of fundamental variables like energy and pressure are strongly correlated. Results from computer simulations showing that this is the case for a number of simple glass-forming liquids, as well...

  6. Atomistic approach to predict the glass-forming ability in Zr–Cu–Al ternary metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Yu, C.Y. [Center for Advanced Structural Materials, Department of Mechanical and Biomedical Engineering, College of Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong (China); Liu, X.J. [State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083 (China); Zheng, G.P. [Department of Mechanical Engineering, The Hong Kong Polytechnic University, Kowloon, Hong Kong (China); Niu, X.R. [Center for Advanced Structural Materials, Department of Mechanical and Biomedical Engineering, College of Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong (China); Liu, C.T., E-mail: chainliu@cityu.edu.hk [Center for Advanced Structural Materials, Department of Mechanical and Biomedical Engineering, College of Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong (China)

    2015-04-05

    Highlights: • An atomistic approach has been developed to predict the glass forming ability (GFA) in Zr–Cu–Al ternary alloy system. • Both of the thermodynamic and structure-dependent kinetic effects to glass formation have been taken into account. • The first-principles calculation and molecular dynamics simulation have been performed. • The approach predicts the best glass former in the model Zr–Cu–Al alloy system. • The predicted GFA is consistent with various experimental results. - Abstract: Prediction of composition-dependent glass-forming ability (GFA) remains to be a key scientific challenge in the metallic-glass community, especially in multi-component alloy systems. In the present study, we apply an atomistic approach to predict the trend of GFA effectively in the Zr–Cu–Al ternary alloy system from alloy compositions alone. This approach is derived from the first-principles calculations based on the density-functional theory and molecular dynamic (MD) simulations. By considering of both the thermodynamic and atomic-structure induced kinetic effects, the predicted GFA trend from this approach shows an excellent agreement with experimental data available in this alloy system, manifesting its capability of seeking metallic glasses with superior GFA in ternary alloy systems.

  7. Basaltic glasses from Iceland and the deep sea: Natural analogues to borosilicate nuclear waste-form glass

    International Nuclear Information System (INIS)

    Jercinovic, M.J.; Ewing, R.C.

    1987-12-01

    The report provides a detailed analysis of the alteration process and products for natural basaltic glasses. Information of specific applicability to the JSS project include: * The identification of typical alteration products which should be expected during the long-term corrosion process of low-silica glasses. The leached layers contain a relatively high proportion of crystalline phases, mostly in the form of smectite-type clays. Channels through the layer provide immediate access of solutions to the fresh glass/alteration layer interface. Thus, glasses are not 'protected' from further corrosion by the surface layer. * Corrosion proceeds with two rates - an initial rate in silica-undersaturated environments and a long-term rate in silica-saturated environments. This demonstrates that there is no unexpected change in corrosion rate over long periods of time. The long-term corrosion rate is consistent with that of borosilicate glasses. * Precipitation of silica-containing phases can result in increased alteration of the glass as manifested by greater alteration layer thicknesses. This emphasizes the importance of being able to predict which phases form during the reaction sequence. * For natural basaltic glasses the flow rate of water and surface area of exposed glass are critical parameters in minimizing glass alteration over long periods of time. The long-term stability of basalt glasses is enhanced when silica concentrations in solution are increased. In summary, there is considerable agreement between corrosion phenomena observed for borosilicate glasses in the laboratory and those observed for natural basalt glasses of great age. (With 121 refs.) (authors)

  8. Glass ceramic toughened with tetragonal zirconia

    Science.gov (United States)

    Keefer, Keith D.; Michalske, Terry A.

    1986-01-01

    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. Nucleating 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.degree. to 1700.degree. C. and is then heat-treated at a temperature within the range of 800.degree. to 1200.degree. 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.

  9. The separation of solid and liquid components of mixtures

    International Nuclear Information System (INIS)

    Hunter, W.M.

    1980-01-01

    An improved method of separating solid and liquid components of mixtures is described which is particularly suited for use in automated radioimmunoassay systems in the analysis of bound and free fractions. A second liquid, having a density intermediate between those of the solid and liquid components, is delivered to the solid/ liquid mixture to form a discrete layer below the mixture and the solid separates into this lower liquid layer assisted by centrifugal force. The second liquid of intermediate density is an aqueous solution of a highly hydrophilic and electrically non-polar solute, such as an aqueous sucrose solution. Further liquids of intermediate density and progressively higher density may be delivered to form further discrete layers below the initial layer of the second dense liquid. After separation of the solid and liquid components of the mixture, the supernatant liquid component of the original mixture is removed in a controlled and non-turbulent manner. The method is illustrated in radioimmunoassays for platelet β-thromboglobulin and human follicle stimulating hormone. (U.K.)

  10. Tungstate-based glass-ceramics for the immobilization of radio cesium

    Science.gov (United States)

    Drabarek, Elizabeth; McLeod, Terry I.; Hanna, John V.; Griffith, Christopher S.; Luca, Vittorio

    2009-02-01

    The preparation of tungstate-containing glass-ceramic composites (GCC) for the potential immobilization of radio cesium has been considered. The GCC materials were prepared by blending two oxide precursor compositions in various proportions. These included a preformed Cs-containing hexagonal tungsten bronze (HTB) phase (Cs 0.3Ti 0.2W 0.8O 3, P6 3/ mcm) and a blend of silica and other oxides. The use of the HTB phase was motivated on the assumption that a HTB-based adsorbent could be used to remove cesium directly from aqueous high level liquid waste feeds. In the absence of the HTB, glass-ceramics were relatively easily prepared from the Cs-containing glass-forming oxide blend. On melting the mixture a relative complex GCC phase assemblage formed. The principal components of this phase assemblage were determined using X-ray powder diffraction, 133Cs MAS-NMR, and cross-sectional SEM and included glass, various zeolites, scheelite (CaWO 4) and a range of other oxide phases and Cs-containing aluminosilicate. Importantly, under no circumstance was cesium partitioned into the glass phase irrespective of whether or not the composition included the preformed Cs-containing HTB compound. For compositions containing the HTB, cesium was partitioned into one of four major phases including zeolite; Cs-silica-tungstate bronze, pollucite (CsAlSi 2O 6), and an aluminosilicate with an Al/Si ratio close to one. The leach resistance of all materials was evaluated and related to the cesium distribution within the GCC phase assemblages. In general, the GCCs prepared from the HTB had superior durability compared with materials not containing tungsten. Indeed the compositions in many cases had leach resistances comparable to the best ceramics or glass materials.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-04-15

    Sodium oxide is present in the majority of commercial and waste glasses as a viscosity-reducing component. In some nuclear waste glasses, its source is the waste itself. As such, it can limit the waste loading because of its deleterious effect on the resistance of the glass to attack by aqueous media. The maximum tolerable content of Na{sub 2}O in glass depends on the presence and concentration of components that interact with it. To assess the acceptability limits of Na{sub 2}O in the composition region of nuclear waste glasses, we formulated 11 baseline compositions by varying the content of oxides of Si, B, Al, Ca, Zr, and Li. In each of these compositions, we varied the Na{sub 2}O fraction from 8–16 mass% to 23–30 mass%. To each of 146 glasses thus formulated, we applied the seven-day Product Consistency Test (PCT) to determine normalized B and Na releases (r{sub i}, where i ≡ B or Na). Fitting approximation functions ln(r{sub i}/gm{sup −2}) = Σb{sub ij}g{sub j} to r{sub i} data (g{sub j} is the j-th component mass fraction and b{sub ij} the corresponding component coefficient), we showed that the r{sub B} (and, consequently, the initial glass alteration rate) was proportional to the glass component mass fractions in the order Al{sub 2}O{sub 3}glass structure would fall apart or beyond which a continuous nondurable phase would be separated. Specific examples are given to demonstrate restrictions imposed on the boundary of the composition region of acceptable glasses by the maximum allowable r{sub B} and by the melt viscosity required for glass melter operation. Finally, the role that PCT data may play in understanding the evolution of the glass alteration process is discussed.

  12. Immobilization of gadolinium in iron borophosphate glasses and iron borophosphate based glass-ceramics: Implications for the immobilization of plutonium(Ⅲ)

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Fu, E-mail: wangfu@swust.edu.cn; Liao, Qilong, E-mail: liaoqilong@swust.edu.cn; Dai, Yunya; Zhu, Hanzhen

    2016-08-15

    Immobilization of gadolinium (Gd), a nonradioactive surrogate for Pu{sup 3+}, in iron borophosphate glasses/glass-ceramics (IBP glasses/glass-ceramics) has been investigated. The IBP glass containing 4 mol% Gd{sub 2}O{sub 3} is homogeneously amorphous. At higher Gd{sub 2}O{sub 3} concentrations, additional Gd is retained in the glasses as crystalline inclusions of monazite GdPO{sub 4} crystalline phase detected with X-ray diffraction. Moreover, Gd{sub 2}O{sub 3} addition increases the T{sub g} of the IBP glasses in glass formation range, which is consistent with the structural modification of the glasses. The structure of the Gd{sub 2}O{sub 3}-loaded IBP glasses/glass-ceramics is mainly based on pyrophosphate units. The chemical durability of Gd{sub 2}O{sub 3}-loaded IBP glasses/glass-ceramics is comparable to widely used borosilicate glass waste forms and the existence of monazite GdPO{sub 4} crystalline phase does not degrade the aqueous chemical durability of the IBP glasses/glass-ceramics. The Gd-loading results imply that the solubility should not be a limiting factor in processing nuclide Pu{sup 3+} if the formed crystalline phase(s) have high chemical durability. - Highlights: • Monazite GdPO{sub 4} are identified in the IBP glasses containing up to 6 mol% Gd{sub 2}O{sub 3}. • R{sub L} of the Gd{sub 2}O{sub 3}-loaded IBP glasses/glass-ceramics are about 10{sup −2} g m{sup −2} d{sup −1}. • Existence of GdPO{sub 4} does not degrade aqueous chemical durability of the IBP glass. • T{sub g} increases with increasing Gd{sub 2}O{sub 3} content in glass formation range. • IBP glasses are potential hosts for the immobilization of Pu{sup 3+} containing HLWs.

  13. Investigation into interaction of mixture of zinc and neodymium nitrates with sodium tungstates in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Rozantsev, G M; Krivobok, V I [Donetskij Gosudarstvennyj Univ. (Ukrainian SSR)

    1978-09-01

    The methods of residual concentrations, pH-potentiometry, and conductometry have been used for studying interaction between the mixture of zinc and neodymium nitrates with sodium tungstate in aqueous solutions. It has been established that independent of the ratio between the components the reaction product is a mixture of simultaneously precipitated zinc and neodymium orthotungstates. Thermal treatment of such mixtures at 650-700 deg C for 40 h and subsequent hardening yields solid solution of the structure ..cap alpha..-Eu/sub 2/(WO/sub 4/)/sub 3/ within the concentration range 85-100 mol % of Nd/sub 2/(WO/sub 4/)/sub 3/.

  14. Evaluation of lead-iron-phosphate glass as a high-level waste form

    International Nuclear Information System (INIS)

    Chick, L.A.; Bunnell, L.R.; Strachan, D.M.; Kissinger, H.E.; Hodges, F.N.

    1986-09-01

    The lead-iron-phosphate (Pb-Fe-P) glass developed at Oak Ridge National Laboratory was evaluated for its potential as an improvement over the current reference nuclear waste form, borosilicate (B-Si) glass. The evaluation was conducted as part of the Second Generation HLW Technology Subtask of the Nuclear Waste Treatment Program at Pacific Northwest Laboratory. The purpose of this work was to investigate possible alternatives to B-Si glass as second-generation waste forms. While vitreous Pb-Fe-P glass appears to have substantially better chemical durability than B-Si glass, severe crystallization or devitrification leading to deteriorated chemical durability would result if this glass were poured into large canisters as is the procedure with B-Si glass. Cesium leach rates from this crystallized material are orders of magnitude greater than those from B-Si glass. Therefore, to realize the potential performance advantages of the Pb-Fe-P material in a nuclear waste form, the processing method would have to cool the material rapidly to retain its vitreous structure

  15. Characterization of 'strong-fragile' behaviour of glass-forming aqueous solutions by neutron scattering

    CERN Document Server

    Branca, C; Galli, G; Magazù, S; Maisano, G; Migliardo, F

    2002-01-01

    Neutron-scattering measurements have been performed on trehalose/H sub 2 O and sucrose/H sub 2 O mixtures by using the spectrometer MIBEMOL at the Laboratoire Leon Brillouin (LLB, Saclay) as a function of temperature and concentration. In order to characterize the different rigidities of both the disaccharide/H sub 2 O mixtures, we have evaluated the R sub 1 (T sub g) parameter connected to the 'strong-fragile' classification of the systems according to Angell's nomenclature. (orig.)

  16. The effects of crystallization and residual glass on the chemical durability of iron phosphate waste forms containing 40 wt% of a high MoO3 Collins-CLT waste

    Science.gov (United States)

    Hsu, Jen-Hsien; Bai, Jincheng; Kim, Cheol-Woon; Brow, Richard K.; Szabo, Joe; Zervos, Adam

    2018-03-01

    The effects of cooling rate on the chemical durability of iron phosphate waste forms containing up to 40 wt% of a high MoO3 Collins-CLT waste simulant were determined at 90 °C using the product consistency test (PCT). The waste form, designated 40wt%-5, meets appropriate Department of Energy (DOE) standards when rapidly quenched from the melt (as-cast) and after slow cooling following the CCC (canister centerline cooling)-protocol, although the quenched glass is more durable. The analysis of samples from the vapor hydration test (VHT) and the aqueous corrosion test (differential recession test) reveals that rare earth orthophosphate (monazite) and Zr-pyrophosphate crystals that form on cooling are more durable than the residual glass in the 40wt%-5 waste form. The residual glass in the CCC-treated samples has a greater average phosphate chain length and a lower Fe/P ratio, and those contribute to its faster corrosion kinetics.

  17. Evaluation of final waste forms and recommendations for baseline alternatives to grout and glass

    International Nuclear Information System (INIS)

    Bleier, A.

    1997-09-01

    An assessment of final waste forms was made as part of the Federal Facilities Compliance Agreement/Development, Demonstration, Testing, and Evaluation (FFCA/DDT ampersand E) Program because supplemental waste-form technologies are needed for the hazardous, radioactive, and mixed wastes of concern to the Department of Energy and the problematic wastes on the Oak Ridge Reservation. The principal objective was to identify a primary waste-form candidate as an alternative to grout (cement) and glass. The effort principally comprised a literature search, the goal of which was to establish a knowledge base regarding four areas: (1) the waste-form technologies based on grout and glass, (2) candidate alternatives, (3) the wastes that need to be immobilized, and (4) the technical and regulatory constraints on the waste-from technologies. This report serves, in part, to meet this goal. Six families of materials emerged as relevant; inorganic, organic, vitrified, devitrified, ceramic, and metallic matrices. Multiple members of each family were assessed, emphasizing the materials-oriented factors and accounting for the fact that the two most prevalent types of wastes for the FFCA/DDT ampersand E Program are aqueous liquids and inorganic sludges and solids. Presently, no individual matrix is sufficiently developed to permit its immediate implementation as a baseline alternative. Three thermoplastic materials, sulfur-polymer cement (inorganic), bitumen (organic), and polyethylene (organic), are the most technologically developed candidates. Each warrants further study, emphasizing the engineering and economic factors, but each also has limitations that regulate it to a status of short-term alternative. The crystallinity and flexible processing of sulfur provide sulfur-polymer cement with the highest potential for short-term success via encapsulation. Long-term immobilization demands chemical stabilization, which the thermoplastic matrices do not offer. Among the properties of the

  18. Changes in glass formation and glass forming ability of Nd2Fe14B by the addition of TiC

    International Nuclear Information System (INIS)

    Branagan, D.J.; Iowa State Univ. of Science and Technology, Ames, IA; McCallum, R.W.; Iowa State Univ. of Science and Technology, Ames, IA

    1996-01-01

    The glass forming ability (GFA) of a stoichiometric Nd 2 Fe 14 B alloy modified with TiC additions was studied. Structural, magnetic, and thermal measurements of as-quenched melt-spun ribbons indicate increasing enhancement of GFA with increasing amounts of TiC addition. The limit of the glass formation range and the amount of glass formed at a particular cooling rate also increased with TiC addition. Enhanced GFA was concurrent with changes in the intrinsic properties of the glass. The crystallization temperature, as well as the transformation rate of crystallization, was raised by TiC addition. The intrinsic magnetic properties of the glass were changed with reductions in saturation magnetization and Curie temperature T c with increasing amounts of TiC addition. The intrinsic glass changes were related to changes in the local short range order of the glass and are consistent with a reduction in free volume and an increased packing efficiency. These changes in local structure of the glass increase the glass stability, which means that less undercooling is needed to prevent crystallization. Thus, at a particular cooling rate, a higher percentage of glass will be formed and the GFA is increased. (orig.)

  19. Composition dependency of the glass forming ability (GFA) in Mg-Ni-Si system by mechanical alloying

    International Nuclear Information System (INIS)

    Xie Haowen; Lin Jianguo; Li Yuncang; Hodgson, Peter D.; Wen Cuie

    2007-01-01

    The pure elemental powder mixtures with the compositions of Mg 65 Ni x Si 35-x (x = 10, 20, 25, 33 at.%) were subject to high-energy ball mill, and the structures of the mixtures at different intervals of milling were characterised by X-ray diffraction (XRD). The compositional dependency of the glass forming ability (GFA) in Mg-Ni-Si system was evaluated based on the experimental results and the theoretical calculation. The compositional dependency of GFA in Mg-Ni-Si system can be understood well by comparing the enthalpies of the crystalline and amorphous phases based on the Miedema's theory for the formation enthalpy of alloys. Increasing the Ni/Mg ratio and/or decreasing Si content can improve the amorphous formability. The calculation results might be of great help in optimising the composition with high GFA in Mg-Ni-Si system

  20. Heat of Absorption of CO2 in Aqueous Solutions of DEEA, MAPA and their Mixture

    DEFF Research Database (Denmark)

    Waseem Arshad, Muhammad; von Solms, Nicolas; Thomsen, Kaj

    2013-01-01

    A reaction calorimeter was used to measure the differential heat of absorption of CO2 in phase change solvents as a function of temperature, CO2 loading and solvent composition. The measurements were taken for aqueous solutions of 2-(diethylamino)ethanol (DEEA), 3-(methylamino)propylamine (MAPA......) and their mixture. The tested compositions were 5M DEEA, 2M MAPA and their mixture, 5M DEEA + 2M MAPA which gives two liquid phases on reacting with CO2. Experimental measurements were also carried out for 30% MEA used as a base case. The measurements were taken isothermally at three different temperatures 40, 80...... and 120°C at a CO2 feed pressure of 600kPa. In single aqueous amine solutions, heat of absorption increases with increase in temperature and depends on thetype of amine used. DEEA, a tertiary amine, has lower heat of absorption compared to MAPA being a diamine with primary and secondary amine functional...

  1. Glass-Forming Ability of Soda Lime Borate Liquids

    DEFF Research Database (Denmark)

    Zheng, Qiuju; Mauro, J.C.; Smedskjær, Morten Mattrup

    2012-01-01

    We investigate the composition dependence of glass-forming ability (GFA) of a series of iron-containing soda lime borate liquids by substituting Na2O for B2O3. We have characterized GFA by measuring the glass stability against crystallization using a differential scanning calorimeter (DSC......). The results show that the GFA decreases when substituting Na2O for B2O3. Moreover, we find that there is no direct link between the kinetic fragility and GFA for the soda lime borate series studied herein. We have also discovered and clarified a striking thermal history dependence of the glass stability...

  2. Understanding the glass-forming ability of active pharmaceutical ingredients for designing supersaturating dosage forms.

    Science.gov (United States)

    Kawakami, Kohsaku; Usui, Toshinori; Hattori, Mitsunari

    2012-09-01

    Amorphous solid dispersions have great potential for enhancing oral absorption of poorly soluble drugs. Crystallization behavior during storage and after exposure to aqueous media must be examined in detail for designing stable and effective amorphous formulations, and it is significantly affected by the intrinsic properties of an amorphous drug. Many attempts have been made to correlate various thermodynamic parameters of pharmaceutical glasses with their crystallization behavior; however, variations in model drugs that could be used for such investigation has been limited because the amorphous characteristics of drugs possessing a high crystallization tendency are difficult to evaluate. In this study, high-speed differential scanning calorimetry, which could inhibit their crystallization using high cooling rates up to 2000°C/s, was employed for assessing such drugs. The thermodynamic parameters of the glasses, including glass transition temperature (T(g)) and fragility, were obtained to show that their crystallization tendency cannot be explained simply by the parameters, although there have been general thought that fragility may be correlated with crystallization tendency. Also investigated was correlation between the thermodynamic parameters and crystallization tendency upon contact with water, which influences in vivo efficacy of amorphous formulations. T(g) was correlated well with the crystallization tendency upon contact with water. Copyright © 2012 Wiley Periodicals, Inc.

  3. Properties of glass-bonded zeolite monoliths

    International Nuclear Information System (INIS)

    Lewis, M.A.; Fischer, D.F.; Murphy, C.D.

    1994-01-01

    It has been shown that mineral waste forms can be used to immobilize waste salt generated during the pyrochemical processing of spent fuel from the Integral Fast Reactor (IFR). Solid, leach resistant monoliths were formed by hot-pressing mixtures of salt-occluded zeolite A powders and glass frit at 990 K and 28 MPa. Additional samples have now been fabricated and tested. Normalized release rates for all elements, including iodide and chloride, were less than 1 g/m 2 d in 28-day tests in deionized water and in brine at 363 K (90 degrees C). Preliminary results indicate that these rates fall with time with both leachants and that the zeolite phase in the glass-bonded zeolite does not function as an ion exchanger. Some material properties were measured. The Poisson ratio and Young's modulus were slightly smaller in glass-bonded zeolite than in borosilicate glass. Density depended on zeolite fraction. The glass-bonded zeolite represents a promising mineral waste form for IFR salt

  4. The production of advanced glass ceramic HLW forms using cold crucible induction melter

    International Nuclear Information System (INIS)

    Rutledge, V.J.; Maio, V.

    2013-01-01

    Cold Crucible Induction Melters (CCIM) will favorably change how High-Level radioactive Waste (from nuclear fuel recovery) is treated in a near future. Unlike the existing Joule-Heated Melters (JHM) currently in operation for the glass-based immobilization of High-Level Waste (HLW), CCIM offers unique material features that will increase melt temperatures, increase throughput, increase mixing, increase loading in the waste form, lower melter foot prints, eliminate melter corrosion and lower costs. These features not only enhance the technology for producing HLW forms, but also provide advantageous attributes to the waste form by allowing more durable alternatives to glass. It is concluded that glass ceramic waste forms that are tailored to immobilize fission products of HLW can be can be made from the HLW processed with the CCIM. The advantageous higher temperatures reached with the CCIM and unachievable with JHM allows the lanthanides, alkali, alkaline earths, and molybdenum to dissolve into a molten glass. Upon controlled cooling they go into targeted crystalline phases to form a glass ceramic waste form with higher waste loadings than achievable with borosilicate glass waste forms. Natural cooling proves to be too fast for the formation of all targeted crystalline phases

  5. Synthesis and devitrification of high glass-forming ability bulk metallic glasses.

    OpenAIRE

    Huang, Hong.

    2007-01-01

    In this thesis, literature on the production, microstructures and properties of bulk metallic glasses (BMG) has been reviewed with particular reference to glass forming ability (GFA) and alloys of the Fe-Zr-B and Zr-based BMG systems. The experimental procedures used in the research are presented and the results for the amorphous Fe80Zr12B8 ribbon and the Zr57Ti5Al10Cu20Ni8, Zr57Nb5Al10Cu20Ni8, Zr53Nb2Al8Cu30Ni7 BMGs are given and discussed. Wedge-shaped ingots of the Zr-based BMGs were produ...

  6. Unusual glass-forming ability induced by changes in the local atomic structure in Ti-based bulk metallic glass

    International Nuclear Information System (INIS)

    Kim, Y C; Chang, H J; Kim, D H; Kim, W T; Cha, P R

    2007-01-01

    The effect of partial replacement of Cu by Be in Ti 50 Cu 32 Ni 15 Sn 3 alloy on the thermal properties, structure, and forming ability of an amorphous phase were investigated by differential scanning calorimetry (DSC), x-ray diffraction (XRD), extended x-ray absorption fine structure (EXAFS), and high-resolution transmission electron microscopy (HRTEM). Ti 50 Cu 25 Ni 15 Sn 3 Be 7 alloy shows enhanced glass-forming ability, enabling one to fabricate a fully amorphous bulk metallic glass sample 2 mm in diameter by injection casting. With the replacement, the supercooled liquid region ΔT x (= T x -T g , where T x is the crystallization temperature and T g is the glass transition temperature) decreased from 73 to 45 K and the reduced glass transition temperature T rg (= T g /T 1 , where T 1 is the liquidus temperature) increased from 0.53 to 0.57. The amorphous Ti 50 Cu 25 Ni 15 Sn 3 Be 7 phase showed a formation of short-range-ordered clusters 1-2 nm in size, which is attributed to the strong interaction between Ti and Be. The results show that ΔT x can be used as a thermal parameter reflecting the glass-forming ability of the alloy only when the phase formed during crystallization is the same as the phase competing with the glass transition during solidification

  7. Evaluation of lead-iron-phosphate glass as a high-level waste form

    International Nuclear Information System (INIS)

    Chick, L.A.; Bunnell, L.R.; Strachan, D.M.; Kissinger, H.E.; Hodges, F.N.

    1986-01-01

    The lead-iron-phosphate (Pb-Fe-P) nuclear waste glass developed at Oak Ridge National Laboratory (ORNL) was evaluated for its potential as an improvement over the current reference waste form, borosilicate (B-Si) glass. Vitreous Pb-Fe-P glass appears to have substantially better chemical durability than B-Si glass. However, severe crystallization leading to deteriorated chemical durability would result if this glass were poured into large canisters, as is presently done with B-Si glass. Cesium leach rates from this crystallized material are orders of magnitude greater than those from B-Si glass. Therefore, to realize the performance advantages of the Pb-Fe-P material in a nuclear waste form, it would be necessary to process it so that it is cooled rapidly, thus retaining its vitreous structure

  8. Evaluation of lead-iron-phosphate glass as a high-level waste form

    International Nuclear Information System (INIS)

    Chick, L.A.; Bunnell, L.R.; Strachan, D.M.; Kissinger, H.E.; Hodges, F.N.

    1986-01-01

    The lead-iron-phosphate nuclear waste glass developed at Oak Ridge National Laboratory (ORNL) was evaluated for its potential as an improvement over the current reference waste form, borosilicate glass. Vitreous lead-iron-phosphate glass appears to have substantially better chemical durability than borosilicate glass. However, severe crystallization leading to deteriorated chemical durability would result if this glass were poured into large canisters as is presently done with borosilicate glass. Cesium leach rates from this crystallized material are orders of magnitude greater than those from borosilicate glass. Therefore, in order to realize the performance advantages of the lead-iron-phosphate material in a nuclear waste form, it would be necessary to process it so that it is rapidly cooled, thus retaining its vitreous structure. 22 refs., 4 figs., 4 tabs

  9. Lead-iron phosophate glass

    International Nuclear Information System (INIS)

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

    1988-01-01

    The lead-iron phosphate nuclear waste glasses (LIPNWG) are the subject of the present chapter. They were discovered in 1984 while the authors were attempting to find a sintering aid for certain types of crystalline monazite ceramic high-level nuclear waste forms. In the present chapter, the term waste glass is synonymous with nuclear waste glass (NWG), and the acronym LIP is often used for lead-iron phosphate. Lead-iron phosphate glasses, like many of the previously studied phosphate glasses, are corrosion resistant in aqueous solutions at temperatures below 100 degrees C, and they can be melted and poured at temperatures that are relatively low in comparison with the processing temperatures required for current silicate glass compositions. Unlike the phosphate glasses investigated previously, however, LIPNWGs do not suffer from alteration due to devitrification during realistic and readily, achievable cooling periods. Additionally, lead-iron phosphate glass melts are not nearly as corrosive as the sodium phosphate melts investigated during the 1960s; and, therefore, they can be melted and processed using crucibles made from a variety of materials

  10. Bulk glass formation and crystallization in zirconium based bulk metallic glass forming alloys

    International Nuclear Information System (INIS)

    Savalia, R.T.; Neogy, S.; Dey, G.K.; Banerjee, S.

    2002-01-01

    The microstructures of Zr based metallic glasses produced in bulk form have been described in the as-cast condition and after crystallization. Various microscopic techniques have been used to characterize the microstructures. The microstructure in the as-cast condition was found to contain isolated crystals and crystalline aggregates embedded in the amorphous matrix. Quenched-in nuclei of crystalline phases were found to be present in fully amorphous regions. These glasses after crystallization gave rise to nanocrystalline solids. (author)

  11. Detection of hypoxanthine, xanthine and uric acid in γ-irradiated aqueous solution of cytosine

    International Nuclear Information System (INIS)

    Kobayashi, Tsuya; Shirai, Kazuo

    1979-01-01

    The aqueous solution of cytosine of 3.6 x 10 -2 M was irradiated with gamma -ray (60 megarad) in nitrogen-saturated glass ampules, and freeze-dried, then the residue obtained was changed to trimethylsilylacid, and this was analyzed by paper chromatography, UV spectrometry, and/or gas-liquid chromatography. Hypoxanthine, xanthine and uric acid were detected in this solution, in addition to some other compounds already known to be produced by gamma -irradiation, e.g., TMS-uracil, TMS-6-hydroxyuracil and TMS-hypoxanthine. It was presumed that these compounds were formed by the recombination of the primary radiolytic products. Uric acid formation by this mechanism was confirmed by gamma -irradiation of the mixture that contained urea, and 5- and 6-hydroxyuracil. (Kaihara, S.)

  12. Predicting glass-forming compositions in the Al-La and Al-La-Ni systems

    International Nuclear Information System (INIS)

    Gargarella, P.; de Oliveira, M.F.; Kiminami, C.S.; Pauly, S.; Kuehn, U.; Bolfarini, C.; Botta, W.J.; Eckert, J.

    2011-01-01

    Research highlights: → The glass-forming ability of the Al-La and Al-La-Ni systems was studied using the λ* and the λ.Δe criteria. → Both criteria predicted with just 1% at. of error the best glass-former verified so far in the Al-La system. → Four new glass-former compositions could be predicted in the Al-La-Ni system using the λ.Δe criterion. → The best glass-former reported so far in the Al-La-Ni system was found. - Abstract: In this work, a criterion considering the topological instability (λ) and the differences in the electronegativity of the constituent elements (Δe) was applied to the Al-La and Al-Ni-La systems in order to predict the best glass-forming compositions. The results were compared with literature data and with our own experimental data for the Al-La-Ni system. The alloy described in the literature as the best glass former in the Al-La system is located near the point with local maximum for the λ.Δe criterion. A good agreement was found between the predictions of the λ.Δe criterion and literature data in the Al-La-Ni system, with the region of the best glass-forming ability (GFA) and largest supercooled liquid region (ΔT x ) coinciding with the best compositional region for amorphization indicated by the λ.Δe criterion. Four new glassy compositions were found in the Al-La-Ni system, with the best predicted composition presenting the best glass-forming ability observed so far for this system. Although the λ.Δe criterion needs further refinements for completely describe the glass-forming ability in the Al-La and Al-La-Ni systems, the results demonstrated that this criterion is a good tool to predict new glass-forming compositions.

  13. Glass-Ceramic Waste Forms for Uranium and Plutonium Residues Wastes - 13164

    International Nuclear Information System (INIS)

    Stewart, Martin W.A.; Moricca, Sam A.; Zhang, Yingjie; Day, R. Arthur; Begg, Bruce D.; Scales, Charlie R.; Maddrell, Ewan R.; Hobbs, Jeff

    2013-01-01

    A program of work has been undertaken to treat plutonium-residues wastes at Sellafield. These have arisen from past fuel development work and are highly variable in both physical and chemical composition. The principal radiological elements present are U and Pu, with small amounts of Th. The waste packages contain Pu in amounts that are too low to be economically recycled as fuel and too high to be disposed of as lower level Pu contaminated material. NNL and ANSTO have developed full-ceramic and glass-ceramic waste forms in which hot-isostatic pressing is used as the consolidation step to safely immobilize the waste into a form suitable for long-term disposition. We discuss development work on the glass-ceramic developed for impure waste streams, in particular the effect of variations in the waste feed chemistry glass-ceramic. The waste chemistry was categorized into actinides, impurity cations, glass formers and anions. Variations of the relative amounts of these on the properties and chemistry of the waste form were investigated and the waste form was found to be largely unaffected by these changes. This work mainly discusses the initial trials with Th and U. Later trials with larger variations and work with Pu-doped samples further confirmed the flexibility of the glass-ceramic. (authors)

  14. Volumetric and acoustical properties of aqueous mixtures of N-methyl-2-hydroxyethylammonium propionate at T = (298.15 to 333.15) K

    International Nuclear Information System (INIS)

    Li, Yang; Figueiredo, Eduardo J.P.; Santos, Mário J.S.F.; Santos, Jaime B.; Talavera-Prieto, Nieves M.C.; Carvalho, Pedro J.; Ferreira, Abel G.M.; Mattedi, Silvana

    2015-01-01

    Highlights: • Density, and speed of sound for aqueous mixtures of [m2HEA]Pr were measured. • Apparent molar volumes and apparent molar isentropic compressibilities were derived. • Excess properties were calculated and correlated using rational functions. • The molar compressibility the aqueous mixtures was calculated from the Wada’s model. • Appreciable interactions between water and [m2HEA] cation were found. - Abstract: The speed of sound in the ionic liquid (IL) N-methyl-2-hydroxyethylammonium propionate (m2HEAPr) was measured at atmospheric pressure, and over the range of temperatures T = (293.15 to 343.15) K. The speed of sound and density were also measured for aqueous mixtures of the ionic liquid throughout the entire concentration range at temperatures T = (298.15 to 333.15) K and atmospheric pressure. The excess molar volume, excess isentropic compressibility, excess speed of sound, apparent molar volume, and isentropic apparent molar compressibility were calculated from the values of the experimental density and speed of sound. The results were analyzed and are discussed from the point of view of structural changes in the aqueous medium. All the above mentioned properties were correlated with selected analytical functions. The Jouyban–Acree model was used to correlate the density of the mixtures studied with the temperature. The model accuracy was evaluated by calculating the absolute average deviation (AAD) for the correlation, which is 0.4%. The speed of sound of the m2HEAPr was predicted with the Wu et al. model with a maximum deviation of 2%. The molar compressibility of m2HEAPr and their aqueous mixtures was calculated from the Wada’s model. To the authors’ knowledge, this is the first time this model is applied to these systems. The results demonstrate that the molar compressibility calculated from Wada’s model is almost a linear function of mole fraction and can be considered as temperature independent for a fixed mole fraction

  15. Thermal forming of glass microsheets for x-ray telescope mirror segments

    DEFF Research Database (Denmark)

    Jimenez-Garate, M.A.; Hailey, C.J.; Craig, W.W.

    2003-01-01

    envisioned for future x-ray observatories. The glass microsheets are shaped into mirror segments at high temperature by use of a guiding mandrel, without polishing. We determine the physical properties and mechanisms that elucidate the formation process and that are crucial to improve surface quality. We......We describe a technology to mass-produce ultrathin mirror substrates for x-ray telescopes of near Wolter-I geometry. Thermal glass forming is a low-cost method to produce high-throughput, spaceborne x-ray mirrors for the 0.1-200-keV energy band. These substrates can provide the collecting area...... develop a viscodynamic model for the glass strain as the forming proceeds to find the conditions for repeatability. Thermal forming preserves the x-ray reflectance and scattering properties of the raw glass. The imaging resolution is driven by a large wavelength figure. We discuss the sources of figure...

  16. Magnesium-phosphate-glass cements with ceramic-type properties

    Science.gov (United States)

    Sugama, T.; Kukacka, L.E.

    1982-09-23

    Rapid setting magnesium phosphate (Mg glass) cementitious materials consisting of magnesium phosphate cement paste, polyborax and water-saturated aggregate, exhibits rapid setting and high early strength characteristics. The magnesium glass cement is prepared from a cation-leachable powder and a bivalent metallic ion-accepting liquid such as an aqueous solution of diammonium phosphate and ammonium polyphosphate. The cation-leachable powder includes a mixture of two different magnesium oxide powders processed and sized differently which when mixed with the bivalent metallic ion-accepting liquid provides the magnesium glass cement consisting primarily of magnesium ortho phosphate tetrahydrate, with magnesium hydroxide and magnesium ammonium phosphate hexahydrate also present. The polyborax serves as a set-retarder. The resulting magnesium mono- and polyphosphate cements are particularly suitable for use as a cementing matrix in rapid repair systems for deteriorated concrete structures as well as construction materials and surface coatings for fireproof structures.

  17. Magnesium phosphate glass cements with ceramic-type properties

    Science.gov (United States)

    Sugama, Toshifumi; Kukacka, Lawrence E.

    1984-03-13

    Rapid setting magnesium phosphate (Mg glass) cementitious materials consisting of magnesium phosphate cement paste, polyborax and water-saturated aggregate exhibiting rapid setting and high early strength characteristics. The magnesium glass cement is prepared from a cation-leachable powder and a bivalent metallic ion-accepting liquid such as an aqueous solution of diammonium phosphate and ammonium polyphosphate. The cation-leachable powder includes a mixture of two different magnesium oxide powders processed and sized differently which when mixed with the bivalent metallic ion-accepting liquid provides the magnesium glass cement consisting primarily of magnesium ortho phosphate tetrahydrate, with magnesium hydroxide and magnesium ammonium phosphate hexahydrate also present. The polyborax serves as a set-retarder. The resulting magnesium mono- and polyphosphate cements are particularly suitable for use as a cementing matrix in rapid repair systems for deteriorated concrete structures as well as construction materials and surface coatings for fireproof structures.

  18. Fast and slow crystal growth kinetics in glass-forming melts

    Energy Technology Data Exchange (ETDEWEB)

    Orava, J.; Greer, A. L., E-mail: alg13@cam.ac.uk [WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan and Department of Materials Science and Metallurgy, 27 Charles Babbage Road, University of Cambridge, Cambridge CB3 0FS (United Kingdom)

    2014-06-07

    Published values of crystal growth rates are compared for supercooled glass-forming liquids undergoing congruent freezing at a planar crystal-liquid interface. For the purposes of comparison pure metals are considered to be glass-forming systems, using data from molecular-dynamics simulations. For each system, the growth rate has a maximum value U{sub max} at a temperature T{sub max} that lies between the glass-transition temperature T{sub g} and the melting temperature T{sub m}. A classification is suggested, based on the lability (specifically, the propensity for fast crystallization), of the liquid. High-lability systems show “fast” growth characterized by a high U{sub max}, a low T{sub max} / T{sub m}, and a very broad peak in U vs. T / T{sub m}. In contrast, systems showing “slow” growth have a low U{sub max}, a high T{sub max} / T{sub m}, and a sharp peak in U vs. T / T{sub m}. Despite the difference of more than 11 orders of magnitude in U{sub max} seen in pure metals and in silica, the range of glass-forming systems surveyed fit into a common pattern in which the lability increases with lower reduced glass-transition temperature (T{sub g} / T{sub m}) and higher fragility of the liquid. A single parameter, a linear combination of T{sub g} / T{sub m} and fragility, can show a good correlation with U{sub max}. For all the systems, growth at U{sub max} is coupled to the atomic/molecular mobility in the liquid. It is found that, across the diversity of glass-forming systems, T{sub max} / T{sub g} = 1.48 ± 0.15.

  19. Measurements of thermodynamic and optical properties of selected aqueous organic and organic-inorganic mixtures of atmospheric relevance.

    Science.gov (United States)

    Lienhard, Daniel M; Bones, David L; Zuend, Andreas; Krieger, Ulrich K; Reid, Jonathan P; Peter, Thomas

    2012-10-11

    Atmospheric aerosol particles can exhibit liquid solution concentrations supersaturated with respect to the dissolved organic and inorganic species and supercooled with respect to ice. In this study, thermodynamic and optical properties of sub- and supersaturated aqueous solutions of atmospheric interest are presented. The density, refractive index, water activity, ice melting temperatures, and homogeneous ice freezing temperatures of binary aqueous solutions containing L(+)-tartaric acid, tannic acid, and levoglucosan and ternary aqueous solutions containing levoglucosan and one of the salts NH(4)HSO(4), (NH(4))(2)SO(4), and NH(4)NO(3) have been measured in the supersaturated concentration range for the first time. In addition, the density and refractive index of binary aqueous citric acid and raffinose solutions and the glass transition temperatures of binary aqueous L(+)-tartaric acid and levoglucosan solutions have been measured. The data presented here are derived from experiments on single levitated microdroplets and bulk solutions and should find application in thermodynamic and atmospheric aerosol models as well as in food science applications.

  20. Transparent form-active system with structural glass

    NARCIS (Netherlands)

    Nikolaou, M.S.N.; Veer, F.A.; Eigenraam, P.

    2015-01-01

    Free-form transparent wide-span spatial structures which have being constructed so far, are based on the concept of three sets of components, the structural components, usually steel elements to ensure both compressive and tensional capacity; the glass cladding elements for expressing transparency;

  1. Glass forming ability: Miedema approach to (Zr, Ti, Hf)-(Cu, Ni) binary and ternary alloys

    Energy Technology Data Exchange (ETDEWEB)

    Basu, Joysurya [Department of Chemical, Materials and Biomolecular Engineering, 191 Auditorium Road, University of Connecticut, Storrs 06269, CT (United States)], E-mail: jbasu@engr.uconn.edu; Murty, B.S. [Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600036 (India); Ranganathan, S. [Department of Materials Engineering, Indian Institute of Science, Bangalore 560012 (India)

    2008-10-06

    Miedema's approach has been useful in determining the glass forming composition range for a particular alloy system. The concept of mixing enthalpy and mismatch entropy can be used in order to quantify Inoue's criteria of bulk metallic glass formation. In the present study, glass forming composition range has been determined for different binary and ternary (Zr, Ti, Hf)-(Cu, Ni) alloys based on the mixing enthalpy and mismatch entropy calculations. Though copper and nickel appear next to each other in the periodic table, the glass forming ability of the copper and nickel bearing alloys is different. Thermodynamic analysis reveals that the glass forming behaviour of Zr and Hf is similar, whereas it is different from that of Ti. The smaller atomic size of Ti and the difference in the heat of mixing of Ti, Zr, Hf with Cu and Ni leads to the observed changes in the glass forming behaviour. Enthalpy contour plots can be used to distinguish the glass forming compositions on the basis of the increasing negative enthalpy of the composition. This method reveals the high glass forming ability of binary Zr-Cu, Hf-Cu, Hf-Ni systems over a narrow composition range.

  2. A new parameter to evaluate the glass-forming ability of bulk metallic glasses

    International Nuclear Information System (INIS)

    Suo, Z.Y.; Qiu, K.Q.; Li, Q.F.; You, J.H.; Ren, Y.L.; Hu, Z.Q.

    2010-01-01

    Research highlights: → Develop a new criterion, i.e., Q=((T g +T x )/T l ).(ΔE/ΔH). → The reliability and benefits of the new criterion have been demonstrated in a wide range of BMG alloys. → It corresponds well with the critical diameter of BMGs investigated up to now. - Abstract: Based on the consideration of the liquid phase stability, the resistance to crystallization and the glass transition enthalpy, a new criterion Q, defined as ((T g + T x )/T l ).(ΔE/ΔH), where the T g , T x , T l , ΔE and ΔH are the glass transition temperature, the onset crystallization temperature, the liquidus temperature, the crystalline enthalpy and the fusion enthalpy, respectively, has been proposed for evaluating the glass-forming ability of bulk metallic glasses. The new criterion Q exhibits better correlation with the maximum cross section thickness (D m ) for glass formation compared with γ (=T x /(T l + T g )), T rg (=T g /T l ) and ΔT x (=T x - T g ) respectively. The available data from literatures and experiments have confirmed the effectiveness of the newly developed criterion.

  3. R7T7 glass alteration mechanism in an aqueous closed system: understanding and modelling the long term alteration kinetic

    International Nuclear Information System (INIS)

    Chave, T.

    2007-10-01

    The long term alteration rate of the French R7T7 nuclear glass has been investigated since many years because it will define the overall resistance of the radionuclide containment matrix. Recent studies have shown that the final rate remains constant or is slightly decreasing with time. It never reaches zero. Though this residual rate is very low, only 5 nm per year at 50 C, it would be the dominant alteration phenomenon in a geological repository. Two mechanisms are suggested for explaining such behaviour: diffusion in solution of elements from glass through an amorphous altered layer and precipitation of neo-formed phases. The diffusion processes are in agreement with a solid state diffusion mechanism and can lead to secondary phase precipitation due to solution concentration increases. Observed phases are mainly phyllosilicates and zeolites, in specific conditions. Phyllosilicates are expected to maintain the residual kinetic rate whereas alteration resumption could be observed in presence of zeolites at very high pH or temperature (10.5 at 90 C or temperature above 150 C). Both diffusion and neo-formed phase precipitation have been investigated in order to better understand their impact on the residual alteration rate and have then been modelled by a calculation code, coupling chemistry and transport, in order to be able to better anticipate the long term behaviour of the glass R7T7 in an aqueous closed system. (author)

  4. The use of positrons to survey alteration layers on synthetic nuclear waste glasses

    International Nuclear Information System (INIS)

    Reiser, Joelle T.; Parruzot, Benjamin; Weber, Marc H.; Ryan, Joseph V.; McCloy, John S.; Wall, Nathalie A.

    2017-01-01

    In order to safeguard society and the environment, understanding radioactive waste glass alteration mechanisms in interactions with solutions and near-field materials, such as Fe, is essential to nuclear waste repository performance assessments. Alteration products are formed at the surface of glasses after reaction with solution. In this study, glass altered in the presence of Fe 0 in aqueous solution formed two alteration layers: one embedded with Fe closer to the surface and one without Fe found deeper in the sample. Both layers were found to be thinner than the alteration layer found in glass altered in aqueous solution only. For the first time, Doppler Broadening Positron Annihilation Spectroscopy (DB-PAS) is used to non-destructively characterize the pore structures of glass altered in the presence of Fe 0 . Advantages and disadvantages of DB-PAS compared to other techniques used to analyze pore structures for altered glass samples are discussed. Ultimately, DB-PAS has shown to be an excellent choice for pore structure characterization for glasses with multiple alteration layers. Monte Carlo modeling predicted positron trajectories through the layers, and helped explain DB-PAS data, which showed that the deeper alteration layer without Fe had a similar composition and pore structure to layers on glass altered in water only.

  5. The use of positrons to survey alteration layers on synthetic nuclear waste glasses

    Energy Technology Data Exchange (ETDEWEB)

    Reiser, Joelle T. [Washington State University, Chemistry Department, Pullman, WA 99164 (United States); Pacific Northwest National Laboratory, Energy and Environment Directorate, Richland, WA 99352 (United States); Parruzot, Benjamin [Pacific Northwest National Laboratory, Energy and Environment Directorate, Richland, WA 99352 (United States); Weber, Marc H. [Washington State University, Center for Materials Research, Pullman, WA 99164 (United States); Ryan, Joseph V., E-mail: joe.ryan@pnnl.gov [Pacific Northwest National Laboratory, Energy and Environment Directorate, Richland, WA 99352 (United States); McCloy, John S. [Washington State University, Chemistry Department, Pullman, WA 99164 (United States); Pacific Northwest National Laboratory, Energy and Environment Directorate, Richland, WA 99352 (United States); Washington State University, School of Mechanical and Materials Engineering, Pullman, WA 99164 (United States); Wall, Nathalie A., E-mail: nawall@wsu.edu [Washington State University, Chemistry Department, Pullman, WA 99164 (United States)

    2017-07-15

    In order to safeguard society and the environment, understanding radioactive waste glass alteration mechanisms in interactions with solutions and near-field materials, such as Fe, is essential to nuclear waste repository performance assessments. Alteration products are formed at the surface of glasses after reaction with solution. In this study, glass altered in the presence of Fe{sup 0} in aqueous solution formed two alteration layers: one embedded with Fe closer to the surface and one without Fe found deeper in the sample. Both layers were found to be thinner than the alteration layer found in glass altered in aqueous solution only. For the first time, Doppler Broadening Positron Annihilation Spectroscopy (DB-PAS) is used to non-destructively characterize the pore structures of glass altered in the presence of Fe{sup 0}. Advantages and disadvantages of DB-PAS compared to other techniques used to analyze pore structures for altered glass samples are discussed. Ultimately, DB-PAS has shown to be an excellent choice for pore structure characterization for glasses with multiple alteration layers. Monte Carlo modeling predicted positron trajectories through the layers, and helped explain DB-PAS data, which showed that the deeper alteration layer without Fe had a similar composition and pore structure to layers on glass altered in water only.

  6. The use of positrons to survey alteration layers on synthetic nuclear waste glasses

    Science.gov (United States)

    Reiser, Joelle T.; Parruzot, Benjamin; Weber, Marc H.; Ryan, Joseph V.; McCloy, John S.; Wall, Nathalie A.

    2017-07-01

    In order to safeguard society and the environment, understanding radioactive waste glass alteration mechanisms in interactions with solutions and near-field materials, such as Fe, is essential to nuclear waste repository performance assessments. Alteration products are formed at the surface of glasses after reaction with solution. In this study, glass altered in the presence of Fe0 in aqueous solution formed two alteration layers: one embedded with Fe closer to the surface and one without Fe found deeper in the sample. Both layers were found to be thinner than the alteration layer found in glass altered in aqueous solution only. For the first time, Doppler Broadening Positron Annihilation Spectroscopy (DB-PAS) is used to non-destructively characterize the pore structures of glass altered in the presence of Fe0. Advantages and disadvantages of DB-PAS compared to other techniques used to analyze pore structures for altered glass samples are discussed. Ultimately, DB-PAS has shown to be an excellent choice for pore structure characterization for glasses with multiple alteration layers. Monte Carlo modeling predicted positron trajectories through the layers, and helped explain DB-PAS data, which showed that the deeper alteration layer without Fe had a similar composition and pore structure to layers on glass altered in water only.

  7. Removal and recovery of nitrogen and sulfur oxides from gaseous mixtures containing them

    International Nuclear Information System (INIS)

    Cooper, H.B.H.

    1984-01-01

    A cyclic process for removing lower valence nitrogen oxides from gaseous mixtures includes treating the mixtures with an aqueous media including alkali metal carbonate and alkali metal bicarbonate and a preoxygen oxidant to form higher valence nitrogen oxides and to capture these oxides as alkali metal salts, expecially nitrites and nitrates, in a carbonate/bicarbonate-containing product aqueous media. Highly selective recovery of nitrates in high purity and yield may then follow, as by crystallization, with the carbonate and bicarbonate alkali metal salts strongly increasing the selectivity and yield of nitrates. The product nitrites are converted to nitrates by oxidation after lowering the product aqueous media pH to below about 9. A cyclic process for removing sulfur oxides from gas mixtures includes treating these mixtures includes treating these mixtures with aqueous media including alkali metal carbonate and alkali metal bicarbonate where the ratio of alkali metal to sulfur dioxide is not less than 2. The sulfur values may be recovered from the resulting carbonate/bicarbonate/-sulfite containing product aqueous media as alkali metal sulfate or sulfite salts which are removed by crystallization from the carbonate-containing product aqueous media. As with the nitrates, the carbonate/bicarbonate system strongly increases yield of sulfate or sulfite during crystallization. Where the gas mixtures include both sulfur dioxide and lower valence nitrogen oxides, the processes for removing lower valence nitrogen oxides and sulfur dioxide may be combined into a single removal/recovery system, or may be effected in sequence

  8. Low sintering temperature glass waste forms for sequestering radioactive iodine

    Science.gov (United States)

    Nenoff, Tina M.; Krumhansl, James L.; Garino, Terry J.; Ockwig, Nathan W.

    2012-09-11

    Materials and methods of making low-sintering-temperature glass waste forms that sequester radioactive iodine in a strong and durable structure. First, the iodine is captured by an adsorbant, which forms an iodine-loaded material, e.g., AgI, AgI-zeolite, AgI-mordenite, Ag-silica aerogel, ZnI.sub.2, CuI, or Bi.sub.5O.sub.7I. Next, particles of the iodine-loaded material are mixed with powdered frits of low-sintering-temperature glasses (comprising various oxides of Si, B, Bi, Pb, and Zn), and then sintered at a relatively low temperature, ranging from 425.degree. C. to 550.degree. C. The sintering converts the mixed powders into a solid block of a glassy waste form, having low iodine leaching rates. The vitrified glassy waste form can contain as much as 60 wt % AgI. A preferred glass, having a sintering temperature of 500.degree. C. (below the silver iodide sublimation temperature of 500.degree. C.) was identified that contains oxides of boron, bismuth, and zinc, while containing essentially no lead or silicon.

  9. Effects of aqueous environment on long-term durability of phosphate-bonded ceramic waste forms

    International Nuclear Information System (INIS)

    Singh, D.; Wagh, A.S.; Jeong, S.Y.

    1996-01-01

    Over the last few years, Argonne National Laboratory has been developing room-temperature-setting chemically-bonded phosphate ceramics for solidifying and stabilizing low-level mixed wastes. This technology is crucial for stabilizing waste streams that contain volatile species and off-gas secondary waste streams generated by high-temperature treatment of such wastes. Magnesium phosphate ceramic has been developed to treat mixed wastes such as ash, salts, and cement sludges. Waste forms of surrogate waste streams were fabricated by acid-base reactions between the mixtures of magnesium oxide powders and the wastes, and phosphoric acid or acid phosphate solutions. Dense and hard ceramic waste forms are produced in this process. The principal advantage of this technology is that the contaminants are immobilized by both chemical stabilization and subsequent microencapsulation of the reaction products. This paper reports the results of durability studies conducted on waste forms made with ash waste streams spiked with hazardous and radioactive surrogates. Standard leaching tests such as ANS 16.1 and TCLP were conducted on the final waste forms. Fates of the contaminants in the final waste forms were established by electron microscopy. In addition, stability of the waste forms in aqueous environments was evaluated with long-term water-immersion tests

  10. Technetium Immobilization Forms Literature Survey

    Energy Technology Data Exchange (ETDEWEB)

    Westsik, Joseph H.; Cantrell, Kirk J.; Serne, R. Jeffrey; Qafoku, Nikolla

    2014-05-01

    Of the many radionuclides and contaminants in the tank wastes stored at the Hanford site, technetium-99 (99Tc) is one of the most challenging to effectively immobilize in a waste form for ultimate disposal. Within the Hanford Tank Waste Treatment and Immobilization Plant (WTP), the Tc will partition between both the high-level waste (HLW) and low-activity waste (LAW) fractions of the tank waste. The HLW fraction will be converted to a glass waste form in the HLW vitrification facility and the LAW fraction will be converted to another glass waste form in the LAW vitrification facility. In both vitrification facilities, the Tc is incorporated into the glass waste form but a significant fraction of the Tc volatilizes at the high glass-melting temperatures and is captured in the off-gas treatment systems at both facilities. The aqueous off-gas condensate solution containing the volatilized Tc is recycled and is added to the LAW glass melter feed. This recycle process is effective in increasing the loading of Tc in the LAW glass but it also disproportionally increases the sulfur and halides in the LAW melter feed which increases both the amount of LAW glass and either the duration of the LAW vitrification mission or the required supplemental LAW treatment capacity.

  11. LIQUIDUS TEMPERATURE AND ONE PERCENT CRYSTAL CONTENT MODELS FOR INITIAL HANFORD HLW GLASSES

    International Nuclear Information System (INIS)

    Vienna, John D.; Edwards, Tommy B.; Crum, Jarrod V.; Kim, Dong-Sang; Peeler, David K.

    2005-01-01

    Preliminary models for liquidus temperature (TL) and temperature at 1 vol% crystal (T01) applicable to WTP HLW glasses in the spinel primary phase field were developed. A series of literature model forms were evaluated using consistent sets of data form model fitting and validation. For TL, the ion potential and linear mixture models performed best, while for T01 the linear mixture model out performed all other model forms. TL models were able to predict with smaller uncertainty. However, the lower T01 values (even with higher prediction uncertainties) were found to allow for a much broader processing envelope for WTP HLW glasses

  12. Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

    Directory of Open Access Journals (Sweden)

    N. Sareen

    2016-11-01

    Full Text Available Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols, leading to the formation of secondary organic aerosol (SOAAQ. Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS. Hydroxyl (OH⚫ radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS. Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS spectra and tandem MS (MS–MS fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and

  13. The Production of Advanced Glass Ceramic HLW Forms using Cold Crucible Induction Melter

    Energy Technology Data Exchange (ETDEWEB)

    Veronica J Rutledge; Vince Maio

    2013-10-01

    Cold Crucible Induction Melters (CCIMs) will favorably change how High-Level radioactive Waste (from nuclear fuel recovery) is treated in the 21st century. Unlike the existing Joule-Heated Melters (JHMs) currently in operation for the glass-based immobilization of High-Level Waste (HLW), CCIMs offer unique material features that will increase melt temperatures, increase throughput, increase mixing, increase loading in the waste form, lower melter foot prints, eliminate melter corrosion and lower costs. These features not only enhance the technology for producing HLW forms, but also provide advantageous attributes to the waste form by allowing more durable alternatives to glass. This paper discusses advantageous features of the CCIM, with emphasis on features that overcome the historical issues with the JHMs presently utilized, as well as the benefits of glass ceramic waste forms over borosilicate glass waste forms. These advantages are then validated based on recent INL testing to demonstrate a first-of-a-kind formulation of a non-radioactive ceramic-based waste form utilizing a CCIM.

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

    International Nuclear Information System (INIS)

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

    1993-02-01

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

  15. Contribution of electron microscopy to the study of alteration layers formed on the surface of glasses

    International Nuclear Information System (INIS)

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

    1985-01-01

    In order to understand the whole process of glass corrosion in aqueous solutions, the analysis of the reagent must be completed by a study of the actual alteration layers on the glass surface. Transmission electron microscopy on ultramicrotomic thin sections turns out to be a most suitable tool to achieve this. It enables to supplement the conventional methods of surface investigation, such as A.E.S., ESCA, IRRS, SIMS. Two examples are given. The first deals with a (SiO 2 -CaO-Na 2 O-P 2 O 5 )- glass leached in a buffer solution of tris-hydromethyl-aminomethane at 40 0 C. The major feature is ion exchange within a residual porous glass, followed by the precipitation of hydroxyapatite. In the second example, a basaltic glass is altered in sea-water at 50 0 C. The glass constituents are dissolved simultaneously and the alteration layer is a precipitate of crystalline and amorphous phases which have reached their saturation level [fr

  16. Liquid -to-glass transition in bulk glass-forming Cu55-xZr45Agx alloys using molecular dynamic simulations

    Directory of Open Access Journals (Sweden)

    Celtek M.

    2011-05-01

    Full Text Available We report results from molecular dynamics (MD studies concerning the microscopic structure of the ternary, bulk metallic glass-forming Cu55-x Zr45Agx (x=0,10,20 alloys using tight-binding potentials. Understanding of the nature of Glass Forming Ability (GFA of studied alloys, GFA parameters, glass transition temperature (T-g, melting temperature (T-m, reduced glass transition temperature (T-g/T-m, the supercooled liquid region and other parameters were simulated and compared with experiments. The computed pair distribution functions reproduce well experimental x-ray data of Inoue and co-workers. Structure analysis of the Cu-Zr-Ag alloy based on MD simulation will be also presented

  17. Using mixture experiments to develop cementitious waste forms

    International Nuclear Information System (INIS)

    Spence, R.D.; Anderson, C.M.; Piepel, G.F.

    1993-01-01

    Mixture experiments are presented as a means to develop cementitious waste forms. The steps of a mixture experiment are (1) identifying the waste form ingredients; (2) determining the compositional constraints of these ingredients; (3) determining the extreme vertices, edge midpoints, and face centroids of the constrained multidimensional volume (these points along with some interior points represent the set of possible compositions for testing); (4) picking a subset of these points for the experimental design; (5) measuring the properties of the selected subset; and (6) generating the response surface models. The models provide a means for predicting the properties within the constrained region. This article presents an example of this process for one property: unconfined compressive strength

  18. Development of basic data for modelling the residual alteration rate in aqueous media of AVM nuclear glasses

    International Nuclear Information System (INIS)

    Thien, B.

    2010-01-01

    During their aqueous alteration, AVM French nuclear glasses exhibit a large range of behaviour, in spite of a small range of composition. AVM glasses alteration rates are controlled by two phenomena: (i) precipitation of secondary phases, mostly aluminous hectorites, and (ii) diffusion of water across a more or less protective gel. The magnesium contained in these glasses increases the precipitation of these secondary phases, leading to a partial or total dissolution of the gel layer. This dissolution increases the glass alteration rates. On the other hand, Mg also incorporates in the gel, increasing his passivation properties. The predominance of one of these two phenomena depends on the initial composition of the glass, the pH of the solution, and the alteration conditions. In presence of Bure geological disposal site water (Mg and Ca rich), AVM glasses undergo less alteration than in initially pure water, in spite of larger amounts of secondary phase precipitates. This results from incorporation of calcium in the gel instead of sodium and magnesium, improving its passivating properties. We have adapted the geochemical GRAAL model for AVM glasses. In spite of its limitations, this model allows us to describe the differences of behaviour between these glasses, in function of their composition. Moreover, GRAAL can be proposed as a basis of a future operational model for predicting the alteration of AVM glasses. (author) [fr

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

    International Nuclear Information System (INIS)

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

    1994-01-01

    The dissolution kinetics of the French open-quotes R7T7close 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 -1 , showed that the glass dissolution surface reaction is catalyzed by humic acids. With higher degrees of reaction progress (SA/V = 100 m -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 -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

  20. Economic comparison of crystalline ceramic and glass waste forms for HLW disposal

    International Nuclear Information System (INIS)

    McKee, R.W.; Daling, P.M.; Wiles, L.E.

    1983-05-01

    A titanate-based, crystalline ceramic produced by hot isostatic pressing has been proposed as a potentially more stable and improved waste form for high-level nuclear waste disposal compared to the currently favored borosilicate glass waste form. This paper describes the results of a study to evaluate the relative costs for disposal of high-level waste from a 70,000 metric ton equivalent (MTE) system. The entire waste management system, including waste processing and encapsulation, transportation, and final repository disposal, was included in this analysis. The repository concept is based on the current basalt waste isolation project (BWIP) reference design. A range of design basis alternatives is considered to determine if this would influence the relative economics of the two waste forms. A thermal analysis procedure was utilized to define optimum canister sizes to assure that each waste form was compared under favorable conditions. Repository costs are found to favor the borosilicate glass waste form while transportation costs greatly favor the crystalline ceramic waste form. The determining component in the cost comparison is the waste processing cost, which strongly favors the borosilicate glass process because of its relative simplicity. A net cost advantage on the order of 12% to 15% on a waste management system basis is indicated for the glass waste form

  1. Preparation of glass-forming materials from granulated blast furnace slag

    Science.gov (United States)

    Alonso, M.; Sáinz, E.; Lopez, F. A.

    1996-10-01

    Glass precursor materials, to be used for the vitrification of hazardous wastes, have been prepared from blast furnace slag powder through a sol-gel route. The slag is initially reacted with a mixture of alcohol (ethanol or methanol) and mineral acid (HNO3 or H2SO4) to give a sol principally consisting of Si, Ca, Al, and Mg alkoxides. Gelation is carried out with variable amounts of either ammonia or water. The gelation rate can be made as fast as desired by adding excess hydrolizing agent or else by distilling the excess alcohol out of the alkoxide solution. The resulting gel is first dried at low temperature and ground. The powder thus obtained is then heat treated at several temperatures. The intermediate and final materials are characterized by thermal analysis, infrared (IR) spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), and chemical analysis. From the results, the operating conditions yielding a variety of glass precursors differing in their composition are established. The method, in comparison with direct vitrification of slag, presents a number of advantages: (1) the glass precursor obtained devitrifies at higher temperatures; (2) it enables the adjustment, to a certain extent, of the chemical composition of the glass precursor; and (3) it permits recovering marketable materials at different stages of the process.

  2. Hydrophobic fluorine mediated switching of the hydrogen bonding site as well as orientation of water molecules in the aqueous mixture of monofluoroethanol: IR, molecular dynamics and quantum chemical studies.

    Science.gov (United States)

    Mondal, Saptarsi; Biswas, Biswajit; Nandy, Tonima; Singh, Prashant Chandra

    2017-09-20

    The local structures between water-water, alcohol-water and alcohol-alcohol have been investigated for aqueous mixtures of ethanol (ETH) and monofluoroethanol (MFE) by the deconvolution of IR bands in the OH stretching region, molecular dynamics simulation and quantum chemical calculations. It has been found that the addition of a small amount of ETH into the aqueous medium increases the strength of the hydrogen bonds between water molecules. In an aqueous mixture of MFE, the substitution of a single fluorine induces a change in the orientation as well as the hydrogen bonding site of water molecules from the oxygen to the fluorine terminal of MFE. The switching of the hydrogen bonding site of water in the aqueous mixture of MFE results in comparatively strong hydrogen bonds between MFE and water molecules as well as less clustering of water molecules, unlike the case of the aqueous mixture of ETH. These findings about the modification of a hydrogen bond network by the hydrophobic fluorine group probably make fluorinated molecules useful for pharmaceutical as well as biological applications.

  3. Study of L-ascorbic acid (vitamin C)/H 2O mixture across glass transition

    Science.gov (United States)

    Migliardo, F.; Branca, C.; Faraone, A.; Magazù, S.; Migliardo, P.

    2001-07-01

    In this paper, we report quasi elastic neutron scattering (QENS) spectra of vitamin C aqueous solutions, obtained using MIBEMOL spectrometer (LLB). The main purpose of this work is to characterize the relaxational and vibrational properties of the Vitamin C/H 2O system below and above the glass transition temperature by analysing the low-frequency neutron scattering spectra. The determination of the relative weight of vibrational over relaxational contributions allows to get information on the fragility degree of this peculiar hydrogen-bond system.

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

    International Nuclear Information System (INIS)

    Pavel Hrma; Pert Schill; Lubomir Nemec

    2002-01-01

    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

  5. Linking structure to fragility in bulk metallic glass-forming liquids

    International Nuclear Information System (INIS)

    Wei, Shuai; Stolpe, Moritz; Gross, Oliver; Gallino, Isabella; Hembree, William; Busch, Ralf; Evenson, Zach; Bednarcik, Jozef; Kruzic, Jamie J.

    2015-01-01

    Using in-situ synchrotron X-ray scattering, we show that the structural evolution of various bulk metallic glass-forming liquids can be quantitatively connected to their viscosity behavior in the supercooled liquid near T g . The structural signature of fragility is identified as the temperature dependence of local dilatation on distinct key atomic length scales. A more fragile behavior results from a more pronounced thermally induced dilatation of the structure on a length scale of about 3 to 4 atomic diameters, coupled with shallower temperature dependence of structural changes in the nearest neighbor environment. These findings shed light on the structural origin of viscous slowdown during undercooling of bulk metallic glass-forming liquids and demonstrate the promise of predicting the properties of bulk metallic glasses from the atomic scale structure

  6. Linking structure to fragility in bulk metallic glass-forming liquids

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Shuai, E-mail: shuai.wei@asu.edu, E-mail: m.stolpe@mx.uni-saarland.de [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287 (United States); Stolpe, Moritz, E-mail: shuai.wei@asu.edu, E-mail: m.stolpe@mx.uni-saarland.de; Gross, Oliver; Gallino, Isabella; Hembree, William; Busch, Ralf [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Evenson, Zach [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und Raumfahrt (DLR), 51170 Köln (Germany); Bednarcik, Jozef [Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, D-22603 Hamburg (Germany); Kruzic, Jamie J. [Material Science, School of Mechanical, Industrial, and Manufacturing Engineering, Oregon State University, Corvallis, Oregon 97331 (United States)

    2015-05-04

    Using in-situ synchrotron X-ray scattering, we show that the structural evolution of various bulk metallic glass-forming liquids can be quantitatively connected to their viscosity behavior in the supercooled liquid near T{sub g}. The structural signature of fragility is identified as the temperature dependence of local dilatation on distinct key atomic length scales. A more fragile behavior results from a more pronounced thermally induced dilatation of the structure on a length scale of about 3 to 4 atomic diameters, coupled with shallower temperature dependence of structural changes in the nearest neighbor environment. These findings shed light on the structural origin of viscous slowdown during undercooling of bulk metallic glass-forming liquids and demonstrate the promise of predicting the properties of bulk metallic glasses from the atomic scale structure.

  7. Glass composite waste forms for iodine confined in bismuth-embedded SBA-15

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jae Hwan [Nuclear Fuel Cycle Process Development Division, Korea Atomic Energy Research Institute, 989-111 Daeduk-daero, Yuseong-gu, Daejeon, 305-353 (Korea, Republic of); Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon, 305-701 (Korea, Republic of); Park, Hwan Seo; Ahn, Do-Hee [Nuclear Fuel Cycle Process Development Division, Korea Atomic Energy Research Institute, 989-111 Daeduk-daero, Yuseong-gu, Daejeon, 305-353 (Korea, Republic of); Yim, Man-Sung, E-mail: msyim@kaist.ac.kr [Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon, 305-701 (Korea, Republic of)

    2016-11-15

    The aim of this study was to stabilize bismuth-embedded SBA-15 that captured iodine gas by fabrication of monolithic waste forms. The iodine containing waste was mixed with Bi{sub 2}O{sub 3} (a stabilizing additive) and low-temperature sintering glass followed by pelletizing and the sintering process to produce glass composite materials. Iodine volatility during the sintering process was significantly affected by the ratio of Bi{sub 2}O{sub 3} and the glass composition. It was confirmed that BiI{sub 3}, the main iodine phase within bismuth-embedded SBA-15, was effectively transformed to the mixed phases of Bi{sub 5}O{sub 7}I and BiOI. The initial leaching rates of iodine from the glass composite waste forms ranged 10{sup −3}–10{sup −2} g/m{sup 2} day, showing the stability of the iodine phases encapsulated by the glassy networks. It was also observed that common groundwater anions (e.g., chloride, carbonate, sulfite, and fluoride) elevated the iodine leaching rate by anion exchange reactions. The present results suggest that the glass composite waste form of bismuth-embedded SBA-15 could be a candidate material for stable storage of {sup 129}I. - Highlights: • Glass composite waste forms were developed to stabilize iodine confined in Bi-embedded SBA-15. • BiI{sub 3} within Bi-embedded SBA-15 was transformed to BiOI and Bi{sub 5}O{sub 7}I during sintering process. • Iodine volatility was significantly affected by glass composition and Bi{sub 2}O{sub 3} additive. • Iodine leaching rates were 10{sup −3}–10{sup −2} g/m{sup 2} day due to the stable iodine phases encapsulated by glassy networks. • Glass composite waste form of Bi-embedded SBA-15 is expected to be a candidate material for stable storage of {sup 129}I.

  8. Glass polymorphism in glycerol–water mixtures: II. Experimental studies

    Science.gov (United States)

    Bachler, Johannes; Fuentes-Landete, Violeta; Jahn, David A.; Wong, Jessina; Giovambattista, Nicolas

    2016-01-01

    We report a detailed experimental study of (i) pressure-induced transformations in glycerol–water mixtures at T = 77 K and P = 0–1.8 GPa, and (ii) heating-induced transformations of glycerol–water mixtures recovered at 1 atm and T = 77 K. Our samples are prepared by cooling the solutions at ambient pressure at various cooling rates (100 K s–1–10 K h–1) and for the whole range of glycerol mole fractions, χ g. Depending on concentration and cooling rates, cooling leads to samples containing amorphous ice (χ g ≥ 0.20), ice (χ g ≤ 0.32), and/or “distorted ice” (0 HDA). PIA of ice domains within the glycerol–water mixtures is shown to be possible only up to χ g ≈ 0.32 (T = 77 K). This is rather surprising since it has been known that at χ g HDA upon compression. Upon heating samples recovered at 1 atm, we observe a rich phase behavior. Differential scanning calorimetry indicates that only at χ g ≤ 0.15, the water domains within the sample exhibit polyamorphism, i.e., the HDA-to-LDA (low-density amorphous ice) transformation. At 0.15 HDA domains. All samples (χ g ≤ 0.38) show: the crystallization of amorphous ice domains, followed by the glass transition of the vitrified glycerol–water domains and, finally, the melting of ice at high temperatures. Our work exemplifies the complex “phase” behavior of glassy binary mixtures due to phase-separation (ice formation) and polyamorphism, and the relevance of sample preparation, concentration as well as cooling rates. The presence of the distorted ice (called “interphase” by us) also explains the debated “drift anomaly” upon melting. These results are compatible with the high-pressure study by Suzuki and Mishima indicating disappearance of polyamorphism at P ≈ 0.03–0.05 GPa at χ g ≈ 0.12–0.15 [J. Chem. Phys., 2014, 141, 094505]. PMID:27044677

  9. Glass-Forming Ability and Early Crystallization Kinetics of Novel Cu-Zr-Al-Co Bulk Metallic Glasses

    Directory of Open Access Journals (Sweden)

    Xiaoliang Han

    2016-09-01

    Full Text Available In recent years, CuZr-based bulk metallic glass (BMG composites ductilized by a shape memory B2 CuZr phase have attracted great attention owing to their outstanding mechanical properties. However, the B2 CuZr phase for most CuZr-based glass-forming compositions is only stable at very high temperatures, leading to the uncontrollable formation of B2 crystals during quenching. In this work, by introducing Co (i.e., 4, 5, and 6 at. % and 10 at. % Al into CuZr-based alloys, the relatively good glass-forming ability (GFA of CuZr-based alloys still can be achieved. Meanwhile, the B2 phase can be successfully stabilized to lower temperatures than the final temperatures of crystallization upon heating CuZr-based BMGs. Unlike previous reported CuZr-based BMGs, the primary crystallization products upon heating are mainly B2 CuZr crystals but not CuZr2 and Cu10Zr7 crystals. Furthermore, the primary precipitates during solidification are still dominated by B2 crystals, whose percolation threshold is detected to lie between 10 ± 2 vol. % and 31 ± 2 vol. %. The crystallization kinetics underlying the precipitation of B2 crystals was also investigated. Our results show that the present glass-forming composites are promising candidates for the fabrication of ductile CuZr-based BMG composites.

  10. Glass Forming Ability of Amorphous Drugs Investigated by Continuous Cooling and Isothermal Transformation.

    Science.gov (United States)

    Blaabjerg, Lasse I; Lindenberg, Eleanor; Löbmann, Korbinian; Grohganz, Holger; Rades, Thomas

    2016-09-06

    The aim of this study was to investigate the glass forming ability of 12 different drugs by the determination of continuous cooling and isothermal transformation diagrams in order to elucidate if an inherent differentiation between the drugs with respect to their the glass forming ability can be made. Continuous-cooling-transformation (CCT) and time-temperature-transformation (TTT) diagrams of the drugs were developed in order to predict the critical cooling rate necessary to convert the drug from the melt into an amorphous form. While TTT diagrams overestimated the actual critical cooling rate, they allowed an inherent differentiation of glass forming ability for the investigated drugs into drugs that are extremely difficult to amorphize (>750 °C/min), drugs that require modest cooling rates (>10 °C/min), and drugs that can be made amorphous even at very slow cooling rates (>2 °C/min). Thus, the glass forming ability can be predicted by the use of TTT diagrams. In contrast to TTT diagrams, CCT diagrams may not be suitable for small organic molecules due to poor separation of exothermic events, which makes it difficult to determine the zone of recrystallization. In conclusion, this study shows that glass forming ability of drugs can be predicted by TTT diagrams.

  11. Role of lead as modifier on the properties of lead iron phosphate nuclear waste glasses

    International Nuclear Information System (INIS)

    Hazra, G.; Mitra, P.; Das, T.

    2011-01-01

    Lead-iron phosphate glasses are a promising new waste form for the safe immobilization of both high level defence and high level commercial radioactive waste for long term disposal. Lead iron phosphate glasses have several advantages such as lower aqueous corrosion rate, lower processing temperature etc. (author)

  12. UTILIZATION OF AQUEOUS-TAR CONDENSATES FORMED DURING GASIFICATION

    Directory of Open Access Journals (Sweden)

    Anna Kwiecińska

    2016-11-01

    Full Text Available Gasification of solid fuels is an alternative process for energy production using conventional and renewable fuels. Apart from desired compounds, i.e. carbon oxide, hydrogen and methane, the produced gas contains complex organic (tars and inorganic (carbonizate, ammonia contaminants. Those substances, together with water vapor, condensate during cooling of the process gas, what results in the formation of aqueous-tar condensate, which requires proper methods of utilization. The management of this stream is crucial for commercialization and application of the gasification technology. In the paper the treatment of aqueous-tar condensates formed during biomass gasification process is discussed. The removal of tars from the stream was based on their spontaneous separation. The aqueous stream was subjected to ultrafiltration operated at different pressures. Such a treatment configuration enabled to obtain highly concentrated retentate, which could be recycled to the gasifier, and filtrate, which could be subjected to further treatment.

  13. Lead-iron phosphate glass: a stable storage medium for high-level nuclear waste

    International Nuclear Information System (INIS)

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

    1984-01-01

    Results are presented which show that lead-iron phosphate glasses are a promising new waste form for the safe immobilization of both high-level defense and high-level commercial radioactive waste. Relative to the borosilicate nuclear waste glasses that are currently the ''reference'' waste form for the long-term disposal of nuclear waste, lead-iron phosphate glasses have several distinct advantages: (1) an aqueous corrosion rate that is about 1000 times lower, (2) a processing temperature that is 100 0 to 250 0 C lower and, (3) a much lower melt viscosity in the temperature range from 800 0 to 1000 0 C. Most significantly, the lead-iron phosphate waste form can be processed using a technology similar to that developed for borosilicate nuclear waste glasses

  14. High level waste forms: glass marbles and thermal spray coatings

    International Nuclear Information System (INIS)

    Treat, R.L.; Oma, K.H.; Slate, S.C.

    1982-01-01

    A process that converts high-level waste to glass marbles and then coats the marbles has been developed at Pacific Northwest Laboratory (PNL) under sponsorship of the US Department of Energy. The process consists of a joule-heated glass melter, a marble-making device based on a patent issued to Corning Glass Works, and a coating system that includes a plasma spray coater and a marble tumbler. The process was developed under the Alternative Waste Forms Program which strived to improve upon monolithic glass for immobilizing high-level wastes. Coated glass marbles were found to be more leach-resistant, and the marbles, before coating were found to be very homogeneous, highly impact resistant, and conductive to encapsulation in a metal matric for improved heat transfer and containment. Marbles are also ideally suited for quality assurance and recycling. However, the marble process is more complex, and marbles require a larger number of canisters for waste containment and have a higher surface area than do glass monoliths

  15. Study on mechanical properties of fly ash impregnated glass fiber reinforced polymer composites using mixture design analysis

    International Nuclear Information System (INIS)

    Satheesh Raja, R.; Manisekar, K.; Manikandan, V.

    2014-01-01

    Highlights: • FRP with and without fly ash filler were prepared. • Mechanical properties of composites were analyzed. • Mixture Design Method was used to model the system. • Experimental and mathematical model results were compared. - Abstract: This paper describes the mechanical behavior of fly ash impregnated E-glass fiber reinforced polymer composite (GFRP). Initially the proportion of fiber and resin were optimized from the analysis of the mechanical properties of the GFRP. It is observed that the 30 wt% of E-glass in the GFRP without filler material yields better results. Then, based on the optimized value of resin content, the varying percentage of E-glass and fly ash was added to fabricate the hybrid composites. Results obtained in this study were mathematically evaluated using Mixture Design Method. Predictions show that 10 wt% addition of fly ash with fiber improves the mechanical properties of the composites. The fly ash impregnated GFRP yields significant improvement in mechanical strength compared to the GFRP without filler material. The surface morphologies of the fractured specimens were characterized using Scanning Electron Microscope (SEM). The chemical composition and surface morphology of the fly ash is analyzed by using Energy Dispersive Spectroscopy (EDS) and Scanning Electron Microscope

  16. Glass composite waste forms for iodine confined in bismuth-embedded SBA-15

    Science.gov (United States)

    Yang, Jae Hwan; Park, Hwan Seo; Ahn, Do-Hee; Yim, Man-Sung

    2016-11-01

    The aim of this study was to stabilize bismuth-embedded SBA-15 that captured iodine gas by fabrication of monolithic waste forms. The iodine containing waste was mixed with Bi2O3 (a stabilizing additive) and low-temperature sintering glass followed by pelletizing and the sintering process to produce glass composite materials. Iodine volatility during the sintering process was significantly affected by the ratio of Bi2O3 and the glass composition. It was confirmed that BiI3, the main iodine phase within bismuth-embedded SBA-15, was effectively transformed to the mixed phases of Bi5O7I and BiOI. The initial leaching rates of iodine from the glass composite waste forms ranged 10-3-10-2 g/m2 day, showing the stability of the iodine phases encapsulated by the glassy networks. It was also observed that common groundwater anions (e.g., chloride, carbonate, sulfite, and fluoride) elevated the iodine leaching rate by anion exchange reactions. The present results suggest that the glass composite waste form of bismuth-embedded SBA-15 could be a candidate material for stable storage of 129I.

  17. Study of the Boson Peak and Fragility of Bioprotectant Glass-Forming Mixtures by Neutron Scattering

    Directory of Open Access Journals (Sweden)

    F. Migliardo

    2013-01-01

    Full Text Available The biological relevance of trehalose, glycerol, and their mixtures in several anhydrobiotic and cryobiotic organisms has recently promoted both experimental and simulation studies. In addition, these systems are employed in different industrial fields, such as pharmaceutical and cosmetic industries, as additives in mixtures for cryopreservation and in several formulations. This review article shows an overview of Inelastic Neutron Scattering (INS data, collected at different temperature values by the OSIRIS time-of-flight spectrometer at the ISIS Facility (Rutherford Appleton Laboratory, Oxford, UK and by the IN4 and IN6 spectrometers at the Institut Laue Langevin (ILL, Grenoble, France, on trehalose/glycerol mixtures as a function of the glycerol content. The data analysis allows determining the Boson peak behavior and discussing the findings in terms of fragility in relation to the bioprotective action of trehalose and glycerol.

  18. Polyphase ceramic and glass-ceramic forms for immobilizing ICPP high-level nuclear waste

    International Nuclear Information System (INIS)

    Harker, A.B.; Flintoff, J.F.

    1984-01-01

    Polyphase ceramic and glass-ceramic forms have been consolidated from simulated Idaho Chemical Processing Plant wastes by hot isostatic pressing calcined waste and chemical additives by 1000 0 C or less. The ceramic forms can contain over 70 wt% waste with densities ranging from 3.5 to 3.85 g/cm 3 , depending upon the formulation. Major phases are CaF 2 , CaZrTi 207 , CaTiO 3 , monoclinic ZrO 2 , and amorphous intergranular material. The relative fraction of the phases is a function of the chemical additives (TiO 2 , CaO, and SiO 2 ) and consolidation temperature. Zirconolite, the major actinide host, makes the ceramic forms extremely leach resistant for the actinide simulant U 238 . The amorphous phase controls the leach performance for Sr and Cs which is improved by the addition of SiO 2 . Glass-ceramic forms were also consolidated by HIP at waste loadings of 30 to 70 wt% with densities of 2.73 to 3.1 g/cm 3 using Exxon 127 borosilicate glass frit. The glass-ceramic forms contain crystalline CaF 2 , Al 203 , and ZrSi 04 (zircon) in a glass matrix. Natural mineral zircon is a stable host for 4+ valent actinides. 17 references, 3 figures, 5 tables

  19. Selection of a glass-ceramic formulation to immobilize fluorinel- sodium calcine

    International Nuclear Information System (INIS)

    Staples, B.A.; Wood, H.C.

    1994-12-01

    One option for immobilizing calcined high level wastes produced by nuclear fuel reprocessing activities at the Idaho Chemical Processing Plant (ICPP) is conversion to a glass-ceramic form through hot isostatic pressing. Calcines exist in several different chemical compositions, and thus candidate formulations have been developed for converting each to glass-ceramic forms which are potentially resistant to aqueous corrosion and stable enough to qualify for repository storage. Fluorinel/Na, a chemically complex calcine type, is one of the types being stored at ICPP, and development efforts have identified three formulations with potential for immobilizing it. These are a glass forming additive that uses aluminum metal to enhance reactivity, a second glass forming additive that uses titanium metal to enhance reactivity and a third that uses not only a combination of silicon and titanium metals but enough phosphorous pentoxide to form a calcium phosphate host phase in the glass-ceramic product. Glass-ceramics of each formulation performed well in restricted characterization tests. However, none of the three was subjected to rigorous testing that would provide information on whether each was processable, that is able to retain favorable characteristics over a practical range of processing conditions

  20. A slow atomic diffusion process in high-entropy glass-forming metallic melts

    Science.gov (United States)

    Chen, Changjiu; Wong, Kaikin; Krishnan, Rithin P.; Embs, Jan P.; Chathoth, Suresh M.

    2018-04-01

    Quasi-elastic neutron scattering has been used to study atomic relaxation processes in high-entropy glass-forming metallic melts with different glass-forming ability (GFA). The momentum transfer dependence of mean relaxation time shows a highly collective atomic transport process in the alloy melts with the highest and lowest GFA. However, a jump diffusion process is the long-range atomic transport process in the intermediate GFA alloy melt. Nevertheless, atomic mobility close to the melting temperature of these alloy melts is quite similar, and the temperature dependence of the diffusion coefficient exhibits a non-Arrhenius behavior. The atomic mobility in these high-entropy melts is much slower than that of the best glass-forming melts at their respective melting temperatures.

  1. Diffusion in confinement as a microscopic relaxation mechanism in glass-forming liquids

    International Nuclear Information System (INIS)

    Mamontov, Eugene

    2012-01-01

    Using quasielastic neutron scattering, we compare dynamics in single-element liquids, glass-forming selenium and non glass-forming gallium. There is a single jump-diffusion process in gallium, whereas in selenium there is also a faster, spatially localized process. The fast and slow processes describe β- and α-relaxation, respectively. We then analyze an archetypical glass-former, glycerol, to show that the two-component fit, with β- and α-relaxations explicitly separated, yields the correct value for the translational diffusion coefficient and provides information on the spatial localization of the β-relaxation that is not experimentally accessible otherwise.

  2. Effect of high pressure on the relaxation dynamics of glass-forming liquids

    Energy Technology Data Exchange (ETDEWEB)

    Paluch, M; Grzybowska, K; Grzybowski, A [Institute of Physics, Silesian University, ulica Uniwersytecka 4, 40-007 Katowice (Poland)

    2007-05-23

    A glass is usually formed by cooling a liquid at a rate sufficient to avoid crystallization. In the vicinity of the glass transition the structural relaxation time increases with lowering temperature in a non-Arrhenius fashion and the structural relaxation function reveals a non-Debye behaviour. However, liquid can be also vitrified by keeping it at a constant temperature and increasing the pressure. This pressure-induced transition to the glassy state is also accompanied by dramatic changes in the relaxation dynamics. Herein we discuss the behaviour of the structural relaxation times of glass-forming liquids and polymer melts under high pressure.

  3. Effect of high pressure on the relaxation dynamics of glass-forming liquids

    International Nuclear Information System (INIS)

    Paluch, M; Grzybowska, K; Grzybowski, A

    2007-01-01

    A glass is usually formed by cooling a liquid at a rate sufficient to avoid crystallization. In the vicinity of the glass transition the structural relaxation time increases with lowering temperature in a non-Arrhenius fashion and the structural relaxation function reveals a non-Debye behaviour. However, liquid can be also vitrified by keeping it at a constant temperature and increasing the pressure. This pressure-induced transition to the glassy state is also accompanied by dramatic changes in the relaxation dynamics. Herein we discuss the behaviour of the structural relaxation times of glass-forming liquids and polymer melts under high pressure

  4. Plan for glass waste form testing for NNWSI [Nevada Nuclear Waste Storage Investigations

    International Nuclear Information System (INIS)

    Aines, R.D.

    1987-09-01

    The purpose of glass waste form testing is to determine the rate of release of radionuclides from breached glass waste containers. This information will be used to qualify glass waste forms with respect to the release requirements. It will be the basis of the source term from glass waste for repository performance assessment modeling. This information will also serve as part of the source term in the calculation of cumulative releases after 100,000 years in the site evaluation process. It will also serve as part of the source term input for calculation of cumulative releases to the accessible environment for 10,000 years after disposal, to determine compliance with EPA regulations. This investigation will provide data to resolve information needs. Information about the waste forms which is provided by the producer will be accumulated and evaluated; the waste form will be tested, properties determined, and mechanisms of degradation determined; and models providing long-term evaluation of release rates designed and tested. 23 refs

  5. Component effects in mixture experiments

    International Nuclear Information System (INIS)

    Piepel, G.F.

    1980-01-01

    In a mixture experiment, the response to a mixture of q components is a function of the proportions x 1 , x 2 , ..., x/sub q/ of components in the mixture. Experimental regions for mixture experiments are often defined by constraints on the proportions of the components forming the mixture. The usual (orthogonal direction) definition of a factor effect does not apply because of the dependence imposed by the mixture restriction, /sup q/Σ/sub i=1/ x/sub i/ = 1. A direction within the experimental region in which to compute a mixture component effect is presented and compared to previously suggested directions. This new direction has none of the inadequacies or errors of previous suggestions while having a more meaningful interpretation. The distinction between partial and total effects is made. The uses of partial and total effects (computed using the new direction) in modification and interpretation of mixture response prediction equations are considered. The suggestions of the paper are illustrated in an example from a glass development study in a waste vitrification program. 5 figures, 3 tables

  6. Effect of aluminum and silicon reactants and process parameters on glass-ceramic waste form characteristics for immobilization of high-level fluorinel-sodium calcined waste

    International Nuclear Information System (INIS)

    Vinjamuri, K.

    1993-06-01

    In this report, the effects of aluminum and silicon reactants, process soak time and the initial calcine particle size on glass-ceramic waste form characteristics for immobilization of the high-level fluorinel-sodium calcined waste stored at the Idaho Chemical Processing Plant (ICPP) are investigated. The waste form characteristics include density, total and normalized elemental leach rates, and microstructure. Glass-ceramic waste forms were prepared by hot isostatically pressing (HIPing) a pre-compacted mixture of pilot plant fluorinel-sodium calcine, Al, and Si metal powders at 1050 degrees C, 20,000 psi for 4 hours. One of the formulations with 2 wt % Al was HIPed for 4, 8, 16 and 24 hours at the same temperature and pressure. The calcine particle size range include as calcined particle size smaller than 600 μm (finer than -30 mesh, or 215 μm Mass Median Diameter, MMD) and 180 μm (finer than 80 mesh, or 49 μm MMD)

  7. Durability, mechanical, and thermal properties of experimental glass-ceramic forms for immobilizing ICPP high level waste

    International Nuclear Information System (INIS)

    Vinjamuri, K.

    1990-01-01

    The high-level liquid waste generated at the Idaho Chemical Processing Plant (ICPP) is routinely solidified into granular calcined high-level waste (HLW) and stored onsite. Research is being conducted at the ICPP on methods of immobilizing the HLW, including developing a durable glass-ceramic form which has the potential to significantly reduce the final waste volume by up to 60% compared to a glass form. Simulated, pilot plant, non-radioactive, calcines similar to the composition of the calcined HLW and glass forming additives are used to produce experimental glass-ceramic forms. The objective of the research reported in this paper is to study the impact of ground calcine particle size on durability and mechanical and thermal properties of experimental glass-ceramic forms

  8. Molecular glasses for nuclear waste encapsulation

    International Nuclear Information System (INIS)

    Ropp, R.C.

    1982-01-01

    The use of a molecular glass based upon a polymerized phosphate of aluminum (PAP), indium or gallium overcomes all of the prior objections to use of glass as a high-level nuclear waste (HLW) encapsulation agent. This HLW glass product could not be made to devitrify, dissolved all of the oxides found in calcine, including the difficultly soluble ones, did not form microcrystallites in the melt or subsequent glass-casting, and possessed a hydrolytic etching rate to boiling water even lower than that of HLW-ZBS glass. A precursor compound, M(H 2 PO 4 ) 3 , is prepared, where M is a trivalent metal selected from the group consisting of aluminum, indium and gallium. The impurity level is carefully controlled so as not to exceed 300 ppm total. The precursor crystals may be washed to remove excess phosphoric acid as desired. HLW is added to the crystals and the mixture is then heated at a controlled heating rate to induce solid state polymerization and to form a melt at 1350 degrees C in which the HLW oxides dissolve rapidly

  9. Mie scattering in heavy-metal fluoride glasses

    International Nuclear Information System (INIS)

    Edgar, A.

    1996-01-01

    Heavy-metal fluoride glasses comprise mixtures of heavy-cation fluorides such as those of zirconium, barium, and lanthanum together with some stabilising fluorides such as AlF 3 . For particular relative proportions, the mixtures form a glass rather than a polycrystalline material when quenched from the melt. The particularly useful features of these glasses are the wide spectral region (∼200nm-8000nm) over which they are transparent, the low minimum attenuation at the centre of the spectral window, and the ease with which optically-active rare-earth ions can be incorporated, leading to potential applications in passive and active fibre optics. The minimal attenuation, which is potentially lower than for silica fibre, is generally limited by wavelength-independent scattering by particle and gas bubble inclusions. We have observed a new wavelength-dependent scattering effect in fluoride glass of the well-known composition ZLABN20. In this paper, we report on work in progress on the optical extinction and scattering spectrum of the fluoride glasses, and discuss the spectra in terms of Mie's scattering theory. The chemical nature of the scattering centres in these nominally 'pure' glasses is at present a puzzle, and relative merits of various possible models will be compared

  10. Waste E-glass particles used in cementitious mixtures

    International Nuclear Information System (INIS)

    Chen, C.H.; Huang, R.; Wu, J.K.; Yang, C.C.

    2006-01-01

    The properties of concretes containing various waste E-glass particle contents were investigated in this study. Waste E-glass particles were obtained from electronic grade glass yarn scrap by grinding to small particle size. The size distribution of cylindrical glass particle was from 38 to 300 μm and about 40% of E-glass particle was less than 150 μm. The E-glass mainly consists of SiO 2 , Al 2 O 3 , Ca O and MgO, and is indicated as amorphous by X-ray diffraction (XRD) technique. Compressive strength and resistance of sulfate attack and chloride ion penetration were significantly improved by utilizing proper amount of waste E-glass in concrete. The compressive strength of specimen with 40 wt.% E-glass content was 17%, 27% and 43% higher than that of control specimen at age of 28, 91 and 365 days, respectively. E-glass can be used in concrete as cementitious material as well as inert filler, which depending upon the particle size, and the dividing size appears to be 75 μm. The workability decreased as the glass content increased due to reduction of fineness modulus, and the addition of high-range water reducers was needed to obtain a uniform mix. Little difference was observed in ASR testing results between control and E-glass specimens. Based on the properties of hardened concrete, optimum E-glass content was found to be 40-50 wt.%

  11. Effects of Cu substitution for Fe on the glass-forming ability and soft magnetic properties for Fe-based bulk metallic glasses

    International Nuclear Information System (INIS)

    Dou, Lintao; Liu, Haishun; Hou, Long; Xue, Lin; Yang, Weiming; Zhao, Yucheng; Chang, Chuntao

    2014-01-01

    The effects of Cu substitution for Fe on the glass-forming ability (GFA) and soft magnetic properties for Fe 72−x Cu x B 20 Si 4 Nb 4 (x=0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) bulk metallic glasses (BMGs) are investigated. It is found that the investigated BMGs exhibit large GFA as well as excellent soft magnetic properties, and proper substitution of Fe by Cu improves the saturation magnetization, coercive force, and effective permeability without obvious deterioration of the GFA. - Highlights: • Fully glassy rods of Fe 72−x Cu x B 20 Si 4 Nb 4 BMGs were produced above 1 mm in diameter. • Investigated BMGs exhibit large glass-forming ability and excellent soft magnetic properties. • Proper Cu substitution improves magnetic properties without obvious deterioration of glass-forming ability

  12. Investigating the atomic level influencing factors of glass forming ability in NiAl and CuZr metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Sedighi, Sina; Kirk, Donald Walter; Singh, Chandra Veer, E-mail: chandraveer.singh@utoronto.ca; Thorpe, Steven John [Department of Materials Science and Engineering, University of Toronto, Room 140, 184 College Street, Toronto, Ontario M5S 3E4 (Canada)

    2015-09-21

    Bulk metallic glasses are a relatively new class of amorphous metal alloy which possess unique mechanical and magnetic properties. The specific concentrations and combinations of alloy elements needed to prevent crystallization during melt quenching remains poorly understood. A correlation between atomic properties that can explain some of the previously identified glass forming ability (GFA) anomalies of the NiAl and CuZr systems has been identified, with these findings likely extensible to other transition metal–transition metal and transition metal–metalloid (TM–M) alloy classes as a whole. In this work, molecular dynamics simulation methods are utilized to study thermodynamic, kinetic, and structural properties of equiatomic CuZr and NiAl metallic glasses in an attempt to further understand the underlying connections between glass forming ability, nature of atomic level bonding, short and medium range ordering, and the evolution of structure and relaxation properties in the disordered phase. The anomalous breakdown of the fragility parameter as a useful GFA indicator in TM–M alloy systems is addressed through an in-depth investigation of bulk stiffness properties and the evolution of (pseudo)Gruneisen parameters over the quench domain, with the efficacy of other common glass forming ability indicators similarly being analyzed through direct computation in respective CuZr and NiAl systems. Comparison of fractional liquid-crystal density differences in the two systems revealed 2-3 times higher values for the NiAl system, providing further support for its efficacy as a general purpose GFA indicator.

  13. Glass-bonded iodosodalite waste form for immobilization of 129I

    Science.gov (United States)

    Chong, Saehwa; Peterson, Jacob A.; Riley, Brian J.; Tabada, Diana; Wall, Donald; Corkhill, Claire L.; McCloy, John S.

    2018-06-01

    Immobilization of radioiodine is an important requirement for current and future nuclear fuel cycles. Iodosodalite [Na8(AlSiO4)6I2] was synthesized hydrothermally from metakaolin, NaI, and NaOH. Dried unwashed sodalite powders were used to synthesize glass-bonded iodosodalite waste forms (glass composite materials) by heating pressed pellets at 650, 750, or 850 °C with two types of sodium borosilicate glass binders. These heat-treated specimens were characterized with X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal analysis, porosity and density measurements, neutron activation analysis, and inductively-coupled plasma mass spectrometry. For the best waste form produced (pellets mixed with 10 mass% of glass binder and heat-treated at 750 °C), the maximum possible elemental iodine loading was 19.8 mass%, but only ∼8-9 mass% waste loading of iodine was retained in the waste form after thermal processing. Other pellets with higher iodine retention either contained higher porosity or were incompletely sintered. ASTM C1308 and C1285 (product consistency test, PCT) experiments were performed to understand chemical durability under diffusive and static conditions. The C1308 test resulted in significantly higher normalized loss compared to the C1285 test, most likely because of the strong effect of neutral pH solution renewal and prevention of ion saturation in solution. Both experiments indicated that release rates of Na and Si were higher than for Al and I, probably due to a poorly durable Na-Si-O phase from the glass bonding matrix or from initial sodalite synthesis; however the C1308 test result indicated that congruent dissolution of iodosodalite occurred. The average release rates of iodine obtained from C1308 were 0.17 and 1.29 g m-2 d-1 for 80 or 8 m-1, respectively, and the C1285 analysis gave a value of 2 × 10-5 g m-2 d-1, which is comparable to or better than the durability of

  14. Sharp separation of C2/C3 hydrocarbon mixtures by zeolitic imidazolate framework-8 (ZIF-8) membranes synthesized in aqueous solutions

    KAUST Repository

    Pan, Yichang

    2011-01-01

    Exceptional high quality ZIF-8 membranes prepared through a novel seeded growth method in aqueous solutions at near room temperature exhibit excellent separation performance for C2/C3 hydrocarbon mixtures. The separation factors for mixtures of ethane/propane, ethylene/propylene and ethylene/propane are ∼80, ∼10 and ∼167, respectively. © 2011 The Royal Society of Chemistry.

  15. Thermodynamics of the Gd/sub 63.2/Co/sub 36.8/ glass-forming eutectic

    International Nuclear Information System (INIS)

    Baricco, M.; Antonione, C.; Battezzati, L.

    1987-01-01

    In the last years a tendency has consolidated to investigate the properties of the liquid phase in relation to amorphization. The thermodynamic properties of glass-forming liquids show some remarkable similarities and provide a unifying picture for the understanding of glass formation. In particular the specific heat difference between liquid and crystal phases, C/sub P/, seem always positive thus enabling the liquid entropy to approach that of the solid on under-cooling towards the glass transition temperature, T/sub g/. The enthalpy of mixing in glass-forming alloys is strongly negative and depends on temperature giving rise to an excess specific heat. As the liquid and crystalline pure elements have similar specific heat and the Newmann-Kopp law is usually obeyed by solid alloys, the excess specific heat can be assimilated to G. This last quantity, therefore, determines the trend of the thermodynamic properties in the undercooling regime and ultimately the glass-forming tendency of the liquid systems. Specific heat data are available for some liquid alloys but only a few of them refer to glass-forming systems. Typical examples are Au/sub 77/Ge/sub 13.6/Si/sub 9.4/ among metal-metalloid and Mg/sub 85.5/Cu/sub 14.5/ among metal-metal systems. The authors present here a complete determination of the thermodynamic properties of the Gd/sub 63.2/Co/sub 36.8/ eutectic as an example for anthanide transition metal glass-formers. This alloy is low melting so that its liquid state is accessible by differential scanning calorimetry. It forms glasses readily by means of liquid quenching

  16. Spinel dissolution via addition of glass forming chemicals. Results of preliminary experiments

    Energy Technology Data Exchange (ETDEWEB)

    Fox, K. M. [Savannah River Site (SRS), Aiken, SC (United States); Johnson, F. C. [Savannah River Site (SRS), Aiken, SC (United States)

    2015-11-01

    Increased loading of high level waste in glass can lead to crystallization within the glass. Some crystalline species, such as spinel, have no practical impact on the chemical durability of the glass, and therefore may be acceptable from both a processing and a product performance standpoint. In order to operate a melter with a controlled amount of crystallization, options must be developed for remediating an unacceptable accumulation of crystals. This report describes preliminary experiments designed to evaluate the ability to dissolve spinel crystals in simulated waste glass melts via the addition of glass forming chemicals (GFCs).

  17. Characterization and durability testing of a glass-bonded ceramic waste form

    International Nuclear Information System (INIS)

    Johnson, S. G.

    1998-01-01

    Argonne National Laboratory is developing a glass bonded ceramic waste form for encapsulating the fission products and transuranics from the conditioning of metallic reactor fuel. This waste form is currently being scaled to the multi-kilogram size for encapsulation of actual high level waste. This paper will present characterization and durability testing of the ceramic waste form. An emphasis on results from application of glass durability tests such as the Product Consistency Test and characterization methods such as X-ray diffraction and scanning electron microscopy. The information presented is based on a suite of tests utilized for assessing product quality during scale-up and parametric testing

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

    International Nuclear Information System (INIS)

    Day, Delbert D.

    2000-01-01

    As mentioned above, the overall goal of this research project was to collect the scientific information essential to develop iron phosphate glass based nuclear wasteforms. The specific objectives of the project were: (1) Investigate the structure of binary iron phosphate glasses and it's dependence on the composition and melting atmosphere: Understand atomic arrangements and nature of the bonding. Establish structure-property relationships. Determine the compositions and melting conditions which optimize the critical properties of the base glass. (2) Understand the structure of iron phosphate wasteforms and it's dependence on the composition and melting atmosphere: Investigate how the waste elements are bonded and coordinated within the glass structure. Establish structure-property relationships for the waste glasses. Determine the compositions and melting atmosphere for which the critical properties of the waste forms would be optimum. (3) Determine the role(s) played by the valence states of iron ions and it's dependence on the composition and melting atmosphere: Understand the different roles of iron(II) and iron(III) ions in determining the critical properties of the base glass and the waste forms. Investigate how the iron valence and its significance depend on the composition and melting atmosphere. (4) Investigate glass forming and crystallization processes of the iron phosphate glasses and their waste forms: Understand the dependence of the glass forming and crystallization characteristics on overall glass composition and valence states of iron ions. Identify the products of devitrification and investigate the critical properties of these crystalline compounds which may adversely affect the chemical and physical properties of the waste forms

  19. Health effects of acid aerosols formed by atmospheric mixtures

    International Nuclear Information System (INIS)

    Kleinman, M.T.; Phalen, R.F.; Mautz, W.J.; Mannix, R.C.; McClure, T.R.; Crocker, T.T.

    1989-01-01

    Under ambient conditions, sulfur and nitrogen oxides can react with photochemical products and airborne particles to form acidic vapors and aerosols. Inhalation toxicological studies were conducted, exposing laboratory animals, at rest and during exercise, to multicomponent atmospheric mixtures under conditions favorable to the formation of acidic reaction products. Effects of acid and ozone mixtures on early and late clearance of insoluble radioactive particles in the lungs of rats appeared to be dominated by the oxidant component (i.e., the mixture did cause effects that were significantly different from those of ozone alone). Histopathological evaluations showed that sulfuric acid particles alone did not cause inflammatory responses in centriacinar units of rat lung parenchyma (expressed in terms of percent lesion area) but did cause significant damage (cell killing followed by a wave of cell replication) in nasal respiratory epithelium, as measured by uptake of tritiated thymidine in the DNA of replicating cells. Mixtures of ozone and nitrogen dioxide, which form nitric acid, caused significant inflammatory responses in lung parenchyma (in excess of effects seen in rats exposed to ozone alone), but did not damage nasal epithelium. Mixtures containing acidic sulfate particles, ozone, and nitrogen dioxide damaged both lung parenchyma and nasal epithelia. In rats exposed at rest, the response of the lung appeared to be dominated by the oxidant gas-phase components, while responses in the nose were dominated by the acidic particles. In rats exposed at exercise, however, mixtures of ozone and sulfuric acid particles significantly (2.5-fold) elevated the degree of lung lesion formation over that seen in rats exposed to ozone alone under an identical exercise protocol

  20. Effect of Nb on glass forming ability and plasticity of (Ti-Cu)-based bulk metallic glasses

    International Nuclear Information System (INIS)

    Suo, Z.Y.; Qiu, K.Q.; Li, Q.F.; Ren, Y.L.; Hu, Z.Q.

    2010-01-01

    A Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 bulk metallic glass has been developed by Nb partial substitution for Zr in Ti 33 Cu 47 Zr 11 Ni 6 Sn 2 Si 1 alloy. The glass forming ability Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 alloy has been investigated using differential scanning calorimetry and X-ray diffractometry. Partial Nb substitutes for Zr promote the glass forming ability. Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 BMG with diameter of 3 mm can be fabricated by Cu-mold injection casting method. The glass forming ability of Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 alloy is enhanced by stabilizing the undercooled liquid against crystallization. The plastic strain up to 2.5% was obtained for Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 BMG compared to 0.15% for Ti 33 Cu 47 Zr 11 Ni 6 Sn 2 Si 1 BMG, which demonstrates that small amount of Nb addition can have a dramatic effect on plasticity enhancement in Ti-Cu-based BMG. The intersection and branching of the shear bands are observed. The plastic strain of the Ti 33 Cu 47 Zr 9 Ni 6 Sn 2 Si 1 Nb 2 BMG can be improved by the generation of nanocrystalline particles, which lead to multiple shear bands.

  1. The fundamental structural factor in determining the glass-forming ability and mechanical behavior in the Cu-Zr metallic glasses

    International Nuclear Information System (INIS)

    Sha, Z.D.; Feng, Y.P.; Li, Y.

    2011-01-01

    Research highlights: → A weak but significant hump in trend of the coordinate number and density was observed, respectively. → Our findings indicate our simulation is more accurate to describe the atomic structure of Cu-Zr MGs. The composition-structure-properties correlation was established. → And the effective structural unit for this correlation is the Cu-centered full icosahedra. - Abstract: Using the large-scale atomic/molecular massively parallel simulator, the quantitative composition-structure-properties (including glass-forming ability (GFA) and mechanical behavior) correlations in the Cu-Zr metallic glasses were established. The atomic-level origin of these correlations was tracked down. It was found that the Cu-centered full icosahedron is the microscopic factor that fundamentally influences both GFA and mechanical behavior. Our findings have implications for understanding the nature, forming ability and properties of metallic glasses, and for searching novel metallic glasses with unique functional properties.

  2. The influence of ZnO incorporation on the aqueous leaching characteristics of a borosilicate glass

    Science.gov (United States)

    Vance, E. R.; Gregg, D. J.; Karatchevtseva, I.; Griffiths, G. J.; Olufson, K.; Rees, Gregory J.; Hanna, John V.

    2017-10-01

    With increasing ZnO content, short term aqueous durability enhancement of all elements in borosilicate glasses containing 1.0 and 3.85 wt% ZnO was evident in 7-day PCT-B tests. In 14-day MCC-1 type leach tests conducted at 90 °C, surface alteration was very clear in the undoped glass via the formation of strongly altered amorphous material which tended to spall off the surface. No sign of crystallinity was detected by grazing incidence X-ray diffraction or electron microscopy of the surface layers and the surface material was very rich in silica. For the ZnO-bearing glasses, significant growth of particles following PCT leaching for 7 days was observed, due to a build-up of surface ZnO-containing Si-rich material and possible agglomeration. This alteration layer was also observed in MCC-1 type experiments in which cross-section SEM-EDS data were obtained. Raman, infrared and 11B and 29Si MAS NMR spectroscopy showed only slight changes in boron speciation on the addition of up to 9.1 wt% ZnO. Bulk positron annihilation lifetime spectra (PALS) of glasses containing 0-3.85 wt% ZnO could be analysed with three distinct lifetimes and also showed only slight differences. These results indicate that the basic glass structure was essentially not influenced by the ZnO content and that the passivation of the alteration layer is promoted by ZnO content.

  3. Characterization of 'strong-fragile' behaviour of glass-forming aqueous solutions by neutron scattering

    Energy Technology Data Exchange (ETDEWEB)

    Branca, C.; Faraone, A.; Galli, G.; Magazu' , S.; Maisano, G.; Migliardo, F. [Dipartimento di Fisica and INFM, Universita' di Messina, PO Box 55, 98166 Messina (Italy)

    2002-07-01

    Neutron-scattering measurements have been performed on trehalose/H{sub 2}O and sucrose/H{sub 2}O mixtures by using the spectrometer MIBEMOL at the Laboratoire Leon Brillouin (LLB, Saclay) as a function of temperature and concentration. In order to characterize the different rigidities of both the disaccharide/H{sub 2}O mixtures, we have evaluated the R{sub 1}(T{sub g}) parameter connected to the 'strong-fragile' classification of the systems according to Angell's nomenclature. (orig.)

  4. Measurements of the Poisson ratio and fragility of glass-forming liquids

    DEFF Research Database (Denmark)

    Christensen, Tage Emil; Olsen, Niels Boye

    Recently much attention has been given to models and phenomenology of glass-forming liquids that correlates fast and slow degrees of freedom . In particular the Poisson ratio has been correlated with fragility. We present data on shear - and bulk modulus obtained by the techniques...... of the piezoelectric transducers PBG and PSG on a number of glass-forming liquids. Hereby the Poisson ratio can be found. Furthermore the PSG also gives the temperature dependence of shear viscosity and thereby the fragility. The validity of the conjectured relation is discussed...

  5. Undercooling Limits and Thermophysical Properties in Glass Forming Alloys

    Science.gov (United States)

    Rhim, Won-Kyu; Ohsaka, Kenichi; Spjut, R. Erik

    1999-01-01

    The primary objective of this program is to produce deeply undercooled metallic liquids and to identify factors that limit undercooling and glass formation. The main research objectives are: (1) Investigating undercooling limits in glass-forming alloys and identifying factors that affect undercooling; (2) Measuring thermophysical properties and investigating the validity of the classical nucleation theory and other existing theories in the extreme undercooled states; and (3) To investigate the limits of electrostatic levitation technology in the ground base and to identify thermophysical parameters that might require reduced-g environment.

  6. Comparison of SRP high-level waste disposal costs for borosilicate glass and crystalline ceramic waste forms

    International Nuclear Information System (INIS)

    McDonell, W.R.

    1982-04-01

    An evaluation of costs for the immobilization and repository disposal of SRP high-level wastes indicates that the borosilicate glass waste form is less costly than the crystalline ceramic waste form. The wastes were assumed immobilized as glass with 28% waste loading in 10,300 reference 24-in.-diameter canisters or as crystalline ceramic with 65% waste loading in either 3400 24-in.-diameter canisters or 5900 18-in.-diameter canisters. After an interim period of onsite storage, the canisters would be transported to the federal repository for burial. Total costs in undiscounted 1981 dollars of the waste disposal operations, excluding salt processing for which costs are not yet well defined, were about $2500 million for the borosilicate glass form in reference 24-in.-diameter canisters, compared to about $2900 million for the crystalline ceramic form in 24-in.-diameter canisters and about $3100 million for the crystalline ceramic form in 18-in.-diameter canisters. No large differences in salt processing costs for the borosilicate glass and crystalline ceramic forms are expected. Discounting to present values, because of a projected 2-year delay in startup of the DWPF for the crystalline ceramic form, preserved the overall cost advantage of the borosilicate glass form. The waste immobilization operations for the glass form were much less costly than for the crystalline ceramic form. The waste disposal operations, in contrast, were less costly for the crystalline ceramic form, due to fewer canisters requiring disposal; however, this advantage was not sufficient to offset the higher development and processing costs of the crystalline ceramic form. Changes in proposed Nuclear Regulatory Commission regulations to permit lower cost repository packages for defense high-level wastes would decrease the waste disposal costs of the more numerous borosilicate glass forms relative to the crystalline ceramic forms

  7. The analysis of lightweight brick strength pressure with mixture of glass powder and silica fume

    Science.gov (United States)

    Nursyamsi; Liang, William

    2018-03-01

    Little by little the engineers research how the development of concrete that can utilize waste. In the utilization of the waste, it can be functioned as mixing material which the chemical or the physical traits of the used goods contain similarity to the mixture of concrete in general, one of them is glass powder as the substitute of cement. The glass powder that utilizes is the one that is sifted through sieve No. 200 as much as 10% of the weight of the cement. The testing specimen of the concrete brick is make of the mixture with the ratio of 1:7, then is added with the foaming agent (1:30) and silica fume (10% of the weight of the cement). Furthermore, visual examination, absorption, net weight and testing specimen compressive strength. The data analysis uses the reference of SNI 03 – 0349 – 1989 regarding Concrete Brick for the Match for the Wall. Foaming Agent is make by using modified hand drill and brace. The testing specimen uses the brick mold with the size of 40 cm x 20cm x 10 cm. Based on this research, it shows that the quality that results from brick is still qualified based on SNI 03 – 0349 – 1989.

  8. Thermodynamic and relative approach to compute glass-forming

    Indian Academy of Sciences (India)

    This study deals with the evaluation of glass-forming ability (GFA) of oxides and is a critical reading of Sun and Rawson thermodynamic approach to quantify this aptitude. Both approaches are adequate but ambiguous regarding the behaviour of some oxides (tendency to amorphization or crystallization). Indeed, ZrO2 and ...

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

    International Nuclear Information System (INIS)

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

    1994-01-01

    The R7T7 and synthetic basaltic glasses were submitted to corrosion in a saline MgCl 2 dominated solution at 190 degrees C. For both glasses, the early alteration product is a hydrotalcite-like compound in which HPO 4 2- , SO 4 2- and Cl - substitutes to CO 3 2- . The measured d 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

  10. Infrared spectroscopy study of structural changes in glass-forming salol.

    Science.gov (United States)

    Baran, J; Davydova, N A

    2010-03-01

    We report the investigation of glass-forming salol upon different courses of the temperature changes from liquid to glass state and back using FT-IR spectroscopy measurements in the wide spectral and temperature ranges. The formation of the ordered clusters in supercooled liquid salol has been observed at 250 K. When the temperature is decreased further to 11 K these ordered clusters become an element of the glass structure. With increasing temperature to 270 K through the glass transition noticeable evolutions of the IR spectrum occurs up till the ordered clusters are developed into crystal. So produced crystal melts in the temperature range 300-310 K, that corresponds to the melting temperature of the metastable phase (Tmelt=302 K) . Thus, the crystalline structure of the ordered clusters corresponds to the structure of metastable phase and is monoclinic.

  11. Glass and nuclear wastes

    International Nuclear Information System (INIS)

    Sombret, C.

    1982-10-01

    Glass shows interesting technical and economical properties for long term storage of solidified radioactive wastes by vitrification or embedding. Glass composition, vitrification processes, stability under irradiation, thermal stability and aqueous corrosion are studied [fr

  12. Radiation effects in glass waste forms for high-level waste and plutonium disposal

    International Nuclear Information System (INIS)

    Weber, W.J.; Ewing, R.C.

    1997-01-01

    A key challenge in the permanent disposal of high-level waste (HLW), plutonium residues/scraps, and excess weapons plutonium in glass waste forms is the development of predictive models of long-term performance that are based on a sound scientific understanding of relevant phenomena. Radiation effects from β-decay and α-decay can impact the performance of glasses for HLW and Pu disposition through the interactions of the α-particles, β-particles, recoil nuclei, and γ-rays with the atoms in the glass. Recently, a scientific panel convened under the auspices of the DOE Council on Materials Science to assess the current state of understanding, identify important scientific issues, and recommend directions for research in the area of radiation effects in glasses for HLW and Pu disposition. The overall finding of the panel was that there is a critical lack of systematic understanding on radiation effects in glasses at the atomic, microscopic, and macroscopic levels. The current state of understanding on radiation effects in glass waste forms and critical scientific issues are presented

  13. Study of dosimetric systems-ferrous sulfate-ferric sulfate, glass slides and dyed aqueous solutions

    International Nuclear Information System (INIS)

    Fernandes, L.

    1979-01-01

    The effect of some variables which can effect the preparation of the ferrous sulfate used as dosimetric solution has been studied. Among these variables the purity of the water used for the preparation of the solution and the presence (or absence) of oxygen in the dosimetric solution were considered. The dose rate distribution according to the transverse and longitudinal sections of the Co 60 irradiator was studied experimentally, using the dosimetric solution, and theoretically, using a computer program (KIFE). The results obtained with the ferrous sulface dosimetric solution were used as reference for the study of the application of EM and MSG glass slide as a dosimetric system. For this purpose the effects of the weakening of the coloration induced in the glass by gamma rays (Co 60 ) and the relationship between the absorbed dose of radiation and the ratio between the variation in absorbation value and the thickness of the glass irradiated, were studied. A study was also made of the use of the dye indicators bromothymol-blue, methyl-orange, Congo-red, neutral-red and p-nitrophenol, in aqueous solution, for radiation dose measurements. The bleaching of each indicator solution, under gamma-radiation (Co 60 ) was studied in oxygen and nitrogen atmospheres.(Author) [pt

  14. Forming of bulk metallic glass microcomponents

    DEFF Research Database (Denmark)

    Wert, John A.; Thomsen, Christian; Jensen, Rune Debel

    2009-01-01

    The present article considers forward extrusion, closed-die forging and backward extrusion processes for fabrication of individual microcomponents from two bulk metallic glass (BMG) compositions: Mg60Cu30Y10 and Zr44Cu40Ag8Al8. Two types of tooling were used in the present work: relatively massive...... die sets characteristic of cold forming operations for crystalline metals and lightweight die sets adapted to the special characteristics of BMGs. In addition to demonstrating that microcomponents of several geometries can be readily fabricated from BMGs, rheological properties are combined...

  15. Supercooled dynamics of glass-forming liquids and polymers under hydrostatic pressure

    Energy Technology Data Exchange (ETDEWEB)

    Roland, C M [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States); Hensel-Bielowka, S [Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice (Poland); Paluch, M [Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice (Poland); Casalini, R [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States); Chemistry Department, George Mason University, Fairfax, VA 22030 (United States)

    2005-06-01

    An intriguing problem in condensed matter physics is understanding the glass transition, in particular the dynamics in the equilibrium liquid close to vitrification. Recent advances have been made by using hydrostatic pressure as an experimental variable. These results are reviewed, with an emphasis in the insight provided into the mechanisms underlying the relaxation properties of glass-forming liquids and polymers.

  16. Toward a consistent model for glass dissolution

    International Nuclear Information System (INIS)

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

    1994-01-01

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

  17. Thermodynamic and relative approach to compute glass-forming ...

    Indian Academy of Sciences (India)

    models) characteristic: the isobaric heat capacity (Cp) of oxides, and execute a mathematical treatment of oxides thermodynamic data. We note this coefficient as thermodynamical relative glass-forming ability (ThRGFA) and for- mulate a model to compute it. Computed values of 2nd, 3rd, 4th and 5th period metal oxides ...

  18. Sorption of a phenols mixture in aqueous solution with activated carbon

    International Nuclear Information System (INIS)

    Mejia M, D.

    2004-01-01

    The constant population growth and the quick industrialization have caused severe damages to our natural aquifer resources for a great variety of organic and inorganic pollutants. Among these they are those phenol compounds that are highly toxic, resistant (to the degradation chemistry) and poorly biodegradable. The phenolic compounds is used in a great variety of industries, like it is the production of resins, nylon, plastifiers, anti-oxidants, oil additives, drugs, pesticides, colorants, explosives, disinfectants and others. The disseminated discharges or effluents coming from the industrial processes toward lakes and rivers are causing a growing adverse effect in the environment, as well as a risk for the health. Numerous studies exist on the phenols removal and phenols substituted for very varied techniques, among them they are the adsorption in activated carbon. This finishes it has been used successfully for the treatment of residual waters municipal and industrial and of drinking waters and it is considered as the best technique available to eliminate organic compounds not biodegradable and toxic present in aqueous solution (US EPA, 1991). However a little information exists on studies carried out in aqueous systems with more of a phenolic compound. The activated carbon is broadly used as adsorbent due to its superficial properties in the so much treatment of water as of aqueous wastes, adsorbent for the removal of organic pollutants. The main objective of this work is the adsorption of a aqueous mixture of phenol-4 chloro phenol of different concentrations in activated carbon of mineral origin of different meshes and to diminish with it their presence in water. The experiments were carried out for lots, in normal conditions of temperature and pressure. The experimental results show that the removal capacity depends so much of the superficial properties of the sorbent like of the physical properties and chemical of the sorbate. The isotherms were carried

  19. Statistical experimental design for saltstone mixtures

    International Nuclear Information System (INIS)

    Harris, S.P.; Postles, R.L.

    1991-01-01

    We used a mixture experimental design for determining a window of operability for a process at the Savannah River Site Defense Waste Processing Facility (DWPF). The high-level radioactive waste at the Savannah River Site is stored in large underground carbon steel tanks. The waste consists of a supernate layer and a sludge layer. 137 Cs will be removed from the supernate by precipitation and filtration. After further processing, the supernate layer will be fixed as a grout for disposal in concrete vaults. The remaining precipitate will be processed at the DWPF with treated waste tank sludge and glass-making chemicals into borosilicate glass. The leach rate properties of the supernate grout, formed from various mixes of solidified salt waste, needed to be determined. The effective diffusion coefficients for NO 3 and Cr were used as a measure of leach rate. Various mixes of cement, Ca(OH) 2 , salt, slag and flyash were used. These constituents comprise the whole mix. Thus, a mixture experimental design was used

  20. BNFL Report Glass Formers Characterization

    Energy Technology Data Exchange (ETDEWEB)

    Schumacher, R.F.

    2000-07-27

    The objective of this task was to obtain powder property data on candidate glass former materials, sufficient to guide conceptual design and estimate the cost of glass former handling facilities as requested under Part B1 of BNFL Technical and Development Support. Twenty-nine glass forming materials were selected and obtained from vendors for the characterization of their physical properties, durability in caustic solution, and powder flow characteristics. A glass former was selected based on the characterization for each of the ten oxide classes required for Envelope A, B, and C mixtures. Three blends (A, B, and C) were prepared based on formulations provided by Vitreous State Laboratory and evaluated with the same methods employed for the glass formers. The properties obtained are presented in a series of attached Tables. It was determined that five of the ten glass formers, (kyanite, iron oxide, titania, zircon, and zinc oxide) have the potential to cause some level of solids f low problems. The problems might include arching or ratholing in the silo/hopper. In addition, all of the blends may require consideration for their handling.

  1. BNFL Report Glass Formers Characterization

    International Nuclear Information System (INIS)

    Schumacher, R.F.

    2000-01-01

    The objective of this task was to obtain powder property data on candidate glass former materials, sufficient to guide conceptual design and estimate the cost of glass former handling facilities as requested under Part B1 of BNFL Technical and Development Support. Twenty-nine glass forming materials were selected and obtained from vendors for the characterization of their physical properties, durability in caustic solution, and powder flow characteristics. A glass former was selected based on the characterization for each of the ten oxide classes required for Envelope A, B, and C mixtures. Three blends (A, B, and C) were prepared based on formulations provided by Vitreous State Laboratory and evaluated with the same methods employed for the glass formers. The properties obtained are presented in a series of attached Tables. It was determined that five of the ten glass formers, (kyanite, iron oxide, titania, zircon, and zinc oxide) have the potential to cause some level of solids f low problems. The problems might include arching or ratholing in the silo/hopper. In addition, all of the blends may require consideration for their handling

  2. Enhanced glass forming ability and refrigerant capacity of a Gd55Ni22Mn3Al20 bulk metallic glass

    International Nuclear Information System (INIS)

    Xia, L.; Chan, K.C.; Tang, M.B.

    2011-01-01

    Highlights: → A new Gd 55 Ni 22 Mn 3 Al 20 bulk metallic glass (BMG) was synthesized by minor Mn addition. → The BMG has enhanced glass forming ability and excellent refrigerant capacity (RC). → The RC of the BMG reaches a high value of 825 J kg -1 under a field of 3979 kA/m. → Its excellent RC is related to its large effective magnetic moment. - Abstract: In this work, a small amount of Mn was added to a Gd 55 Ni 25 Al 20 glass forming alloy, as a replacement for Ni, and a Gd 55 Ni 22 Mn 3 Al 20 bulk metallic glass (BMG) was obtained by suction casting. Its glass forming ability (GFA) was characterized by X-ray diffraction and differential scanning calorimetry, and its magnetic properties were measured using a magnetic property measurement system. It is found that the minor Mn addition can significantly improve both the GFA and the magnetocaloric effect (MCE) of the alloy. The refrigerant capacity (RC) of the BMG can reach a high value of 825 J kg -1 under a field of 3979 kA/m, which is about 29% larger than that of a Gd 55 Ni 25 Al 20 BMG. The effect of the minor Mn addition on the GFA and MCE of the BMG was investigated in the study.

  3. Temperature of maximum density and excess thermodynamics of aqueous mixtures of methanol

    Energy Technology Data Exchange (ETDEWEB)

    González-Salgado, D.; Zemánková, K. [Departamento de Física Aplicada, Universidad de Vigo, Campus del Agua, Edificio Manuel Martínez-Risco, E-32004 Ourense (Spain); Noya, E. G.; Lomba, E. [Instituto de Química Física Rocasolano, CSIC, Calle Serrano 119, E-28006 Madrid (Spain)

    2016-05-14

    In this work, we present a study of representative excess thermodynamic properties of aqueous mixtures of methanol over the complete concentration range, based on extensive computer simulation calculations. In addition to test various existing united atom model potentials, we have developed a new force-field which accurately reproduces the excess thermodynamics of this system. Moreover, we have paid particular attention to the behavior of the temperature of maximum density (TMD) in dilute methanol mixtures. The presence of a temperature of maximum density is one of the essential anomalies exhibited by water. This anomalous behavior is modified in a non-monotonous fashion by the presence of fully miscible solutes that partly disrupt the hydrogen bond network of water, such as methanol (and other short chain alcohols). In order to obtain a better insight into the phenomenology of the changes in the TMD of water induced by small amounts of methanol, we have performed a new series of experimental measurements and computer simulations using various force fields. We observe that none of the force-fields tested capture the non-monotonous concentration dependence of the TMD for highly diluted methanol solutions.

  4. Volumetric and acoustical properties of aqueous mixtures of N-methyl-2-hydroxyethylammonium butyrate and N-methyl-2-hydroxyethylammonium pentanoate at T = (298.15 to 333.15) K

    International Nuclear Information System (INIS)

    Li, Yang; Figueiredo, Eduardo J.P.; Santos, Mário J.; Santos, Jaime B.; Talavera-Prieto, Nieves M.C.; Carvalho, Pedro J.; Ferreira, Abel G.M.; Mattedi, Silvana

    2016-01-01

    Highlights: • Density and speed of sound for aqueous mixtures of m2HEAB and m2HEAP were measured. • Apparent molar volumes and apparent molar isentropic compressibilities were calculated. • Excess properties were correlated using Redlich–Kister and rational functions. • The molar compressibility the aqueous mixtures was calculated from the Wadás model. • Appreciable interactions between water and ionic liquid were found. - Abstract: The speed of sound in the protic ionic liquids (PILs) N-methyl-2-hydroxyethylammonium butyrate (m2HEAB) and N-methyl-2-hydroxyethylammonium pentanoate (m2HEAP) was measured at atmospheric pressure, and over the range of temperatures T = (293.15 to 343.15) K. The speed of sound and density of aqueous mixtures of the ionic liquid were also determined throughout the entire concentration range, within the (298.15 to 333.15) K temperature range and at atmospheric pressure. The excess molar volume, excess isentropic compressibility, excess speed of sound, apparent molar volume and apparent molar isentropic compressibility were calculated from the experimental density and speed of sound values. Furthermore, all the properties were correlated with selected analytical functions. The apparent molar volume of aqueous PILs was analysed by Pitzer–Simonson theory. The speed of sound of the PILs was predicted with the Wu et al. model and the molar compressibility of the same PILs and their aqueous mixtures were calculated from Wadás model. The results demonstrate that the molar compressibility calculated from Wadás model is almost a linear function of mole fraction and can be considered as temperature independent for a fixed mole fraction over the whole composition range. The results were analysed and discussed from the structural changes point of view in aqueous medium.

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

    International Nuclear Information System (INIS)

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

    2013-01-01

    Tri-Structural Isotropic (TRISO) coated particle-fuel is a key component in designs for future high temperature nuclear reactors. This study investigated the suitability of three soda lime silicate glass compositions, for the encapsulation of simulant TRISO particle fuel. A cold press and sinter (CPS) methodology was employed to produce TRISO particle–glass composites. Composites produced were determined to have an aqueous durability, fracture toughness and Vickers’ hardness comparable to glasses currently employed for the disposal of high level nuclear wastes. Sintering at 700 °C for 30 min was found to remove all interconnected porosity from the composite bodies and oxidation of the outer pyrolytic carbon layer during sintering was prevented by processing under a 5% H 2 /N 2 atmosphere. However, the outer pyrolytic carbon layer was not effectively wetted by the encapsulating glass matrix. The aqueous durability of the TRISO particle–glass composites was investigated using PCT and MCC-1 tests combined with geochemical modelling. It was found that durability was dependent on silicate and calcium solution saturation. This study provides significant advancements in the preparation of TRISO particle encapsulant waste forms. The potential for the use of non-borosilicate sintered glass composites for TRISO particle encapsulation has been confirmed, although further refinements are required

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

    Energy Technology Data Exchange (ETDEWEB)

    Heath, Paul G.; Corkhill, Claire L.; Stennett, Martin C.; Hand, Russell J. [Immobilisation Science Laboratory, Department of Materials Science and Engineering, Robert Hadfield Building, University of Sheffield, Sheffield S1 3JD (United Kingdom); Meyer, Willem C.H.M. [Necsa, South African Nuclear Energy Corporation, PO Box 582, Pretoria, Gauteng (South Africa); Hyatt, Neil C., E-mail: n.c.hyatt@sheffield.ac.uk [Immobilisation Science Laboratory, Department of Materials Science and Engineering, Robert Hadfield Building, University of Sheffield, Sheffield S1 3JD (United Kingdom)

    2013-05-15

    Tri-Structural Isotropic (TRISO) coated particle-fuel is a key component in designs for future high temperature nuclear reactors. This study investigated the suitability of three soda lime silicate glass compositions, for the encapsulation of simulant TRISO particle fuel. A cold press and sinter (CPS) methodology was employed to produce TRISO particle–glass composites. Composites produced were determined to have an aqueous durability, fracture toughness and Vickers’ hardness comparable to glasses currently employed for the disposal of high level nuclear wastes. Sintering at 700 °C for 30 min was found to remove all interconnected porosity from the composite bodies and oxidation of the outer pyrolytic carbon layer during sintering was prevented by processing under a 5% H{sub 2}/N{sub 2} atmosphere. However, the outer pyrolytic carbon layer was not effectively wetted by the encapsulating glass matrix. The aqueous durability of the TRISO particle–glass composites was investigated using PCT and MCC-1 tests combined with geochemical modelling. It was found that durability was dependent on silicate and calcium solution saturation. This study provides significant advancements in the preparation of TRISO particle encapsulant waste forms. The potential for the use of non-borosilicate sintered glass composites for TRISO particle encapsulation has been confirmed, although further refinements are required.

  7. Polarographic reduction of Yb/sup +3/ benzoate and salicylate complexes in aqueous-nonaqueous mixtures at D. M. E

    Energy Technology Data Exchange (ETDEWEB)

    Zutshi, K; Gupta, K C [Rajasthan Univ., Jaipur (India). Dept. of Chemistry

    1977-01-01

    The reduction of Yb/sup +3/ and Yb/sup +3/-benzoate and salicylate complexes was studied polarographically at constant ionic strength at 25 +- 0.02/sup 0/C in aqueous-nonaqueous mixtures. The reduction was found to be diffusion-controlled, but the electrode process was irreversible in all cases. The kinetic parameters were determined by Koutecky's method.

  8. Characterization of aqueous interactions of copper-doped phosphate-based glasses by vapour sorption.

    Science.gov (United States)

    Stähli, Christoph; Shah Mohammadi, Maziar; Waters, Kristian E; Nazhat, Showan N

    2014-07-01

    Owing to their adjustable dissolution properties, phosphate-based glasses (PGs) are promising materials for the controlled release of bioinorganics, such as copper ions. This study describes a vapour sorption method that allowed for the investigation of the kinetics and mechanisms of aqueous interactions of PGs of the formulation 50P2O5-30CaO-(20-x)Na2O-xCuO (x=0, 1, 5 and 10mol.%). Initial characterization was performed using (31)P magic angle spinning nuclear magnetic resonance and attenuated total reflectance-Fourier transform infrared spectroscopy. Increasing CuO content resulted in chemical shifts of the predominant Q(2) NMR peak and of the (POP)as and (PO(-)) Fourier transform infrared absorptions, owing to the higher strength of the POCu bond compared to PONa. Vapour sorption and desorption were gravimetrically measured in PG powders exposed to variable relative humidity (RH). Sorption was negligible below 70% RH and increased exponentially with RH from 70 to 90%, where it exhibited a negative correlation with CuO content. Vapour sorption in 0% and 1% CuO glasses resulted in phosphate chain hydration and hydrolysis, as evidenced by protonated Q(0)(1H) and Q(1)(1H) species. Dissolution rates in deionized water showed a linear correlation (R(2)>0.99) with vapour sorption. Furthermore, cation release rates could be predicted based on dissolution rates and PG composition. The release of orthophosphate and short polyphosphate species corroborates the action of hydrolysis and was correlated with pH changes. In conclusion, the agreement between vapour sorption and routine characterization techniques in water demonstrates the potential of this method for the study of PG aqueous reactions. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  9. Effect of glass composition on waste form durability: A critical review

    International Nuclear Information System (INIS)

    Ellison, A.J.G.; Mazer, J.J.; Ebert, W.L.

    1994-11-01

    This report reviews literature concerning the relationship between the composition and durability of silicate glasses, particularly glasses proposed for immobilization of radioactive waste. Standard procedures used to perform durability tests are reviewed. It is shown that tests in which a low-surface area sample is brought into contact with a very large volume of solution provide the most accurate measure of the intrinsic durability of a glass composition, whereas high-surface area/low-solution volume tests are a better measure of the response of a glass to changes in solution chemistry induced by a buildup of glass corrosion products. The structural chemistry of silicate and borosilicate glasses is reviewed to identify those components with the strongest cation-anion bonds. A number of examples are discussed in which two or more cations engage in mutual bonding interactions that result in minima or maxima in the rheologic and thermodynamic properties of the glasses at or near particular optimal compositions. It is shown that in simple glass-forming systems such interactions generally enhance the durability of glasses. Moreover, it is shown that experimental results obtained for simple systems can be used to account for durability rankings of much more complex waste glass compositions. Models that purport to predict the rate of corrosion of glasses in short-term durability tests are evaluated using a database of short-term durability test results for a large set of glass compositions. The predictions of these models correlate with the measured durabilities of the glasses when considered in large groupings, but no model evaluated in this review provides accurate estimates of durability for individual glass compositions. Use of these models in long-term durability models is discussed. 230 refs

  10. Correlation between relaxations and plastic deformation, and elastic model of flow in metallic glasses and glass-forming liquids

    International Nuclear Information System (INIS)

    Wang Weihua

    2011-01-01

    We study the similarity and correlations between relaxations and plastic deformation in metallic glasses (MGs) and MG-forming liquids. It is shown that the microscope plastic events, the initiation and formation of shear bands, and the mechanical yield in MGs where the atomic sites are topologically unstable induced by applied stress, can be treated as the glass to supercooled liquid state transition induced by external shear stress. On the other hand, the glass transition, the primary and secondary relaxations, plastic deformation and yield can be attributed to the free volume increase induced flow, and the flow can be modeled as the activated hopping between the inherent states in the potential energy landscape. We then propose an extended elastic model to describe the flow based on the energy landscape theory. That is, the flow activation energy density is linear proportional to the instantaneous elastic moduli, and the activation energy density ρ E is determined to be a simple expression of ρ E =(10/11)G+(1/11)K. The model indicates that both shear and bulk moduli are critical parameters accounting for both the homogeneous and inhomogeneous flows in MGs and MG-forming liquids. The elastic model is experimentally certified. We show that the elastic perspectives offers a simple scenario for the flow in MGs and MG-forming liquids and are suggestive for understanding the glass transition, plastic deformation, and nature and characteristics of MGs

  11. XPS study of the passive layers formed on lead in aqueous nitrate solutions

    International Nuclear Information System (INIS)

    Uchida, Miho; Okuwaki, Akitsugu

    1997-01-01

    The analysis of the lead surface immersed in aqueous nitrate solutions by X-ray photoelectron spectroscopy (XPS) shows the formation of passive oxide layer containing nitrogen compound. The oxide layer formed on the lead surface in aqueous ammonium nitrate solution was hydrolyzed and cracked. (author)

  12. Studies of glass waste form performance at Japan Atomic Energy Research Institute

    International Nuclear Information System (INIS)

    Banba, Tsunetaka; Kamizono, Hiroshi; Nakayama, Shinichi; Tashiro, Shingo

    1989-08-01

    The recent studies of glass waste form performance at Japan Atomic Energy Research Institute can be classified into the following three categories; (1) Study on the volatilization of radionuclides from the waste glass, which is necessary to estimate the safety in relation to operation of a storage facility. (2) Study on the radiation (alpha-radiation) effects which have relation to the long-term stability of the waste glass. (3) Study on the leaching behavior of actinides under the repository conditions, which is necessary to predict the long-term release rate of radionuclides from the waste glass. In the present report, the recent results corresponding to the above categories are described. (author)

  13. ESCA studies on leached glass forms

    International Nuclear Information System (INIS)

    Dawkins, B.G.

    1979-01-01

    Electron Spectroscopy for Chemical Analysis (ESCA) results for frit, obsidian, NBS standard, and Savannah River Laboratory (SRL) glass forms that have been subjected to cumulative water leachings of 36 hours show that [Na] exhibits the largest and fastest change of all the elements observed. Leaching of surface Na occurred within minutes. Surface Na depletion increased with leach time. Continuous x-ray irradiation and argon ion milling induced Na mobility, precluding semiquantitative ESCA analysis at normal operating temperatures. However, the sample stage has been equipped with a liquid nitrogen supply and alkali mobility should be eliminated in future work

  14. Volumetric and viscometric study of aqueous binary mixtures of some glycol ethers at T = (275.15 and 283.15) K

    International Nuclear Information System (INIS)

    Dhondge, Sudhakar S.; Pandhurnekar, Chandrashekhar P.; Sheikh, Shaziya; Deshmukh, Dinesh W.

    2011-01-01

    Graphical abstract: Highlights: → Study of aqueous solutions of glycol ethers at low temperatures is presented. → Glycol ethers are industrially important liquids. → Reduction in the volume was observed upon addition of all glycol ethers to water. → Glycol ethers act as structure makers in aqueous medium. - Abstract: The experimental data for the density (ρ) and viscosity (η) are reported for aqueous binary mixtures of different glycol ethers, namely ethylene glycol monomethyl ether (EGMME), ethylene glycol monoethyl ether (EGMEE), diethylene glycol monomethyl ether (DEGMME), and diethylene glycol monoethyl ether (DEGMEE), at different temperatures (T = 275.15 K and 283.15 K) within the concentration range 0 mol . kg -1 to 0.1 mol . kg -1 . The values of density (ρ) and viscosity (η) of the solutions were used to compute different derived parameters, such as apparent molar volume (φ V ) of the solute, excess molar volume (V E ) of the solution, viscosity B and D coefficients of solution and temperature coefficient of viscosity B-coefficient (dB/dT) of solution. The limiting apparent molar volume of the solutes (φ V 0 ) have been obtained for aqueous binary mixtures of these glycol ethers by smooth extrapolation of φ V -m curves to zero concentration. By using the values of φ V 0 , the limiting excess partial molar volumes (V-bar 2 0E ) have also been calculated. The results are interpreted in term of various interactions such as solute-solvent interactions and hydrogen bonding.

  15. Properties of L-ascorbic acid in water and binary aqueous mixtures of D-glucose and D-fructose at different temperatures

    Science.gov (United States)

    Sharma, Ravi; Thakur, R. C.; Sani, Balwinder; Kumar, Harsh

    2017-12-01

    Using density and sound velocity partial molar volumes, partial molar adiabatic compressibilities, partial molar expansibilities and structure of L-ascorbic acid have been determined in water and aqueous mixtures of D-glucose and D-fructose at different concentrations and temperatures. Masson's equation was used to analyze the measured data. The obtained parameters have been interpreted in terms of solute-solute and solute-solvent interactions. It is found that the L-ascorbic acid acts as structure breaker in water as well in binary studied mixtures.

  16. Thermodynamic and topological instability approaches for forecasting glass-forming ability in the ternary Al-Ni-Y system

    International Nuclear Information System (INIS)

    Oliveira, M.F. de; Aliaga, L.C.R.; Bolfarini, C.; Botta, W.J.; Kiminami, C.S.

    2008-01-01

    A thermodynamic approach to predict bulk glass-forming compositions in binary metallic systems was recently proposed. In this approach, the parameter γ* = ΔH amor /(ΔH inter - ΔH amor ) indicates the glass-forming ability (GFA) from the standpoint of the driving force to form different competing phases, and ΔH amor and ΔH inter are the enthalpies for glass and intermetallic formation, respectively. Good glass-forming compositions should have a large negative enthalpy for glass formation and a very small difference for intermetallic formation, thus making the glassy phase easily reachable even under low cooling rates. The γ* parameter showed a good correlation with GFA experimental data in the Ni-Nb binary system. In this work, a simple extension of the γ* parameter is applied in the ternary Al-Ni-Y system. The calculated γ* isocontours in the ternary diagram are compared with experimental results of glass formation in that system. Despite some misfitting, the best glass formers are found quite close to the highest γ* values, leading to the conclusion that this thermodynamic approach can be extended to ternary systems, serving as a useful tool for the development of new glass-forming compositions. Finally the thermodynamic approach is compared with the topological instability criteria used to predict the thermal behavior of glassy Al alloys

  17. Waste vitrification: prediction of acceptable compositions in a lime-soda-silica glass-forming system

    International Nuclear Information System (INIS)

    Gilliam, T.M.; Jantzen, C.M.

    1996-10-01

    A model is presented based upon calculated bridging oxygens which allows the prediction of the region of acceptable glass compositions for a lime-soda-silica glass-forming system containing mixed waste. The model can be used to guide glass formulation studies (e.g., treatability studies) or assess the applicability of vitrification to candidate waste streams

  18. Reversible and Irreversible Behavior of Glass-forming Materials from the Standpoint of Hierarchical Dynamical Facilitation

    Science.gov (United States)

    Keys, Aaron

    2013-03-01

    Using molecular simulation and coarse-grained lattice models, we study the dynamics of glass-forming liquids above and below the glass transition temperature. In the supercooled regime, we study the structure, statistics, and dynamics of excitations responsible for structural relaxation for several atomistic models of glass-formers. Excitations (or soft spots) are detected in terms of persistent particle displacements. At supercooled conditions, we find that excitations are associated with correlated particle motions that are sparse and localized, and the statistics and dynamics of these excitations are facilitated and hierarchical. Excitations at one point in space facilitate the birth and death of excitations at neighboring locations, and space-time excitation structures are microcosms of heterogeneous dynamics at larger scales. Excitation-energy scales grow logarithmically with the characteristic size of the excitation, giving structural-relaxation times that can be predicted quantitatively from dynamics at short time scales. We demonstrate that these same physical principles govern the dynamics of glass-forming systems driven out-of-equilibrium by time-dependent protocols. For a system cooled and re-heated through the glass transition, non-equilibrium response functions, such as heat capacities, are notably asymmetric in time, and the response to melting a glass depends markedly on the cooling protocol by which the glass was formed. We introduce a quantitative description of this behavior based on the East model, with parameters determined from reversible transport data, that agrees well with irreversible differential scanning calorimetry. We find that the observed hysteresis and asymmetric response is a signature of an underlying dynamical transition between equilibrium melts with no trivial spatial correlations and non-equilibrium glasses with correlation lengths that are both large and dependent upon the rate at which the glass is prepared. The correlation

  19. Secondary organic material formed by methylglyoxal in aqueous aerosol mimics

    Directory of Open Access Journals (Sweden)

    N. Sareen

    2010-02-01

    Full Text Available We show that methylglyoxal forms light-absorbing secondary organic material in aqueous ammonium sulfate and ammonium nitrate solutions mimicking tropospheric aerosol particles. The kinetics were characterized using UV-Vis spectrophotometry. The results suggest that the bimolecular reaction of methylglyoxal with an ammonium or hydronium ion is the rate-limiting step for the formation of light-absorbing species, with kNH4+II=5×10−6 M−1 min−1 and kH3O+II≤10−3 M−1 min−1. Evidence of aldol condensation products and oligomeric species up to 759 amu was found using chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol-CIMS. Tentative identifications of carbon-nitrogen species and a sulfur-containing compound were also made using Aerosol-CIMS. Aqueous solutions of methylglyoxal, with and without inorganic salts, exhibit significant surface tension depression. These observations add to the growing body of evidence that dicarbonyl compounds may form secondary organic material in the aerosol aqueous phase, and that secondary organic aerosol formation via heterogeneous processes may affect seed aerosol properties.

  20. Atmospheric Processing of Volcanic Glass: Effects on Iron Solubility and Redox Speciation.

    Science.gov (United States)

    Maters, Elena C; Delmelle, Pierre; Bonneville, Steeve

    2016-05-17

    Volcanic ash from explosive eruptions can provide iron (Fe) to oceanic regions where this micronutrient limits primary production. Controls on the soluble Fe fraction in ash remain poorly understood but Fe solubility is likely influenced during atmospheric transport by condensation-evaporation cycles which induce large pH fluctuations. Using glass powder as surrogate for ash, we experimentally simulate its atmospheric processing via cycles of pH 2 and 5 exposure. Glass fractional Fe solubility (maximum 0.4%) is governed by the pH 2 exposure duration rather than by the pH fluctuations, however; pH 5 exposure induces precipitation of Fe-bearing nanoparticles which (re)dissolve at pH 2. Glass leaching/dissolution release Fe(II) and Fe(III) which are differentially affected by changes in pH; the average dissolved Fe(II)/Fetot ratio is ∼0.09 at pH 2 versus ∼0.18 at pH 5. Iron release at pH 2 from glass with a relatively high bulk Fe(II)/Fetot ratio (0.5), limited aqueous Fe(II) oxidation at pH 5, and possibly glass-mediated aqueous Fe(III) reduction may render atmospherically processed ash a significant source of Fe(II) for phytoplankton. By providing new insight into the form(s) of Fe associated with ash as wet aerosol versus cloud droplet, we improve knowledge of atmospheric controls on volcanogenic Fe delivery to the ocean.

  1. Method of producing homogeneous mixed metal oxides and metal-metal oxide mixtures

    International Nuclear Information System (INIS)

    Quinby, T.C.

    1980-01-01

    A method for preparing particulate metal or metal oxide of controlled partile size comprises contacting an an aqueous solution containing dissolved metal values with excess urea at a temperature sufficient to cause urea to react with water to provide a molten urea solution containing the metal values; heating the molten urea solution to cause the metal values to precipitate, forming a mixture containing precipitated metal values; heating the mixture containing precipitated metal values to evaporate volatile material leaving a dry powder containing said metal values. The dry powder can be calcined to provide particulate metal oxide or reduced to provide particulate metal. Oxide mixtures are provided when the aqueous solution contains values of more than one metal. Homogeneousmetal-metal oxide mistures for preparing cermets can be prepared by selectively reducing at least one of the metal oxides. (auth)

  2. Hydrophobicity attainment and wear resistance enhancement on glass substrates by atmospheric plasma-polymerization of mixtures of an aminosilane and a fluorocarbon

    Energy Technology Data Exchange (ETDEWEB)

    Múgica-Vidal, Rodolfo, E-mail: rodolfo.mugica@alum.unirioja.es [Department of Mechanical Engineering, University of La Rioja, c/ Luis de Ulloa 20, 26004, Logroño, La Rioja (Spain); Alba-Elías, Fernando, E-mail: fernando.alba@unirioja.es [Department of Mechanical Engineering, University of La Rioja, c/ Luis de Ulloa 20, 26004, Logroño, La Rioja (Spain); Sainz-García, Elisa, E-mail: elisa.sainzg@unirioja.es [Department of Mechanical Engineering, University of La Rioja, c/ Luis de Ulloa 20, 26004, Logroño, La Rioja (Spain); Pantoja-Ruiz, Mariola, E-mail: mpruiz@ing.uc3m.es [Materials Science and Engineering Department, IAAB, Materials Performance Group, University Carlos III of Madrid, Av. Universidad 30, 28911, Leganés, Madrid (Spain)

    2015-08-30

    Graphical abstract: - Highlights: • APTES and PFH were used to coat glass by non-thermal atmospheric jet plasma. • A mixture of 75% of APTES and 25% PFH produced the best sample of this work. • Hydrophobicity was achieved by changes in surface morphology and chemistry. • Wear resistance was enhanced by the formation of siloxane groups. - Abstract: Mixtures of different proportions of two liquid precursors were subjected to plasma-polymerization by a non-thermal atmospheric jet plasma system in a search for a coating that achieves a hydrophobic character on a glass substrate and enhances its wear resistance. 1-Perfluorohexene (PFH) was chosen as a low-surface-energy precursor to promote a hydrophobic character. Aminopropyltriethoxysilane (APTES) was chosen for its contribution to the improvement of wear resistance by the formation of siloxane bonds. The objective of this work was to determine which of the precursors’ mixtures that were tested provides the coating with the most balanced enhancement of both hydrophobicity and wear resistance, given that coatings deposited with fluorocarbon-based precursors such as PFH are usually low in resistance to wear and coatings deposited with APTES are generally hydrophilic. The coatings obtained were analyzed by Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Fourier Transform Infra-Red (FTIR) spectroscopy, X-ray Photoelectron Spectroscopy (XPS), static Water Contact Angle (WCA) measurements, tribological ball-on-disc tests and contact profilometry. A relationship between the achievement of a hydrophobic character and the modifications to roughness and surface morphology and the incorporation of fluorocarbon groups in the surface chemistry was observed. Also, it was seen that the wear resistance was influenced by the SiOSi content of the coatings. In turn, the SiOSi content appears to be directly related to the percentage of APTES used in the mixture of precursors. The best conjunction of

  3. Thermodynamic promotion of carbon dioxide-clathrate hydrate formation by tetrahydrofuran, cyclopentane and their mixtures

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

    2013-01-01

    Gas clathrate hydrate dissociation pressures are reported for mixtures of carbon dioxide, water and thermodynamic promoters forming structure II hydrates.Hydrate (H)-aqueous liquid (Lw)-vapour (V) equilibrium pressures for the ternary system composed of water, tetrahydrofuran (THF), and carbon....... It is shown that upon adding THF to the pure aqueous phase to form a 4mass percent solution, the equilibrium pressure of the formed hydrates may be lowered compared to the ternary system of water, cyclopentane and carbon dioxide. © 2013 Elsevier Ltd....... dioxide (CO2), with 5.0mole percent THF in the initial aqueous phase, are presented in the temperature range from 283.3K to 285.2K. At 283.3K, the three-phase equilibrium pressure is determined to be 0.61MPa (absolute pressure).Four-phase hydrate (H)-aqueous liquid (Lw)-organic liquid (La)-vapour (V...

  4. Electron microprobe analysis (WDS EPMA) of Zhamanshin glass reveals the impactor and a common role of accretion in the origin of splash-form impact glass

    International Nuclear Information System (INIS)

    Vetvicka, I; Frank, J; Drtina, J

    2010-01-01

    Impact glass samples collected during expeditions to the Zhamashin and Lonar craters were subjected to a morphology survey and compared to Wabar, Henbury and Darwin impact glasses to reveal that the accretion of fibres and spherules is not exclusive for irghizites but occurs in other splash form glasses over the world. WDS EPMA and LA-ICP-MS assays of Zhamanshin and Lonar glasses enabled the definition of akmurynites as Zhamanshin glass of specific morphology, chemistry and absence of extraterrestrial contamination. However, extraterrestrial contamination in irghizites was verified and further WDS EPMA analyses led to the conclusion that the Zhamanshin crater had been formed by the impact of a primitive achondrite of Lodran chemistry.

  5. Y and Er minor addition effect on glass forming ability of a Ni–Nb–Zr alloy

    International Nuclear Information System (INIS)

    Deo, L.P.; Oliveira, M.F. de

    2015-01-01

    Highlights: • A theoretical selection criterion to predict the GFA was used for Ni–Nb–Zr–RE alloys. • The prediction agrees very well with thermal parameter gm used to evaluate experimentally the GFA. • RE doped alloys showed higher GFA than the base alloy. • Y and Er elements showed similar effects to improve the GFA of the base alloy. - Abstract: Since the discovering of amorphous alloys in 1960, the actual causes of why some alloys can be easily formed into glasses while others cannot, are not clearly known, thus there is no universal theory to predict the glass forming ability in metallic systems. It is well known that the minor amount addition of proper rare-earth elements can greatly enhance the glass forming ability of some glass-forming alloys. In the present study, a selection criterion was successfully used to predict the glass forming ability improvement of Ni 67.3 Nb 28.4 Zr 4.3 alloy with minor additions of Y or Er. The actual glass forming ability of the base alloy and rare-earth doped alloys were evaluated by the thermal parameter γ m and the results agree very well with the tendency predicted by the calculation. The amorphous nature of alloys was mainly analyzed by X-ray diffraction and differential scanning calorimetry. This work also presents a brief and complementary consideration about oxygen contamination quantified by the inert gas fusion method

  6. Criticality of mixtures of plutonium and high enriched uranium

    International Nuclear Information System (INIS)

    Grolleau, E.; Lein, M.; Leka, G.; Maidou, B.; Klenov, P.

    2003-01-01

    This paper presents a criticality evaluation of moderated homogeneous plutonium-uranium mixtures. The fissile media studied are homogeneous mixtures of plutonium and high enriched uranium in two chemical forms: aqueous mixtures of metal and mixtures of nitrate solutions. The enrichment of uranium considered are 93.2wt.% 235 U and 100wt.% 235 U. The 240 Pu content in plutonium varies from 0wt.% 240 Pu to 12wt.% 240 Pu. The critical parameters (radii and masses of a 20 cm water reflected sphere) are calculated with the French criticality safety package CRISTAL V0. The comparison of the calculated critical parameters as a function of the moderator-to-fuel atomic ratio shows significant ranges in which high enriched uranium systems, as well as plutonium-uranium mixtures, are more reactive than plutonium systems. (author)

  7. Relating structural parameters to leachability in a glass-bonded ceramic waste form

    International Nuclear Information System (INIS)

    Frank, S. M.; Johnson, S. G.; Moschetti, T. L.

    1998-01-01

    Lattice parameters for a crystalline material can be obtained by several methods, notably by analyzing x-ray powder diffraction patterns. By utilizing a computer program to fit a pattern, one can follow the evolution or subtle changes in a structure of a crystalline species in different environments. This work involves such a study for an essential component of the ceramic waste form that is under development at Argonne National Laboratory. Zeolite 4A and zeolite 5A are used to produce two different types of waste forms: a glass-bonded sodalite and a glass-bonded zeolite, respectively. Changes in structure during production of the waste forms are discussed. Specific salt-loadings in the sodalite waste form are related to relative peak intensities of certain reflections in the XRD patterns. Structural parameters for the final waste forms will also be given and related to leachability under standard conditions

  8. The analysis of aqueous mixtures using liquid chromatography-electrospray mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Steven [Iowa State Univ., Ames, IA (United States)

    1999-02-12

    The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide variety of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The determination of electrochemical incineration products of 4-chlorophenol by liquid chromatography-electrospray mass spectrometry; and Chapter 5: Determination of small carboxylic acids by capillary electrophoresis with electrospray mass spectrometry.

  9. Length scales in glass-forming liquids and related systems: a review

    International Nuclear Information System (INIS)

    Karmakar, Smarajit; Dasgupta, Chandan; Sastry, Srikanth

    2016-01-01

    The central problem in the study of glass-forming liquids and other glassy systems is the understanding of the complex structural relaxation and rapid growth of relaxation times seen on approaching the glass transition. A central conceptual question is whether one can identify one or more growing length scale(s) associated with this behavior. Given the diversity of molecular glass-formers and a vast body of experimental, computational and theoretical work addressing glassy behavior, a number of ideas and observations pertaining to growing length scales have been presented over the past few decades, but there is as yet no consensus view on this question. In this review, we will summarize the salient results and the state of our understanding of length scales associated with dynamical slow down. After a review of slow dynamics and the glass transition, pertinent theories of the glass transition will be summarized and a survey of ideas relating to length scales in glassy systems will be presented. A number of studies have focused on the emergence of preferred packing arrangements and discussed their role in glassy dynamics. More recently, a central object of attention has been the study of spatially correlated, heterogeneous dynamics and the associated length scale, studied in computer simulations and theoretical analysis such as inhomogeneous mode coupling theory. A number of static length scales have been proposed and studied recently, such as the mosaic length scale discussed in the random first-order transition theory and the related point-to-set correlation length. We will discuss these, elaborating on key results, along with a critical appraisal of the state of the art. Finally we will discuss length scales in driven soft matter, granular fluids and amorphous solids, and give a brief description of length scales in aging systems. Possible relations of these length scales with those in glass-forming liquids will be discussed. (review article)

  10. Application of waste glass in translucent and photocatalytic concrete

    NARCIS (Netherlands)

    Lieshout, van B.; Spiesz, P.R.; Brouwers, H.J.H.

    2012-01-01

    Container glass aggregates and glass powder are waste products of the glass recycling industry. In this research, these products are incorporated in self-compacting concrete (SCC) mixtures, replacing conventional aggregates and fine powders. The SCC mixtures were designed using a particle packing

  11. Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature.

    Science.gov (United States)

    Mallamace, Francesco; Branca, Caterina; Corsaro, Carmelo; Leone, Nancy; Spooren, Jeroen; Chen, Sow-Hsin; Stanley, H Eugene

    2010-12-28

    It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T. In an Arrhenius plot, ln η vs 1/T, a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel-Fulcher-Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η(×), where η(×) has the same value, η(×) ≈ 10(3) Poise, for all 84 liquids. The crossover temperature, T(×), located well above the calorimetric glass transition temperature T(g), marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T(×) to Arrhenius behavior below T(×). We also show that below T(×) the familiar Stokes-Einstein relation D/T ∼ η(-1) breaks down and is replaced by a fractional form D/T ∼ η(-ζ), with ζ ≈ 0.85.

  12. Machine Learning Approach for Prediction and Understanding of Glass-Forming Ability.

    Science.gov (United States)

    Sun, Y T; Bai, H Y; Li, M Z; Wang, W H

    2017-07-20

    The prediction of the glass-forming ability (GFA) by varying the composition of alloys is a challenging problem in glass physics, as well as a problem for industry, with enormous financial ramifications. Although different empirical guides for the prediction of GFA were established over decades, a comprehensive model or approach that is able to deal with as many variables as possible simultaneously for efficiently predicting good glass formers is still highly desirable. Here, by applying the support vector classification method, we develop models for predicting the GFA of binary metallic alloys from random compositions. The effect of different input descriptors on GFA were evaluated, and the best prediction model was selected, which shows that the information related to liquidus temperatures plays a key role in the GFA of alloys. On the basis of this model, good glass formers can be predicted with high efficiency. The prediction efficiency can be further enhanced by improving larger database and refined input descriptor selection. Our findings suggest that machine learning is very powerful and efficient and has great potential for discovering new metallic glasses with good GFA.

  13. Devitrification behavior and glass-forming ability of Cu-Zr-Ag alloys

    International Nuclear Information System (INIS)

    Louzguine-Luzgin, Dmitri V.; Xie, Guoqiang; Zhang, Wei; Inoue, Akihisa

    2007-01-01

    This paper presents an influence of Ag addition on the glass-forming ability and devitrification behavior of Cu-Zr glassy alloys on heating. The crystallization kinetics and structure changes in Cu 45 Zr 45 Ag 10 and Cu 35 Zr 45 Ag 20 glassy alloys on heating were studied by X-ray diffraction, transmission electron microscopy, differential scanning and isothermal calorimetry methods. Based on the results obtained one can assume that the improvement of the glass-forming ability of the Cu-Zr alloys by the addition of Ag is connected with a particular crystallization mechanism and a higher reduced glass-transition temperature of the Cu 45 Zr 45 Ag 10 ternary alloy compared to the binary Cu 55 Zr 45 counterpart. As observed in the present work crystallization of the Cu-Zr-Ag alloys is found to cause embitterment of the samples and should be avoided as these alloys are considered to be used as structural materials. The Cu 35 Zr 45 Ag 20 alloy shows possible submicron-scale phase separation upon annealing

  14. Characterization of the alteration products formed at the surface of LaYSiAlO and CeYSiAlO glasses using ERDA and RBS techniques

    International Nuclear Information System (INIS)

    Gavarini, S.; Trocellier, P.; Matzen, G.

    2004-01-01

    Leaching tests have been performed on LnYSiAlO glasses (Ln = La or Ce) that are considered as potential matrices for the specific immobilization of minor actinides. Elastic recoil detection analysis (ERDA) performed on leached samples indicated a superficial hydration of LaYSiAlO glass of about 100-150 nm. This hydrated layer is (Al, Y)-enriched according to SEM-EDS analysis, suggesting the formation of hydroxide (or hydroxycarbonates) compounds including these two elements. This process leads to a very efficient passivation of the material due to the low solubility of Al and Y hydroxides (and hydroxycarbonates) species in near neutral media, even when the solution is rapidly replenished is dynamic leaching experiments. Rutherford Backscattering Spectrometry elemental mapping revealed very localized and significantly Y-enriched deposits at the surface of the sample after leaching. This could be the sign of heterogeneities already present on the pristine glass. These may be correlated with the weak solubility of yttrium (and rare earth) elements in silicate matrices (Y + Ln initial content in the glass ∼11 at.%). In the case of CeYSiAlO glass, a thin layer was formed on the solid after leaching. The simulation of the corresponding RBS spectra showed a surface (Y, Ce)-enrichment and (Al, Si)-depletion in both cases. This could be explained by the oxidation of trivalent cerium initially present in the glass structure during leaching. This might be explained by the low solubility of Ce(IV)-compounds (CeO 2 and/or Ce(OH) 4 ) in solution leading to an enrichment of this element at the glass/solution interface, to form a mixture of amorphous CeO 2 and Y(OH) 3 , as confirmed by XPS and XRD experiments

  15. Mössbauer spectroscopic studies of frozen aqueous solutions of Fe3+ salts

    DEFF Research Database (Denmark)

    Mørup, Steen; Knudsen, J. E.; Nielsen, M. K.

    1976-01-01

    Frozen aqueous solutions (FAS) of Fe3+ salts have been investigated by use of Mössbauer spectroscopy in order to study the conditions for formation of glasses. A general discussion of spin–spin relaxation in glasses is given, and we discuss how changes in the spin–spin relaxation time can...... be attributed to changes in the average separation between the iron ions. In the FeCl3–H2O system, it was found that homogeneous glasses are easily formed when the salt concentration is larger than 3.5 moles FeCl3 per 100 moles H2O. In more dilute samples, ice crystallizes during cooling, while the salt...

  16. Quantitative model of super-Arrhenian behavior in glass forming materials

    Science.gov (United States)

    Caruthers, J. M.; Medvedev, G. A.

    2018-05-01

    The key feature of glass forming liquids is the super-Arrhenian temperature dependence of the mobility, where the mobility can increase by ten orders of magnitude or more as the temperature is decreased if crystallization does not intervene. A fundamental description of the super-Arrhenian behavior has been developed; specifically, the logarithm of the relaxation time is a linear function of 1 /U¯x , where U¯x is the independently determined excess molar internal energy and B is a material constant. This one-parameter mobility model quantitatively describes data for 21 glass forming materials, which are all the materials where there are sufficient experimental data for analysis. The effect of pressure on the loga mobility is also described using the same U¯x(T ,p ) function determined from the difference between the liquid and crystalline internal energies. It is also shown that B is well correlated with the heat of fusion. The prediction of the B /U¯x model is compared to the Adam and Gibbs 1 /T S¯x model, where the B /U¯x model is significantly better in unifying the full complement of mobility data. The implications of the B /U¯x model for the development of a fundamental description of glass are discussed.

  17. Production of a High-Level Waste Glass from Hanford Waste Samples

    International Nuclear Information System (INIS)

    Crawford, C.L.; Farrara, D.M.; Ha, B.C.; Bibler, N.E.

    1998-09-01

    The HLW glass was produced from a HLW sludge slurry (Envelope D Waste), eluate waste streams containing high levels of Cs-137 and Tc-99, solids containing both Sr-90 and transuranics (TRU), and glass-forming chemicals. The eluates and Sr-90/TRU solids were obtained from ion-exchange and precipitation pretreatments, respectively, of other Hanford supernate samples (Envelopes A, B and C Waste). The glass was vitrified by mixing the different waste streams with glass-forming chemicals in platinum/gold crucibles and heating the mixture to 1150 degree C. Resulting glass analyses indicated that the HLW glass waste form composition was close to the target composition. The targeted waste loading of Envelope D sludge solids in the HLW glass was 30.7 wt percent, exclusive of Na and Si oxides. Condensate samples from the off-gas condenser and off-gas dry-ice trap indicated that very little of the radionuclides were volatilized during vitrification. Microstructure analysis of the HLW glass using Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray Analysis (EDAX) showed what appeared to be iron spinel in the HLW glass. Further X-Ray Diffraction (XRD) analysis confirmed the presence of nickel spinel trevorite (NiFe2O4). These crystals did not degrade the leaching characteristics of the glass. The HLW glass waste form passed leach tests that included a standard 90 degree C Product Consistency Test (PCT) and a modified version of the United States Environmental Protection Agency Toxicity Characteristic Leaching Procedure (TCLP)

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

    Science.gov (United States)

    Angel, Paul W.; Hann, Raiford E.

    1991-01-01

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

  19. Glass formation, properties and structure of soda-yttria-silica glasses

    Science.gov (United States)

    Angel, Paul W.; Hann, Raiford E.

    1992-01-01

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

  20. Sealing glasses for titanium and titanium alloys

    Science.gov (United States)

    Brow, Richard K.; McCollister, Howard L.; Phifer, Carol C.; Day, Delbert E.

    1997-01-01

    Barium lanthanoborate sealing-glass compositions are provided comprising various combinations (in terms of mole-%) of boron oxide (B.sub.2 O.sub.3), barium oxide (BaO), lanthanum oxide (La.sub.2 O.sub.3), and at least one other oxide selected from the group consisting of aluminum oxide (Al.sub.2 O.sub.3), calcium oxide (CaO), lithium oxide (Li.sub.2 O), sodium oxide (Na.sub.2 O), silicon dioxide (SiO.sub.2), or titanium dioxide (TiO.sub.2). These sealing-glass compositions are useful for forming hermetic glass-to-metal seals with titanium and titanium alloys having an improved aqueous durability and favorable sealing characteristics. Examples of the sealing-glass compositions are provided having coefficients of thermal expansion about that of titanium or titanium alloys, and with sealing temperatures less than about 900.degree. C., and generally about 700.degree.-800.degree. C. The barium lanthanoborate sealing-glass compositions are useful for components and devices requiring prolonged exposure to moisture or water, and for implanted biomedical devices (e.g. batteries, pacemakers, defibrillators, pumps).

  1. Effects of radionuclide decay on waste glass behavior: A critical review

    International Nuclear Information System (INIS)

    Wronkiewicz, D.J.

    1993-12-01

    This paper is an extension of a chapter in an earlier report [1] that provides an updated review on the status of radiation damage problems in nuclear waste glasses. This report will focus on radiation effects on vitrified borosilicate nuclear waste glasses under conditions expected in the proposed Yucca mountain repository. Radiation effects on high-level waste glasses and their surrounding repository environment are important considerations for radionuclide immobilization because of the potential to alter the glass stability and thereby influence the radionuclide retentive properties of this waste form. The influence of radionuclide decay on vitrified nuclear waste may be manifested by several changes, including volume, stored energy, structure, microstructure, mechanical properties, and phase separation. Radiation may also affect the composition of aqueous fluids and atmospheric gases in relatively close proximity to the waste form. What is important to the radionuclide retentive properties of the repository is how these radiation effects collectively or individually influence the durability and radionuclide release from the glass in the event of liquid water contact

  2. Optimization of β-casein stabilized nanoemulsions using experimental mixture design.

    Science.gov (United States)

    Maher, Patrick G; Fenelon, Mark A; Zhou, Yankun; Kamrul Haque, Md; Roos, Yrjö H

    2011-10-01

    The objective of this study was to determine the effect of changing viscosity and glass transition temperature in the continuous phase of nanoemulsion systems on subsequent stability. Formulations comprising of β-casein (2.5%, 5%, 7.5%, and 10% w/w), lactose (0% to 20% w/w), and trehalose (0% to 20% w/w) were generated from Design of Experiments (DOE) software and tested for glass transition temperature and onset of ice-melting temperature in maximally freeze-concentrated state (T(g) ' & T(m) '), and viscosity (μ). Increasing β-casein content resulted in significant (P mixture design was used to predict the optimum levels of lactose and trehalose required to attain the minimum and maximum T(g) ' and viscosity in solution at fixed protein contents. These mixtures were used to form the continuous phase of β-casein stabilized nanoemulsions (10% w/w sunflower oil) prepared by microfluidization at 70 MPa. Nanoemulsions were analyzed for T(g) ' & T(m) ', as well as viscosity, mean particle size, and stability. Increasing levels of β-casein (2.5% to 10% w/w) resulted in a significant (P mixture DOE was successfully used to predict glass transition and rheological properties for development of a continuous phase for use in nanoemulsions. © 2011 Institute of Food Technologists®

  3. DEFENSE HIGH LEVEL WASTE GLASS DEGRADATION

    International Nuclear Information System (INIS)

    Ebert, W.

    2001-01-01

    The purpose of this Analysis/Model Report (AMR) is to document the analyses that were done to develop models for radionuclide release from high-level waste (HLW) glass dissolution that can be integrated into performance assessment (PA) calculations conducted to support site recommendation and license application for the Yucca Mountain site. This report was developed in accordance with the ''Technical Work Plan for Waste Form Degradation Process Model Report for SR'' (CRWMS M andO 2000a). It specifically addresses the item, ''Defense High Level Waste Glass Degradation'', of the product technical work plan. The AP-3.15Q Attachment 1 screening criteria determines the importance for its intended use of the HLW glass model derived herein to be in the category ''Other Factors for the Postclosure Safety Case-Waste Form Performance'', and thus indicates that this factor does not contribute significantly to the postclosure safety strategy. Because the release of radionuclides from the glass will depend on the prior dissolution of the glass, the dissolution rate of the glass imposes an upper bound on the radionuclide release rate. The approach taken to provide a bound for the radionuclide release is to develop models that can be used to calculate the dissolution rate of waste glass when contacted by water in the disposal site. The release rate of a particular radionuclide can then be calculated by multiplying the glass dissolution rate by the mass fraction of that radionuclide in the glass and by the surface area of glass contacted by water. The scope includes consideration of the three modes by which water may contact waste glass in the disposal system: contact by humid air, dripping water, and immersion. The models for glass dissolution under these contact modes are all based on the rate expression for aqueous dissolution of borosilicate glasses. The mechanism and rate expression for aqueous dissolution are adequately understood; the analyses in this AMR were conducted to

  4. Effect of different glasses in glass bonded zeolite

    International Nuclear Information System (INIS)

    Lewis, M.A.; Ackerman, J.P.; Verma, S.

    1995-01-01

    A mineral waste form has been developed for chloride waste salt generated during the pyrochemical treatment of spent nuclear fuel. The waste form consists of salt-occluded zeolite powders bound within a glass matrix. The zeolite contains the salt and immobilizes the fission products. The zeolite powders are hot pressed to form a mechanically stable, durable glass bonded zeolite. Further development of glass bonded zeolite as a waste form requires an understanding of the interaction between the glass and the zeolite. Properties of the glass that enhance binding and durability of the glass bonded zeolite need to be identified. Three types of glass, boroaluminosilicate, soda-lime silicate, and high silica glasses, have a range of properties and are now being investigated. Each glass was hot pressed by itself and with an equal amount of zeolite. MCC-1 leach tests were run on both. Soda-lime silicate and high silica glasses did not give a durable glass bonded zeolite. Boroaluminosilicate glasses rich in alkaline earths did bind the zeolite and gave a durable glass bonded zeolite. Scanning electron micrographs suggest that the boroaluminosilicate glasses wetted the zeolite powders better than the other glasses. Development of the glass bonded zeolite as a waste form for chloride waste salt is continuing

  5. Glass Transition, Crystallization of Glass-Forming Melts, and Entropy

    Directory of Open Access Journals (Sweden)

    Jürn W. P. Schmelzer

    2018-02-01

    Full Text Available A critical analysis of possible (including some newly proposed definitions of the vitreous state and the glass transition is performed and an overview of kinetic criteria of vitrification is presented. On the basis of these results, recent controversial discussions on the possible values of the residual entropy of glasses are reviewed. Our conclusion is that the treatment of vitrification as a process of continuously breaking ergodicity with entropy loss and a residual entropy tending to zero in the limit of zero absolute temperature is in disagreement with the absolute majority of experimental and theoretical investigations of this process and the nature of the vitreous state. This conclusion is illustrated by model computations. In addition to the main conclusion derived from these computations, they are employed as a test for several suggestions concerning the behavior of thermodynamic coefficients in the glass transition range. Further, a brief review is given on possible ways of resolving the Kauzmann paradox and its implications with respect to the validity of the third law of thermodynamics. It is shown that neither in its primary formulations nor in its consequences does the Kauzmann paradox result in contradictions with any basic laws of nature. Such contradictions are excluded by either crystallization (not associated with a pseudospinodal as suggested by Kauzmann or a conventional (and not an ideal glass transition. Some further so far widely unexplored directions of research on the interplay between crystallization and glass transition are anticipated, in which entropy may play—beyond the topics widely discussed and reviewed here—a major role.

  6. Effects of waste content of glass waste forms on Savannah River high-level waste disposal costs

    International Nuclear Information System (INIS)

    McDonell, W.R.; Jantzen, C.M.

    1985-01-01

    Effects of the waste content of glass waste forms of Savannah River high-level waste disposal costs are evaluated by their impact on the number of waste canisters produced. Changes in waste content affect onsite Defense Waste Processing Facility (DWPF) costs as well as offsite shipping and repository emplacement charges. A nominal 1% increase over the 28 wt % waste loading of DWPF glass would reduce disposal costs by about $50 million for Savannah River wastes generated to the year 2000. Waste form modifications under current study include adjustments of glass frit content to compensate for added salt decontamination residues and increased sludge loadings in the DWPF glass. Projected cost reductions demonstrate significant incentives for continued optimization of the glass waste loadings. 13 refs., 3 figs., 3 tabs

  7. Glass-forming ability and crystallization behavior of some binary and ternary Ni-based glassy alloys

    International Nuclear Information System (INIS)

    Louzguine-Luzgin, Dmitri V.; Louzguina-Luzgina, Larissa V.; Xie Guoqiang; Li Song; Zhang Wei; Inoue, Akihisa

    2008-01-01

    The purpose of the current paper is to study the influence of Ti, V, Nb, Al, Sn and Pd additions on the glass-forming ability, formation of a supercooled liquid region and a devitrification process of some Ni-Zr glassy alloys as well as to compare the results with those obtained for similar Cu-based alloys studied earlier. The Ni-based glassy alloys were investigated by using X-ray diffraction, differential scanning and isothermal calorimetries. Although the studied Ni-based alloys showed high values of the reduced glass-transition temperature of about 0.6, their glass-forming ability is quite low. This fact may be explained by low stability of the supercooled liquid against crystallization and formation of the equilibrium intermetallic compounds with a high growth rate compared to those observed in similar Cu-based alloys studied earlier. Relatively low thermal conductivity of Ni-based alloys is also found to be another factor limiting their glass-forming ability

  8. Disposal costs for SRP high-level wastes in borosilicate glass and crystalline ceramic waste forms

    International Nuclear Information System (INIS)

    Rozsa, R.B.; Campbell, J.H.

    1982-01-01

    Purpose of this document is to compare and contrast the overall burial costs of the glass and ceramic waste forms, including processing, storage, transportation, packaging, and emplacement in a repository. Amount of waste will require approximately 10,300 standard (24 in. i.d. x 9-5/6 ft length) canisters of waste glass, each containing about 3260 lb of waste at 28% waste loading. The ceramic waste form requires about one-third the above number of standard canisters. Approximately $2.5 billion is required to process and dispose of this waste, and the total cost is independent of waste form (glass or ceramic). The major cost items (about 80% of the total cost) for all cases are capital and operating expenses. The capital and 20-year operating costs for the processing facility are the same order of magnitude, and their sum ranges from about one-half of the total for the reference glass case to two-thirds of the total for the ceramic cases

  9. On the predictive capabilities of CPA for applications in the chemical industry: Mulficomponent mixtures containing methyl-methacrylate, dimethyl-ether or acetic acid

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Kontogeorgis, Georgios

    2014-01-01

    mixtures exhibiting vapor-liquid (VLE) and/or liquid-liquid (LLE) equilibrium. The first two cases include mixtures of methyl-methacrylate with acetone or methanol and dimethyl-ether with ethanol, respectively. In these two cases, the classical form of CPA is used. The third case involves aqueous mixtures...... for the acetic acid-water system for which different parameter sets at different temperatures can be recommended. Even with the use of CPA-HV mixing rules, modeling of the acetic acid-water system with few interaction parameters remains a challenging task. Excellent simultaneous VLE and LLE correlation...... is obtained for complex systems such as aqueous mixtures with ethers and esters. The multicomponent results are, with a few exceptions, very satisfactory, especially for the vapor-liquid equilibrium cases. For the demanding aqueous acetic acid-water containing systems, one parameter set is recommended...

  10. Distinct atomic structures of the Ni-Nb metallic glasses formed by ion beam mixing

    International Nuclear Information System (INIS)

    Tai, K. P.; Wang, L. T.; Liu, B. X.

    2007-01-01

    Four Ni-Nb metallic glasses are obtained by ion beam mixing and their compositions are measured to be Ni 77 Nb 23 , Ni 55 Nb 45 , Ni 31 Nb 69 , and Ni 15 Nb 85 , respectively, suggesting that a composition range of 23-85 at. % of Nb is favored for metallic glass formation in the Ni-Nb system. Interestingly, diffraction analyses show that the structure of the Nb-based Ni 31 Nb 69 metallic glass is distinctly different from the structure of the Nb-based Ni 15 Nb 85 metallic glass, as the respective amorphous halos are located at 2θ≅38 and 39 deg. To explore an atomic scale description of the Ni-Nb metallic glasses, an n-body Ni-Nb potential is first constructed with an aid of the ab initio calculations and then applied to perform the molecular dynamics simulation. Simulation results determine not only the intrinsic glass forming range of the Ni-Nb system to be within 20-85 at. % of Nb, but also the exact atomic positions in the Ni-Nb metallic glasses. Through a statistical analysis of the determined atomic positions, a new dominant local packing unit is found in the Ni 15 Nb 85 metallic glass, i.e., an icositetrahedron with a coordination number to be around 14, while in Ni 31 Nb 69 metallic glasses, the dominant local packing unit is an icosahedron with a coordination number to be around 12, which has been reported for the other metallic glasses. In fact, with increasing the irradiation dose, the Ni 31 Nb 69 metallic glasses are formed through an intermediate state of face-centered-cubic-solid solution, whereas the Ni 15 Nb 85 metallic glass is through an intermediate state of body-centered-cubic-solid solution, suggesting that the structures of the constituent metals play an important role in governing the structural characteristics of the resultant metallic glasses

  11. Study on the leach mechanism of 90-19/U glass form in underground water of disposal site

    International Nuclear Information System (INIS)

    Sheng Jiawei; Luo Shanggeng; Tang Baolong

    1996-01-01

    The leach behavior of 90-19/U glass form in underground water (UW) of disposal site and in the deionized water (DIW) is studied. The total mass losses of glass form and the normalized element mass losses of B, Li and Si in UW are presented and compared to DIW. It is found that the ions in UW affect the leach behavior of 90-19/U glass. At the beginning of the reaction the reaction rate of the glass is smaller in UW than in DIW due to the low glass dissolution affinity in UW which is defined as (1-c/K). The rate determining step of leach reaction of 90-19/U glass in UW during the entire reaction period is the ion-exchange reaction. The apparent activation energy of glass reaction in UW is 51.6 kJ/mol

  12. Strongly correlated Fermi-Bose mixtures in disordered optical lattices

    International Nuclear Information System (INIS)

    Sanchez-Palencia, L; Ahufinger, V; Kantian, A; Zakrzewski, J; Sanpera, A; Lewenstein, M

    2006-01-01

    We investigate theoretically the low-temperature physics of a two-component ultracold mixture of bosons and fermions in disordered optical lattices. We focus on the strongly correlated regime. We show that, under specific conditions, composite fermions, made of one fermion plus one bosonic hole, form. The composite picture is used to derive an effective Hamiltonian whose parameters can be controlled via the boson-boson and the boson-fermion interactions, the tunnelling terms and the inhomogeneities. We finally investigate the quantum phase diagram of the composite fermions and show that it corresponds to the formation of Fermi glasses, spin glasses and quantum percolation regimes

  13. Strongly correlated Fermi-Bose mixtures in disordered optical lattices

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez-Palencia, L [Laboratoire Charles Fabry de l' Institut d' Optique, CNRS and Universite Paris-Sud XI, Bat 503, Centre scientifique, F-91403 Orsay Cedex (France); Ahufinger, V [ICREA and Grup d' optica, Departament de FIsica, Universitat Autonoma de Barcelona, E-08193 Belaterra (Barcelona) (Spain); Kantian, A [Institut fuer Theoretische Physik, Universitaet Innsbruck, A-6020 Innsbruck (Austria); Zakrzewski, J [Instytut Fizyki imienia Mariana Smoluchowskiego i Centrum Badan Ukladow Zlozonych imienia Marka Kaca, Uniwersytet Jagiellonski, ulica Reymonta 4, PL-30-059 Krakow (Poland); Sanpera, A [ICREA and Grup de FIsica Teorica, Departament de FIsica, Universitat Autonoma de Barcelona, E-08193 Belaterra (Barcelona) (Spain); Lewenstein, M [ICREA and ICFO-Institut de Ciencies Fotoniques, Parc Mediterrani de la TecnologIa, E-08860 Castelldefels (Barcelona) (Spain); Institut fuer Theoretische Physik, Universitaet Hannover, D-30167 Hannover (Germany)

    2006-05-28

    We investigate theoretically the low-temperature physics of a two-component ultracold mixture of bosons and fermions in disordered optical lattices. We focus on the strongly correlated regime. We show that, under specific conditions, composite fermions, made of one fermion plus one bosonic hole, form. The composite picture is used to derive an effective Hamiltonian whose parameters can be controlled via the boson-boson and the boson-fermion interactions, the tunnelling terms and the inhomogeneities. We finally investigate the quantum phase diagram of the composite fermions and show that it corresponds to the formation of Fermi glasses, spin glasses and quantum percolation regimes.

  14. Removal of phenol from aqueous solution using polymer inclusion membrane based on mixture of CTA and CA

    Science.gov (United States)

    Benosmane, Nadjib; Boutemeur, Baya; Hamdi, Safouane M.; Hamdi, Maamar

    2018-03-01

    Nowadays, there are increasingly stringent regulations requiring more and more treatment of industrial effluents to generate product waters which could be easily reused or disposed of to the environment without any harmful effects. In the present work, the removal of phenol from aqueous solution across polymer inclusion membrane (PIM), based on mixture of cellulose triacetate and cellulose acetate as support (75/25%), calix[4]resorcinarene derivative as a carrier and 2-nitrophenyl octyl ether (2-NPOE) as plasticizer was investigated. The experimental part of this investigation involved the influence of carrier nature, plasticizer concentration, pH phases, and phenol initial concentration on the removal efficiency of phenol from synthetic wastewater. A PIM containing 0.1 g (of mixture polymer), (0.15 g/g mixture of polymer) of carrier and (0.03 ml/g mixture of polymer) of 2-NPOE provided the highest percentage of phenol removal efficiency over a 6-day transport; the removal was found to be about 95%, indeed the removal was found to be highly dependent of pH phases. The feed solution in these transport experiments was at pH 2, while the stripping solution contained 0.20 M NaOH. This study claims that the PIM with a mixture of cellulose derivatives can be used effectively to remove phenols from wastewaters.

  15. Waste glass corrosion modeling: Comparison with experimental results

    International Nuclear Information System (INIS)

    Bourcier, W.L.

    1993-11-01

    A chemical model of glass corrosion will be used to predict the rates of release of radionuclides from borosilicate glass waste forms in high-level waste repositories. The model will be used both to calculate the rate of degradation of the glass, and also to predict the effects of chemical interactions between the glass and repository materials such as spent fuel, canister and container materials, backfill, cements, grouts, and others. Coupling between the degradation processes affecting all these materials is expected. Models for borosilicate glass dissolution must account for the processes of (1) kinetically-controlled network dissolution, (2) precipitation of secondary phases, (3) ion exchange, (4) rate-limiting diffusive transport of silica through a hydrous surface reaction layer, and (5) specific glass surface interactions with dissolved cations and anions. Current long-term corrosion models for borosilicate glass employ a rate equation consistent with transition state theory embodied in a geochemical reaction-path modeling program that calculates aqueous phase speciation and mineral precipitation/dissolution. These models are currently under development. Future experimental and modeling work to better quantify the rate-controlling processes and validate these models are necessary before the models can be used in repository performance assessment calculations

  16. Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100- x Al x Metallic Glasses

    Science.gov (United States)

    Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

    2018-06-01

    In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated and 13-coordinated ) and by playing a main role in the structure stability of the Ti-Al MGs.

  17. Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100-x Al x Metallic Glasses

    Science.gov (United States)

    Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

    2018-03-01

    In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated and 13-coordinated ) and by playing a main role in the structure stability of the Ti-Al MGs.

  18. Dynamics of glass-forming liquids

    DEFF Research Database (Denmark)

    Hansen, Henriette Wase

    on alpha relaxation dynamics, and for the two van der Waals liquids, also when we have separation of timescales, i.e. the alpha relaxation is not contributing to the picosecond dynamics. The concept of isomorphs is observed to break down in two cases for the hydrogen bonding system: in density scaling......The overall theme of this work has been to experimentally test the shoving model and isomorph theory related to the dynamics of glass-forming liquids, both of which, rather than being universal explanations, are expected to work in the simplest case. We test the connection between fast and slow...... dynamics in light of the shoving model from the temperature dependence of the mean-squared displacement from neutron scattering at nanosecond timescale and the elastic modulus from shear mechanics. We find the fast dynamics to correlate with the alpha relaxation time and fragility in agreement...

  19. Fluctuations in an Inorganic Glass Forming System Capable of Liquid-Liquid Phase Separation

    Science.gov (United States)

    Bogdanov, V.; Maksimov, L.; Anan'ev, A.; Nemilov, S.; Rusan, V.

    2012-08-01

    Rayleigh and Mandel'shtam-Brillouin scattering (RMBS) spectroscopy and high temperature ultrasonic study (HTUS) are applied to PbO-Al2O3-B2O3 glass forming system characterized by over liquidus miscibility gap. Temperature dependences of ultrasonic velocity of glass melts were measured in 600-1200°C range. "Frozen-in" density fluctuations in two phase glasses were estimated from HTUS data by Macedo-Shroeder formulation. Landau-Placzek ratios were found from RMBS spectra of single phase glasses at room temperature. Results of RMBS and HTUS were compared with well-known SAXS data. It was found that contribution of "frozen-in" density fluctuations into light scattering by two-phase glasses is much smaller than the scattering on particles of the second glassy phase causing opalescence of the glasses. Abnormal "water-like" growth of ultrasonic velocity with melt temperature can be explained by coexistence of two types of packaging of structural elements.

  20. Infrared and Raman investigation of rare-earth phosphate glasses for potential use as radioactive waste forms

    International Nuclear Information System (INIS)

    Morgan, S.H.

    1989-01-01

    This project was designed to investigate the properties of the rare-earth phosphate glass systems CeO 2 -P 2 O 5 and Pr 2 O 3 -P 2 O 5 for potential use as radioactive waste glasses. The glass-forming region and optimum processing parameters of these glass systems were investigated. The structure of the host glasses and glassed loaded with simulated waste elements was investigated using Raman and infrared spectroscopy. Because of the radical differences in the spectra of the molybdenum-loaded glasses, the structure of the MoO 3 -P 2 O 5 glass system was also investigated. 29 refs., 8 figs., 2 tabs

  1. Performance of borosilicate glass, Synroc and spent fuel as nuclear waste forms

    International Nuclear Information System (INIS)

    Lutze, W.; Grambow, B.; Ewing, R.C.

    1990-01-01

    Presently, there are three prominent waste forms under consideration for the disposal of high-level waste: Borosilicate glass and Synroc for high-level radioactive waste from fuel reprocessing and spent fuel as the waste form for non-reprocessed fuel. Using the present experimental data base, one may compare the performance of these three waste forms under repository relevant conditions. In low water flow regimes and at temperatures less than 100 degree C, the fractional release rates of all three waste forms are low, on the order of 10-7/d or less and may decrease with time. Under these conditions the three waste forms behave similarly. At elevated temperatures or in high flow regimes, the durability of borosilicate glass will be much less than that of Synroc, and thus, for certain disposal schemes (e.g., deep burial) Synroc is preferable. All predictions of the long-term behavior are based on the extrapolation of short term experimental data, we point out that appropriate and useful natural analogues are available for each of these waste forms and should be used in the performance assessment of each waste form's long-term behavior. 14 refs

  2. Long-term conversion of 45S5 bioactive glass-ceramic microspheres in aqueous phosphate solution.

    Science.gov (United States)

    Fu, Hailuo; Rahaman, Mohamed N; Day, Delbert E; Huang, Wenhai

    2012-05-01

    The conversion of 45S5 glass and glass-ceramics to a hydroxyapatite (HA)-like material in vitro has been studied extensively, but only for short reaction times (typically glass-ceramic microspheres (designated 45S5c) in an aqueous phosphate solution. Microspheres of 45S5c (75-150 μm) were immersed for 10 years at room temperature (~25 °C) in K(2)HPO(4) solution with a concentration of 0.01 M or 1.0 M, and with a starting pH of 7.0 or 9.5. The reacted 45S5c microspheres and solutions were analyzed using structural and analytical techniques. Only 25-45 vol% of the 45S5c microspheres were converted to an HA-like material after the 10 year reaction. In solutions with a starting pH of 9.5, an increase in the K(2)HPO(4) concentration from 0.01 to 1.0 M resulted in a doubling of the volume of the microspheres converted to an HA-like material but had little effect on the composition of the HA-like product. In comparison, reaction of the 45S5c microspheres in the solution with a starting pH of 7.0 resulted in an HA-like product in the 0.01 M K(2)HPO(4) solution but a calcium pyrophosphate product, Ca(10)K(4)(P(2)O(7))(6).9H(2)O, in the 1.0 M solution. The consequences of these results for the long-term use of 45S5 glass-ceramics in biomedical applications are discussed.

  3. Beating Homogeneous Nucleation and Tuning Atomic Ordering in Glass-Forming Metals by Nanocalorimetry.

    Science.gov (United States)

    Zhao, Bingge; Yang, Bin; Abyzov, Alexander S; Schmelzer, Jürn W P; Rodríguez-Viejo, Javier; Zhai, Qijie; Schick, Christoph; Gao, Yulai

    2017-12-13

    In this paper, the amorphous Ce 68 Al 10 Cu 20 Co 2 (atom %) alloy was in situ prepared by nanocalorimetry. The high cooling and heating rates accessible with this technique facilitate the suppression of crystallization on cooling and the identification of homogeneous nucleation. Different from the generally accepted notion that metallic glasses form just by avoiding crystallization, the role of nucleation and growth in the crystallization behavior of amorphous alloys is specified, allowing an access to the ideal metallic glass free of nuclei. Local atomic configurations are fundamentally significant to unravel the glass forming ability (GFA) and phase transitions in metallic glasses. For this reason, isothermal annealing near T g from 0.001 s to 25,000 s following quenching becomes the strategy to tune local atomic configurations and facilitate an amorphous alloy, a mixed glassy-nanocrystalline state, and a crystalline sample successively. On the basis of the evolution of crystallization enthalpy and overall latent heat on reheating, we quantify the underlying mechanism for the isothermal nucleation and crystallization of amorphous alloys. With Johnson-Mehl-Avrami method, it is demonstrated that the coexistence of homogeneous and heterogeneous nucleation contributes to the isothermal crystallization of glass. Heterogeneous rather than homogeneous nucleation dominates the isothermal crystallization of the undercooled liquid. For the mixed glassy-nanocrystalline structure, an extraordinary kinetic stability of the residual glass is validated, which is ascribed to the denser packed interface between amorphous phase and ordered nanocrystals. Tailoring the amorphous structure by nanocalorimetry permits new insights into unraveling GFA and the mechanism that correlates local atomic configurations and phase transitions in metallic glasses.

  4. Removal of Pb (II from Aqueous Solutions Using Mixtures of Bamboo Biochar and Calcium Sulphate, and Hydroxyapatite and Calcium Sulphate

    Directory of Open Access Journals (Sweden)

    Ahmed Hassan

    2016-01-01

    Full Text Available Sorption characteristics of Pb(II from aqueous solutions through a low-cost adsorbent mixture comprising of Bamboo biochar (BB and Calcium Sulphate (CS, and a more expensive mixture of Hydroxyapatite (HAP and Calcium Sulphate (CS, were investigated. The effects of equilibrium contact time, and adsorbate concentration conducted in batch experiments were studied. Adsorption equilibrium was established in 40 (min. The adsorption mechanism of Pb(II from these two adsorbent mixtures was carried out through a kinetic rate order. A pseudo second-order kinetic model was applied for the adsorption processes. The model yielded good correlation (R2 >0.999 of the experimental data. Adsorption of Pb(II using (BB&CS and (HAP&CS correlated well (R2 >0.99 with both the Langmuir and Freundlich isotherm equations under the concentration range studied. Hence, the effectiveness of an inexpensive natural material (BB&CS mixture in Pb(II removal is established, and is promising for use in other heavy metal adsorptions.

  5. Statistical experimental design for saltstone mixtures

    International Nuclear Information System (INIS)

    Harris, S.P.; Postles, R.L.

    1992-01-01

    The authors used a mixture experimental design for determining a window of operability for a process at the U.S. Department of Energy, Savannah River Site, Defense Waste Processing Facility (DWPF). The high-level radioactive waste at the Savannah River Site is stored in large underground carbon steel tanks. The waste consists of a supernate layer and a sludge layer. Cesium-137 will be removed from the supernate by precipitation and filtration. After further processing, the supernate layer will be fixed as a grout for disposal in concrete vaults. The remaining precipitate will be processed at the DWPF with treated waste tank sludge and glass-making chemicals into borosilicate glass. The leach-rate properties of the supernate grout formed from various mixes of solidified coefficients for NO 3 and chromium were used as a measure of leach rate. Various mixes of cement, Ca(OH) 2 , salt, slag, and fly ash were used. These constituents comprise the whole mix. Thus, a mixture experimental design was used. The regression procedure (PROC REG) in SAS was used to produce analysis of variance (ANOVA) statistics. In addition, detailed model diagnostics are readily available for identifying suspicious observations. For convenience, trillinear contour (TLC) plots, a standard graphics tool for examining mixture response surfaces, of the fitted model were produced using ECHIP

  6. Molecular dynamics study of the ternary Cu50Ti25Zr25 bulk glass forming alloy

    Directory of Open Access Journals (Sweden)

    Celtek M.

    2011-05-01

    Full Text Available The structure and thermodynamic properties of a ternary Cu50Ti25Zr25 metallic glass forming alloy in solid-liquid to glass phases were studied using molecular dynamics (MD method based on tight-binding (TB potentials. An atomic description of the melting, glass formation and crystallization process has been analyzed using different heating and cooling rates. The computed Glass Forming Ability (GFA parameters are in good agreement with experimental data. The structure analysis of the Cu50Ti25Zr25 based on molecular dynamics simulation will be also presented and compared with available MD results. We have also discussed the crystallization transition with two different interatomic potentials used in this work

  7. Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

    Science.gov (United States)

    Smith, Jeremy D; Kinney, Haley; Anastasio, Cort

    2015-04-21

    Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

  8. Method of producing homogeneous mixed metal oxides and metal--metal oxide mixtures

    International Nuclear Information System (INIS)

    Quinby, T.C.

    1978-01-01

    Metal powders, metal oxide powders, and mixtures thereof of controlled particle size are provided by reacting an aqueous solution containing dissolved metal values with excess urea. Upon heating, urea reacts with water from the solution to leave a molten urea solution containing the metal values. The molten urea solution is heated to above about 180 0 C, whereupon metal values precipitate homogeneously as a powder. The powder is reduced to metal or calcined to form oxide particles. One or more metal oxides in a mixture can be selectively reduced to produce metal particles or a mixture of metal and metal oxide particles

  9. Annual report on the development and characterization of solidified forms for nuclear wastes, 1979

    International Nuclear Information System (INIS)

    Chick, L.A.; McVay, G.L.; Mellinger, G.B.; Roberts, F.P.

    1980-12-01

    Development and characterization of solidified nuclear waste forms is a major continuing effort at Pacific Northwest Laboratory. Contributions from seven programs directed at understanding chemical composition, process conditions, and long-term behaviors of various nuclear waste forms are included in this report. The major findings of the report are included in extended figure captions that can be read as brief technical summaries of the research, with additional information included in a traditional narrative format. Waste form development proceeded on crystalline and glass materials for high-level and transuranic (TRU) wastes. Leaching studies emphasized new areas of research aimed at more basic understanding of waste form/aqueous solution interactions. Phase behavior and thermal effects research included studies on crystal phases in defense and TRU waste glasses and on liquid-liquid phase separation in borosilicate waste glasses. Radiation damage effects in crystals and glasses from alpha decay and from transmutation are reported

  10. Glasses used in the solidification of high level radioactive waste: their behaviour in aqueous solutions

    International Nuclear Information System (INIS)

    Grauer, R.

    1983-02-01

    Because of their amorphous structure, glasses are particularly suitable matrixes for the solidification of the mixture of radionuclides included in the high level wastes from reactor fuel reprocessing. They are not sensitive to variations in the fractions present of different waste oxides and are resistent to the effects of irradiation. In particular, borosilicate glasses have been investigated for around 25 years and the vitrification techniques have been tested on the technological scale. The environmental conditions within a final waste repository are expected to be such that the chemical resistance of glasses to attack by groundwaters is of special interest. In the present report the corrosion behaviour is described, with emphasis being placed upon the most significant controlling parameters. Since experimental determination of corrosion rates must be done in relatively short-time experiments, the results of which can depend strongly upon the measurement methods employed, it is necessary to carry out a critical assessment of the techniques commonly used in laboratory work. Experimental results are illustrated by means of selected examples. Particular emphasis is placed upon the effects of increased temperatures and of irradiation. The models which have been proposed for the estimation of the long-term corrosion behaviour of glasses are not yet fully sufficient and improvements are required. Furthermore, the actual corrosion rates which are fed into such models must be replaced by values more appropriate for the actual environmental conditions to which the glasses are most likely to be exposed within high level waste repositories. It should be noted, however, that even with current conservative input data on corrosion rates, typical estimated lifetimes for vitrified waste blocks are of the order of 10 5 years. The report concludes with recommendations concerning the most useful areas for further investigations. (author)

  11. Structural relaxation and thermal conductivity of high-pressure formed, high-density di-n-butyl phthalate glass and pressure induced departures from equilibrium state.

    Science.gov (United States)

    Johari, G P; Andersson, Ove

    2017-06-21

    We report a study of structural relaxation of high-density glasses of di-n-butyl phthalate (DBP) by measuring thermal conductivity, κ, under conditions of pressure and temperature (p,T) designed to modify both the vibrational and configurational states of a glass. Various high-density glassy states of DBP were formed by (i) cooling the liquid under a fixed high p and partially depressurizing the glass, (ii) isothermal annealing of the depressurized glass, and (iii) pressurizing the glass formed by cooling the liquid under low p. At a given low p, κ of the glass formed by cooling under high p is higher than that of the glass formed by cooling under low p, and the difference increases as glass formation p is increased. κ of the glass formed under 1 GPa is ∼20% higher at ambient p than κ of the glass formed at ambient p. On heating at low p, κ decreases until the glass to liquid transition range is reached. This is the opposite of the increase in κ observed when a glass formed under a certain p is heated under the same p. At a given high p, κ of the low-density glass formed by cooling at low p is lower than that of the high-density glass formed by cooling at that high p. On heating at high p, κ increases until the glass to liquid transition range is reached. The effects observed are due to a thermally assisted approach toward equilibrium at p different from the glass formation p. In all cases, the density, enthalpy, and entropy would change until the glasses become metastable liquids at a fixed p, thus qualitatively relating κ to variation in these properties.

  12. The correlation between fragility, density, and atomic interaction in glass-forming liquids.

    Science.gov (United States)

    Wang, Lijin; Guan, Pengfei; Wang, W H

    2016-07-21

    The fragility that controls the temperature-dependent viscous properties of liquids as the glass transition is approached, in various glass-forming liquids with different softness of the repulsive part of atomic interactions at different densities, is investigated by molecular dynamic simulations. We show that the landscape of fragility in purely repulsive systems can be separated into three regions denoted as RI, RII, and RIII, respectively, with qualitatively disparate dynamic behaviors: RI which can be described by "softness makes strong glasses," RII where fragility is independent of softness and can only be tuned by density, and RIII with constant fragility, suggesting that density plays an unexpected role for understanding the repulsive softness dependence of fragility. What is more important is that we unify the long-standing inconsistence with respect to the repulsive softness dependence of fragility by observing that a glass former can be tuned more fragile if nonperturbative attraction is added into it. Moreover, we find that the vastly dissimilar influences of attractive interaction on fragility could be estimated from the structural properties of related zero-temperature glasses.

  13. A Glass-Ceramic Waste Forms for the Immobilization of Rare Earth Oxides from the Pyroprocessing Waste salt

    International Nuclear Information System (INIS)

    Ahn, Byung-Gil; Park, Hwan-Seo; Kim, Hwan-Young; Kim, In-Tae

    2008-01-01

    The fission product of rare earth (RE) oxide wastes are generates during the pyroprocess . Borosilicate glass or some ceramic materials such as monazite, apatite or sodium zirconium phosphate (NZP) have been a prospective host matrix through lots of experimental results. Silicate glasses have long been the preferred waste form for the immobilization of HLW. In immobilization of the RE oxides, the developed process on an industrial scale involves their incorporation into a glass matrix, by melting under 1200 ∼ 1300 .deg. C. Instead of the melting process, glass powder sintering is lower temperature (∼ 900 .deg. C) required for the process which implies less demanding conditions for the equipment and a less evaporation of volatile radionuclides. This study reports the behaviors, direct vitrification of RE oxides with glass frit, glass powder sintering of REceramic with glass frit, formation of RE-apatite (or REmonazite) ceramic according to reaction temperature, and the leach resistance of the solidified waste forms

  14. Comprehension and modelling of chromia-forming alloys corrosion mechanisms in nuclear glasses

    International Nuclear Information System (INIS)

    Schmucker, Eric

    2016-01-01

    Nuclear wastes management consists in the confinement of the radioactive wastes in a glass matrix. This is made by inductive melting in a hot crucible at an operating temperature around 1150 C. These crucibles are constituted of nickel based superalloys with high chromium content. They are submitted to a harsh corrosion by the molten glass, eventually leading to their replacement. The protection of the crucible against corrosion is best provided by the establishment of a protective chromium oxide layer at the surface of the alloy. A binary chromia-forming alloy (Ni-30Cr) is studied in this work. Three different binary and ternary glass compositions are chosen in order to understand the influence of the glass basicity and glass viscosity on the corrosion kinetics. Besides, the de-correlation of the formation and dissolution kinetics of the oxide layer allows the modelling of the overall oxide growth in the molten glass. For that purpose, the oxide formation kinetics in molten glass media is assimilated to the oxidation kinetics of the alloy in gaseous media with oxygen partial pressure that are representative of the redox properties of the glasses. Studies of the oxidation kinetics and of the diffusion mechanisms have shown that the oxidation kinetics is independent on the oxygen pressure in the range of 10"-"1"3 up to 10"-"3 atm O_2 at 1150 C. The present work has shown that the dissolution kinetics of the oxide layer is governed by the diffusion of Cr(III) in the glass melt. This dissolution kinetics has been evaluated from the diffusion coefficient and the solubility limit of Cr(III) in the glass. Finally, the overall growth kinetics of the Cr_2O_3 layer in the glass has been successfully modelled for each glass, thanks to the knowledge of (i) the solubility limit of Cr(III), (ii) its diffusion coefficient in the glasses and (iii) the oxidation kinetics of the alloy. The presented model also allows quantifying the influence of each of these parameters on the

  15. Revealing the Link between Structural Relaxation and Dynamic Heterogeneity in Glass-Forming Liquids.

    Science.gov (United States)

    Wang, Lijin; Xu, Ning; Wang, W H; Guan, Pengfei

    2018-03-23

    Despite the use of glasses for thousands of years, the nature of the glass transition is still mysterious. On approaching the glass transition, the growth of dynamic heterogeneity has long been thought to play a key role in explaining the abrupt slowdown of structural relaxation. However, it still remains elusive whether there is an underlying link between structural relaxation and dynamic heterogeneity. Here, we unravel the link by introducing a characteristic time scale hiding behind an identical dynamic heterogeneity for various model glass-forming liquids. We find that the time scale corresponds to the kinetic fragility of liquids. Moreover, it leads to scaling collapse of both the structural relaxation time and dynamic heterogeneity for all liquids studied, together with a characteristic temperature associated with the same dynamic heterogeneity. Our findings imply that studying the glass transition from the viewpoint of dynamic heterogeneity is more informative than expected.

  16. Revealing the Link between Structural Relaxation and Dynamic Heterogeneity in Glass-Forming Liquids

    Science.gov (United States)

    Wang, Lijin; Xu, Ning; Wang, W. H.; Guan, Pengfei

    2018-03-01

    Despite the use of glasses for thousands of years, the nature of the glass transition is still mysterious. On approaching the glass transition, the growth of dynamic heterogeneity has long been thought to play a key role in explaining the abrupt slowdown of structural relaxation. However, it still remains elusive whether there is an underlying link between structural relaxation and dynamic heterogeneity. Here, we unravel the link by introducing a characteristic time scale hiding behind an identical dynamic heterogeneity for various model glass-forming liquids. We find that the time scale corresponds to the kinetic fragility of liquids. Moreover, it leads to scaling collapse of both the structural relaxation time and dynamic heterogeneity for all liquids studied, together with a characteristic temperature associated with the same dynamic heterogeneity. Our findings imply that studying the glass transition from the viewpoint of dynamic heterogeneity is more informative than expected.

  17. Glass forming ability and mechanical properties of Zr50Cu42Al8 bulk metallic glass

    International Nuclear Information System (INIS)

    Xia, L; Chan, K C; Wang, G; Liu, L

    2008-01-01

    In this work, we report that Zr 50 Cu 42 Al 8 bulk metallic glass (BMG) exhibits excellent glass forming ability and mechanical properties. Zr 50 Cu 42 Al 8 glassy rods with a diameter of 3 mm were prepared using conventional copper mould suction casting. The glassy rod exhibits a modulus of about 115 GPa and a fracture strength of about 2 GPa, and, as compared with other large-scale BMGs, it has excellent room-temperature plasticity of up to 20% under compression. The fracture mechanism of the rod was investigated by microstructural investigations, and it was found that the large plasticity of the as-cast rod is closely related to the in situ formation of nano-crystalline particles embedded in the amorphous matrix.

  18. The Method for Investigating the Structurization of Water-Organic Mixtures

    International Nuclear Information System (INIS)

    Karitskaya, S

    2013-01-01

    The investigation of the properties of micellar systems is of great practical importance, since the microheterogeneous structure, in particular, of aqueous-organic solutions can be used to create reaction centers with designed properties, which will make it possible to increase the efficiency of processes associated with the intramolecular conversion of the electronic excitation energy of a molecule. In the present paper, model systems to stimulate chemical reactions are the spatial-temporal structures (STS) formed as a result of photophysical and photochemical reactions, whose time characteristics are highly sensitive to a change in the solvent compositions. The STS evolution processes are slow and the structures formed have macroscopic sizes, which makes the system under consideration a convenient object for experimental studies. The spectral and time characteristics of the spatial-temporal structures luminescing when exposed to UV radiation in aqueous alcohol solutions of anthraquinone are investigated experimentally depending on the volume content of alcohol in a mixture. It is shown that the microheterogeneous structure of aqueous alcohol solutions considerably influences the behavior of the dissipative structures formed

  19. Effect of similar elements on improving glass-forming ability of La-Ce-based alloys

    International Nuclear Information System (INIS)

    Zhang Tao; Li Ran; Pang Shujie

    2009-01-01

    To date the effect of unlike component elements on glass-forming ability (GFA) of alloys have been studied extensively, and it is generally recognized that the main consisting elements of the alloys with high GFA usually have large difference in atomic size and atomic interaction (large negative heat of mixing) among them. In our recent work, a series of rare earth metal-based alloy compositions with superior GFA were found through the approach of coexistence of similar constituent elements. The quinary (La 0.5 Ce 0.5 ) 65 Al 10 (Co 0.6 Cu 0.4 ) 25 bulk metallic glass (BMG) in a rod form with a diameter up to 32 mm was synthesized by tilt-pour casting, for which the glass-forming ability is significantly higher than that for ternary Ln-Al-TM alloys (Ln = La or Ce; TM = Co or Cu) with critical diameters for glass-formation of several millimeters. We suggest that the strong frustration of crystallization by utilizing the coexistence of La-Ce and Co-Cu to complicate competing crystalline phases is helpful to construct BMG component with superior GFA. The results of our present work indicate that similar elements (elements with similar atomic size and chemical properties) have significant effect on GFA of alloys.

  20. Anomalous Crystallization as a Signature of the Fragile-to-Strong Transition in Metallic Glass-Forming Liquids

    DEFF Research Database (Denmark)

    Yang, X.N.; Zhou, C.; Sun, Q.J.

    2014-01-01

    We study the fragile-to-strong (F−S) transition of metallic glass-forming liquids (MGFLs) by measuring the thermal response during annealing and dynamic heating of La55Al25Ni5Cu15 glass ribbons fabricated at different cooling rates. We find that the glasses fabricated in the intermediate regime o...

  1. Density and glass forming ability in amorphous atomic alloys: The role of the particle softness

    International Nuclear Information System (INIS)

    Douglass, Ian; Hudson, Toby; Harrowell, Peter

    2016-01-01

    A key property of glass forming alloys, the anomalously small volume difference with respect to the crystal, is shown to arise as a direct consequence of the soft repulsive potentials between metals. This feature of the inter-atomic potential is demonstrated to be responsible for a significant component of the glass forming ability of alloys due to the decrease in the enthalpy of fusion and the associated depression of the freezing point.

  2. Density and glass forming ability in amorphous atomic alloys: The role of the particle softness

    Energy Technology Data Exchange (ETDEWEB)

    Douglass, Ian; Hudson, Toby; Harrowell, Peter [School of Chemistry, University of Sydney, Sydney, NSW (Australia)

    2016-04-14

    A key property of glass forming alloys, the anomalously small volume difference with respect to the crystal, is shown to arise as a direct consequence of the soft repulsive potentials between metals. This feature of the inter-atomic potential is demonstrated to be responsible for a significant component of the glass forming ability of alloys due to the decrease in the enthalpy of fusion and the associated depression of the freezing point.

  3. Discontinuities of Plastic Deformation in Metallic Glasses with Different Glass Forming Ability

    Science.gov (United States)

    Hurakova, Maria; Csach, Kornel; Miskuf, Jozef; Jurikova, Alena; Demcak, Stefan; Ocelik, Vaclav; Hosson, Jeff Th. M. De

    The metallic ribbons Fe40Ni40B20, Cu47Ti35Zr11Ni6Si1 and Zr65Cu17.5Ni10Al7.5 with different microhardness and glass forming ability were studied at different loading rates from 0.05 to 100 mN/s. We describe in details the differences in elemental discontinuities on the loading curves for the studied alloys. It was found that the discontinuities began at a certain local deformation independently on the macroscopic mechanical properties of a ribbon. More developed discontinuities at higher deformations are created for the materials with lower microhardness and so lower strength.

  4. Improvement of corrosion resistance in NaOH solution and glass forming ability of as-cast Mg-based bulk metallic glasses by microalloying

    Directory of Open Access Journals (Sweden)

    Peng Hao

    2011-02-01

    Full Text Available The influences of the addition of Ag on the glass forming ability (GFA and corrosion behavior were investigated in the Mg-Ni-based alloy system by X-ray diffraction (XRD and electrochemical polarization in 0.1 mol/L NaOH solution. Results shows that the GFA of the Mg-Ni-based BMGs can be improved dramatically by the addition of an appropriate amount of Ag; and the addition element Ag can improve the corrosion resistance of Mg-Ni-based bulk metallic glass. The large difference in atomic size and large negative mixing enthalpy in alloy system can contribute to the high GFA. The addition element Ag improves the forming speed and the stability of the passive film, which is helpful to decrease the passivation current density and to improve the corrosion resistance of Mg-Ni-based bulk metallic glass.

  5. Preparation and characterization of Zr-based bulk metallic glasses in form of plate

    International Nuclear Information System (INIS)

    Pilarczyk, Wirginia

    2014-01-01

    Highlights: • Zr-based BMGs in form of plate was successful produced by die pressure casting method. • Many techniques have been used to characterize the structure of Zr 55 Cu 30 Ni 5 Al 10 alloy. • The calculated GFA parameters show that the alloy exhibits satisfactory GFA. • The studies reveal that tested as-cast Zr-based alloy is in amorphous state. - Abstract: Zr-based bulk metallic glasses present an interesting combination of physical, chemical and mechanical properties. During the last decade, intensive progress has been made and a number of applications have been suggested for these materials. In order to successfully apply these materials, it is necessary to accurately characterize their structure, thermal stability and other properties accurately. The aim of the presented work is the manufacturing, examination of the structure of selected Zr-based bulk metallic alloys and confirmation of an amorphous structure using X-ray analysis, microscopic observation and thermal analysis. In this work, the Zr-based bulk metallic glasses in form of plate was successful produced by die pressure casting method. Designed scientific station for casting zirconium based amorphous alloys in the form of plates and rods with selected dimensions is in our university a comprehensive method for achieving amorphous materials which enables us to maintain repeatability of as-cast samples with the amorphous structure and the assumed dimensions range. The diffraction pattern and exothermic reaction as well as the fracture surface morphology reveal that studied as-cast Zr-based alloy is in amorphous state. The calculated GFA parameters show that the alloy exhibits satisfactory glass-forming ability in form of studied plate. These obtained values can suggest that studied alloys are suitable materials for further planned practical application at welding process. The success of Zr-based bulk metallic glasses production in form of plate with obtained sizes is important for future

  6. Preparation and characterization of Zr-based bulk metallic glasses in form of plate

    Energy Technology Data Exchange (ETDEWEB)

    Pilarczyk, Wirginia, E-mail: wirginia.pilarczyk@polsl.pl

    2014-12-05

    Highlights: • Zr-based BMGs in form of plate was successful produced by die pressure casting method. • Many techniques have been used to characterize the structure of Zr{sub 55}Cu{sub 30}Ni{sub 5}Al{sub 10} alloy. • The calculated GFA parameters show that the alloy exhibits satisfactory GFA. • The studies reveal that tested as-cast Zr-based alloy is in amorphous state. - Abstract: Zr-based bulk metallic glasses present an interesting combination of physical, chemical and mechanical properties. During the last decade, intensive progress has been made and a number of applications have been suggested for these materials. In order to successfully apply these materials, it is necessary to accurately characterize their structure, thermal stability and other properties accurately. The aim of the presented work is the manufacturing, examination of the structure of selected Zr-based bulk metallic alloys and confirmation of an amorphous structure using X-ray analysis, microscopic observation and thermal analysis. In this work, the Zr-based bulk metallic glasses in form of plate was successful produced by die pressure casting method. Designed scientific station for casting zirconium based amorphous alloys in the form of plates and rods with selected dimensions is in our university a comprehensive method for achieving amorphous materials which enables us to maintain repeatability of as-cast samples with the amorphous structure and the assumed dimensions range. The diffraction pattern and exothermic reaction as well as the fracture surface morphology reveal that studied as-cast Zr-based alloy is in amorphous state. The calculated GFA parameters show that the alloy exhibits satisfactory glass-forming ability in form of studied plate. These obtained values can suggest that studied alloys are suitable materials for further planned practical application at welding process. The success of Zr-based bulk metallic glasses production in form of plate with obtained sizes is

  7. Forty years of the Hrubý glass-forming coefficient via DTA when comparing other criteria in relation to the glass stability and vitrification ability

    Czech Academy of Sciences Publication Activity Database

    Kozmidis-Petrovic, A.; Šesták, Jaroslav

    2012-01-01

    Roč. 110, č. 2 (2012), 997-1004 ISSN 1388-6150 Institutional research plan: CEZ:AV0Z10100521 Keywords : glass transition * Hrubý criterion * glass -forming ability * DTA/DSC Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.982, year: 2012

  8. Strong composition-dependence on glass-forming ability in Ni-(Ti,Zr)-Si pseudo-ternary alloys

    International Nuclear Information System (INIS)

    Yang, H.; Wang, J.Q.; Li, Y.

    2006-01-01

    The glass formation in Ni-(Ti,Zr)-Si pseudo-ternary alloys was studied. For suction casting, by carefully adjusting the alloy composition and studying the microstructure changes, the best glass-forming alloy with a 2 mm diameter is pinpointed in a narrow composition region of 57.5-58.5 at.% Ni, 36.5-38.5 at.% (Ti + Zr) and 5-5.5 at.% Si. The main competing crystalline phases, identified by XRD and SEM, were Ni 10 (Zr,Ti) 7 , Ni(Ti,Zr) and an unidentified Si-containing phase. Our results indicate a clear need for monitoring the microstructure change in the cross section of the ingots to locate the best glass-forming alloys

  9. Effects of Nb addition on icosahedral quasicrystalline phase formation and glass-forming ability of Zr--Ni--Cu--Al metallic glasses

    International Nuclear Information System (INIS)

    Fan, Cang; Li, Chunfei; Inoue, Akihisa; Haas, Volker

    2001-01-01

    This work shows that the crystallization process of Zr--Ni--Cu--Al metallic glass is greatly influenced by adding Nb as an alloying element. Based on the results of the differential scanning calorimetry experiments for metallic glasses Zr 69-x Nb x Ni 10 Cu 12 Al 9 (x=0--15at.%), the crystallization process takes place through two individual stages. For Zr 69 Ni 10 Cu 12 Al 9 (x=0), metastable hexagonal ω-Zr and a small fraction of tetragonal Zr 2 Cu are precipitated upon completion of the first exothermic reaction. Contrary to this alloy, the precipitation of a nanoquasicrystalline phase is detected when 5--10 at.% Nb is added. Furthermore, the crystallization temperature T x , supercooled liquid region ΔT x and reduced temperature T g /T L (T g is the glass transition temperature, T L the liquidus temperature) increase with increasing Nb content. These results indicate that adding Nb content to Zr--Ni--Cu--Al metallic glasses not only induces quasicrystalline phase formation, but also enhances glass-forming ability. Copyright 2001 American Institute of Physics

  10. The borosilicate glass for 'PAMELA'

    International Nuclear Information System (INIS)

    Schiewer, E.

    1986-01-01

    The low enriched waste concentrate (LEWC) stored at Mol, Belgium, will be solidified in the vitrification plant 'PAMELA'. An alkali-borosilicate glass was developed by the Hahn-Meitner-Institut, Berlin, which dissolves (11 +- 3)wt% waste oxides while providing sufficient flexibility for changes in the process parameters. The development of the glass labelled SM513LW11 is described. Important properties of the glass melt (viscosity, resistivity, formation of yellow phase) and of the glass (corrosion in aqueous solutions, crystallization) are reported. The corrosion data of this glass are similar to those of other HLW-glasses. Less than five wt% of crystalline material are produced upon cooling of large glass blocks. Crystallization does not affect the chemical durability. (Auth.)

  11. Calculation of glass forming ranges in Al-Ni-RE (Ce, La, Y) ternary alloys and their sub-binaries based on Miedema's model

    International Nuclear Information System (INIS)

    Sun, S.P.; Yi, D.Q.; Liu, H.Q.; Zang, B.; Jiang, Y.

    2010-01-01

    Research highlights: → A method based on semi-empirical Miedema's and Toop's model for predicting glass forming range of ternary alloy system has been systematically described. → The method is superior to conventional models by considering the effect of the thermodynamic asymmetric component when dealing with a ternary alloy system. → The glass forming ranges of Al-Ni-RE (Al-Ni-Ce, Al-Ni-Y and Al-Ni-La) systems and their sub-binaries have been successfully calculated. → The present calculations using the method are in well agreement with experiments. → This model is especially useful for predicting the glass forming range of ternary alloy system because the calculations do not require experimental data. - Abstract: A method based on the semi-empirical Miedema's and Toop's model for calculating the glass forming range of a ternary alloy system was systematically described. The method is superior to conventional models by considering the effect of the thermodynamic asymmetric component when dealing with a ternary alloy system. Using this method, the glass forming ranges of Al-Ni-RE (Ce, La, Y) systems and their sub-binaries were successfully predicted. The mixing enthalpy and mismatch entropy were calculated, and their effects on the glass forming abilities of Al-Ni-RE (Ce, La, Y) systems were also discussed. The glass forming abilities of Al-Ni-Ce, Al-Ni-La and Al-Ni-Y are found to be close. The calculated glass forming ranges agree with experiments well. Meanwhile, the enthalpy change from amorphous phase to solid solution in the glass forming ranges was calculated, and the results suggest that those alloys close to the Ni-RE sub-binary system have higher glass forming abilities.

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

    International Nuclear Information System (INIS)

    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 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

  13. Preliminary investigation of a technique to separate fission noble metals from fission-product mixtures

    International Nuclear Information System (INIS)

    Mellinger, G.B.; Jensen, G.A.

    1982-08-01

    A variation of the gold-ore fire assay technique was examined as a method for recovering Pd, Rh and Ru from fission products. The mixture of fission product oxides is combined with glass-forming chemicals, a metal oxide such as PbO (scavenging agent), and a reducing agent such as charcoal. When this mixture is melted, a metal button is formed which extracts the noble metals. The remainder cools to form a glass for nuclear waste storage. Recovery depended only on reduction of the scavenger oxide to metal. When such reduction was achieved, no difference in noble metal recovery efficiency was found among the scavengers studied (PbO, SnO, CuO, Bi 2 O 3 , Sb 2 O 3 ). Not all reducing agents studied, however, were able to reduce all scavenger oxides to metal. Only graphite would reduce SnO and CuO and allow noble metal recovery. The scavenger oxides Sb 2 O 3 , Bi 2 O 3 , and PbO, however, were reduced by all of the reducing agents tested. Similar noble metal recovery was found with each. Lead oxide was found to be the most promising of the potential scavengers. It was reduced by all of the reducing agents tested, and its higher density may facilitate the separation. Use of lead oxide also appeared to have no deterimental effect on the glass quality. Charcoal was identified as the preferred reducing agent. As long as a separable metal phase was formed in the melt, noble metal recovery was not dependent on the amount of reducing agent and scavenger oxide. High glass viscosities inhibited separation of the molten scavenger, while low viscosities allowed volatile loss of RuO 4 . A viscosity of approx. 20 poise at the processing temperature offered a good compromise between scavenger separation and Ru recovery. Glasses in which PbO was used as the scavenging agent were homogeneous in appearance. Resistance to leaching was close to that of certain waste glasses reported in the literature. 12 figures. 7 tables

  14. The correlation between fragility, density, and atomic interaction in glass-forming liquids

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lijin; Guan, Pengfei, E-mail: pguan@csrc.ac.cn [Beijing Computational Science Research Center, Beijing 100193 (China); Wang, W. H. [Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China)

    2016-07-21

    The fragility that controls the temperature-dependent viscous properties of liquids as the glass transition is approached, in various glass-forming liquids with different softness of the repulsive part of atomic interactions at different densities, is investigated by molecular dynamic simulations. We show that the landscape of fragility in purely repulsive systems can be separated into three regions denoted as R{sub I,} R{sub II}, and R{sub III}, respectively, with qualitatively disparate dynamic behaviors: R{sub I} which can be described by “softness makes strong glasses,” R{sub II} where fragility is independent of softness and can only be tuned by density, and R{sub III} with constant fragility, suggesting that density plays an unexpected role for understanding the repulsive softness dependence of fragility. What is more important is that we unify the long-standing inconsistence with respect to the repulsive softness dependence of fragility by observing that a glass former can be tuned more fragile if nonperturbative attraction is added into it. Moreover, we find that the vastly dissimilar influences of attractive interaction on fragility could be estimated from the structural properties of related zero-temperature glasses.

  15. The correlation between fragility, density, and atomic interaction in glass-forming liquids

    International Nuclear Information System (INIS)

    Wang, Lijin; Guan, Pengfei; Wang, W. H.

    2016-01-01

    The fragility that controls the temperature-dependent viscous properties of liquids as the glass transition is approached, in various glass-forming liquids with different softness of the repulsive part of atomic interactions at different densities, is investigated by molecular dynamic simulations. We show that the landscape of fragility in purely repulsive systems can be separated into three regions denoted as R I, R II , and R III , respectively, with qualitatively disparate dynamic behaviors: R I which can be described by “softness makes strong glasses,” R II where fragility is independent of softness and can only be tuned by density, and R III with constant fragility, suggesting that density plays an unexpected role for understanding the repulsive softness dependence of fragility. What is more important is that we unify the long-standing inconsistence with respect to the repulsive softness dependence of fragility by observing that a glass former can be tuned more fragile if nonperturbative attraction is added into it. Moreover, we find that the vastly dissimilar influences of attractive interaction on fragility could be estimated from the structural properties of related zero-temperature glasses.

  16. Mean-coordination number dependence of the fragility in Ge-Se-In glass-forming liquids

    International Nuclear Information System (INIS)

    Saffarini, G.; Saiter, A.; Garda, M.R.; Saiter, J.M.

    2007-01-01

    Differential scanning calorimetry measurements have been performed on elemental Se as well as on Ge x Se 94- x In 6 (x=4, 8, and 11 at%) and on Ge y Se 88- y In 12 (y=5, 7, and 9 at%) chalcogenide glasses. From the cooling rate dependence of the fictive temperature, the apparent activation energies, Δh*, and the fragility indices, m, as defined in the strong-fragile glass-forming liquid concept, are determined. It is found that, in Ge-Se-In system, there is an evolution from strong (m=67) to fragile (m=116) glass-forming liquids. The dependence of 'm' on the mean-coordination number, Z, is also obtained. This dependence is rationalized by assuming that, in this glassy alloy system, there is a tendency for the formation of In 2 Se 3 clusters

  17. BNFL Report Glass Formers Characterization

    Energy Technology Data Exchange (ETDEWEB)

    Schumacher, R.F.

    2000-07-27

    The objective of this task was to obtain powder property data on candidate glass former materials, sufficient to guide conceptual design and estimate the cost of glass former handling facilities as requested under Part B1 of BNFL Technical and Development Support. Twenty-nine glass forming materials were selected and obtained from vendors for the characterization of their physical properties, durability in caustic solution, and powder flow characteristics. A glass former was selected based on the characterization for each of the ten oxide classes required for Envelope A, B, and C mixtures. Three blends (A, B, and C) were prepared based on formulations provided by Vitreous State Laboratory and evaluated with the same methods employed for the glass formers. The properties obtained are presented in a series of attached Tables. It was determined that five of the ten glass formers, (kyanite, iron oxide, titania, zircon, and zinc oxide) have the potential to cause some level of solids f low problems. In addition, all of the blends may require consideration for their handling. A number of engineering considerations and recommendations were prepared based on the experimental findings, experience, and other process considerations. Recommendations for future testing are included. In conjunction with future work, it is recommended that a professional consultant be engaged to guide and assist with testing and design input.

  18. BNFL Report Glass Formers Characterization

    International Nuclear Information System (INIS)

    Schumacher, R.F.

    2000-01-01

    The objective of this task was to obtain powder property data on candidate glass former materials, sufficient to guide conceptual design and estimate the cost of glass former handling facilities as requested under Part B1 of BNFL Technical and Development Support. Twenty-nine glass forming materials were selected and obtained from vendors for the characterization of their physical properties, durability in caustic solution, and powder flow characteristics. A glass former was selected based on the characterization for each of the ten oxide classes required for Envelope A, B, and C mixtures. Three blends (A, B, and C) were prepared based on formulations provided by Vitreous State Laboratory and evaluated with the same methods employed for the glass formers. The properties obtained are presented in a series of attached Tables. It was determined that five of the ten glass formers, (kyanite, iron oxide, titania, zircon, and zinc oxide) have the potential to cause some level of solids f low problems. In addition, all of the blends may require consideration for their handling. A number of engineering considerations and recommendations were prepared based on the experimental findings, experience, and other process considerations. Recommendations for future testing are included. In conjunction with future work, it is recommended that a professional consultant be engaged to guide and assist with testing and design input

  19. Comparative study of the physicochemical properties of aqueous solutions of the hydrocarbon and fluorocarbon surfactants and their ternary mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Szymczyk, Katarzyna, E-mail: katarzyna.szymczyk@poczta.umcs.lublin.pl

    2014-03-03

    Highlights: • Acoustic properties of hydrocarbon and fluorocarbon surfactants were studied. • Auerbach’s relation is not proper for mixtures with fluorocarbon surfactants. • Values of the hydration number decreases at concentrations higher than CMC. • FSO100 and its mixtures are the strongest chaotropes. - Abstract: Speed of sound and density of aqueous solutions of hydrocarbon p-(1,1,3,3-tetramethylbutyl) phenoxypoly(ethyleneglycols) (Triton X-100 (TX100), Triton X-165 (TX165)) and fluorocarbon (Zonyl FSN-100 (FSN100), Zonyl FSO-100 (FSO100)) surfactants as well as their ternary mixtures were measured at 293 K. Taking into account these values and the literature data of the surface tension and viscosity of the studied systems, the values of the isentropic compressibility, apparent specific adiabatic compressibility, hydration number, apparent specific volume and Jones Dole’s A and B-coefficients were determined. For the systems containing FSO100 also the values of dB/dT were determined on the basis of the values of viscosity measured at different temperatures. Next, the calculated thermodynamic properties have been discussed in the term of intermolecular interactions between the components of the mixtures.

  20. Effect of Ga substitution on the crystallization behaviour and glass forming ability of Zr-Al-Cu-Ni alloys

    International Nuclear Information System (INIS)

    Singh, Devinder; Yadav, T.P.; Mandal, R.K.; Tiwari, R.S.; Srivastava, O.N.

    2010-01-01

    The crystallization behaviour of melt spun Zr 69.5 Al 7.5-x Ga x Cu 12 Ni 11 (x = 0-7.5; in at.%) metallic glasses has been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The DSC traces showed changes in crystallization behaviour with substitution of Ga. Formation of single nano-quasicrystalline phase by controlled crystallization of glasses has been found only for 0 ≤ x ≤ 1.5. Further increase of Ga content gives rise to formation of the quasicrystals together with Zr 2 Cu type crystalline phase. In addition to this, the substitution of Ga influences the size and shape of nano-quasicrystals. The glass forming abilities (GFAs) of these metallic glasses were assessed by the recognition of glass forming ability indicators, i.e. reduced glass transition temperature (T rg ) and supercooled liquid region (ΔT x ). The glass transition temperature (T g ) has been observed for all the melt spun ribbons.

  1. Physical stability of drugs after storage above and below the glass transition temperature: Relationship to glass-forming ability.

    Science.gov (United States)

    Alhalaweh, Amjad; Alzghoul, Ahmad; Mahlin, Denny; Bergström, Christel A S

    2015-11-10

    Amorphous materials are inherently unstable and tend to crystallize upon storage. In this study, we investigated the extent to which the physical stability and inherent crystallization tendency of drugs are related to their glass-forming ability (GFA), the glass transition temperature (Tg) and thermodynamic factors. Differential scanning calorimetry was used to produce the amorphous state of 52 drugs [18 compounds crystallized upon heating (Class II) and 34 remained in the amorphous state (Class III)] and to perform in situ storage for the amorphous material for 12h at temperatures 20°C above or below the Tg. A computational model based on the support vector machine (SVM) algorithm was developed to predict the structure-property relationships. All drugs maintained their Class when stored at 20°C below the Tg. Fourteen of the Class II compounds crystallized when stored above the Tg whereas all except one of the Class III compounds remained amorphous. These results were only related to the glass-forming ability and no relationship to e.g. thermodynamic factors was found. The experimental data were used for computational modeling and a classification model was developed that correctly predicted the physical stability above the Tg. The use of a large dataset revealed that molecular features related to aromaticity and π-π interactions reduce the inherent physical stability of amorphous drugs. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Origin and evolution of cup-shaped structures on leached nuclear waste containment glass surfaces

    International Nuclear Information System (INIS)

    Dubois, C.; Villa, F.; Chambaudet, A.; Vernaz, E.

    1994-01-01

    A three-dimensional surface microanalysis system equipped with a sensitive topographical probe was used to quantify the evolution of cup-shaped structures formed by aqueous leaching of nuclear waste containment glass. A model of the dissolution phenomenon provides satisfactory correlation between calculated and measured cup radius and depth. Dissolution cups form from cracks on the initially cut glass surface. Large cracks control the phenomenon by forming the largest cups, which gradually absorb smaller ones. The evolution of the size and shape of the dissolution cups was described by a model that assumes a constant dissolution rate on the surface, diminishing with crack depth. The best fit with the experimental data was obtained with a dissolution rate one hundred times lower at the bottom of the crack than at the surface. Moreover, it is predictable that all the cups will gradually disappear as they grow larger and flatter over a leaching period of some 2 years, for the glass composition and experimental leaching procedures used in this work

  3. Influence of minor alloying additions on the glass-forming ability of Mg-Ni-La bulk metallic glasses

    International Nuclear Information System (INIS)

    Gonzalez, S.; Figueroa, I.A.; Todd, I.

    2009-01-01

    Bulk metallic glasses of Mg 60 Ni 23.6 Y x La (16.4-x) and Mg 65 Ni 20 Y x LaMM (15-x) with 0 ≤ x ≤ 1 at.% have been produced by injection casting. For the La-containing alloy a maximum amorphous diameter of 4 mm for x = 0.5 and 0.75 was obtained. The LaMM-containing alloy showed a maximum amorphous diameter of 2 mm for x = 0 and 0.25 but decreased to 1 mm with further Y additions. The glass-forming ability of the Mg 60 Ni 23.6 La 16.4 alloy decreased when La is partially substituted by small amounts of small atoms (Si or B) or by large atoms (Y and Si).

  4. Construction of a 21-Component Layered Mixture Experiment Design Using a New Mixture Coordinate-Exchange Algorithm

    International Nuclear Information System (INIS)

    Piepel, Gregory F.; Cooley, Scott K.; Jones, Bradley

    2005-01-01

    This paper describes the solution to a unique and challenging mixture experiment design problem involving: (1) 19 and 21 components for two different parts of the design, (2) many single-component and multi-component constraints, (3) augmentation of existing data, (4) a layered design developed in stages, and (5) a no-candidate-point optimal design approach. The problem involved studying the liquidus temperature of spinel crystals as a function of nuclear waste glass composition. The statistical objective was to develop an experimental design by augmenting existing glasses with new nonradioactive and radioactive glasses chosen to cover the designated nonradioactive and radioactive experimental regions. The existing 144 glasses were expressed as 19-component nonradioactive compositions and then augmented with 40 new nonradioactive glasses. These included 8 glasses on the outer layer of the region, 27 glasses on an inner layer, 2 replicate glasses at the centroid, and one replicate each of three existing glasses. Then, the 144 + 40 = 184 glasses were expressed as 21-component radioactive compositions, and augmented with 5 radioactive glasses. A D-optimal design algorithm was used to select the new outer layer, inner layer, and radioactive glasses. Several statistical software packages can generate D-optimal experimental designs, but nearly all of them require a set of candidate points (e.g., vertices) from which to select design points. The large number of components (19 or 21) and many constraints made it impossible to generate the huge number of vertices and other typical candidate points. JMP was used to select design points without candidate points. JMP uses a coordinate-exchange algorithm modified for mixture experiments, which is discussed and illustrated in the paper

  5. Gamma-radiolysis effects on leaching of nuclear fuel waste forms

    International Nuclear Information System (INIS)

    Tait, J.C.; Wilkin, D.L.; Hamon, R.F.

    1986-06-01

    Gamma-radiolysis experiments have been conducted on aqueous systems representative of those that might be found in a granite rock disposal vault for immobilized nuclear fuel recycle waste. Sealed capsules containing an air or an oxygen-free atmosphere, synthetic granite or chloride groundwaters, and components of the disposal system (granite, clay, metal containers and glass or glass-ceramic waste form) were irradiated by an external gamma field. Analysis of the gas phase showed the presence of H 2 gas in all capsules. Capsules containing graphite and air showed oxygen depletion. This depletion of O 2 is attributed to radiolytic reactions with iron species leached from the granite. Systems containing bentonite clay showed the production of CO 2 . A computer program, MAKSIMA-CHEMIST, was used to qualitatively predict the observed gas-phase composition by modelling the kinetics of the aqueous radiolysis reactions

  6. Glass packages in interim storage

    International Nuclear Information System (INIS)

    Jacquet-Francillon, N.

    1994-10-01

    This report summarize the current state of knowledge concerning the behavior of type C waste packages consisting of vitrified high-level solutions produced by reprocessing spent fuel. The composition and the physical and chemical properties of the feed solutions are reviewed, and the vitrification process is described. Sodium alumino-borosilicate glass compositions are generally employed - the glass used at la Hague for LWR fuel solutions, for example, contains 45 % SiO 2 . The major physical, chemical, mechanical and thermal properties of the glass are reviewed. In order to allow their thermal power to diminish, the 3630 glass packages produced (as of January 1993) in the vitrification facilities at Marcoule and La Hague are placed in interim storage for several decades. The actual interim storage period has not been defined, as it is closely related to the concept and organization selected for the final destination of the packages: a geological repository. The glass behavior under irradiation is described. Considerable basic and applied research has been conducted to assess the aqueous leaching behavior of nuclear containment glass. The effects of various repository parameters (temperature, flow rate, nature of the environmental materials) have been investigated. The experimental findings have been used to specify a model describing the kinetics of aqueous corrosion of the glass. More generally all the ''source term'' models developed in France by the CEA or by ANDRA are summarized. (author). 152 refs., 33 figs

  7. Collective dynamics of glass-forming polymers at intermediate length scales

    International Nuclear Information System (INIS)

    Colmenero, J.; Alvarez, F.; Arbe, A.

    2015-01-01

    Deep understanding of the complex dynamics taking place in glass-forming systems could potentially be gained by exploiting the information provided by the collective response monitored by coherent neutron scattering. We have revisited the question of the characterization of the collective response of polyisobutylene at intermediate length scales observed by neutron spin echo (NSE) experiments. The model, generalized for sub-linear diffusion - as it is the case of glass-forming polymers - has been successfully applied by using the information on the total self-motions available from MD-simulations properly validated by direct comparison with experimental results. From the fits of the coherent NSE data, the collective time at Q → 0 has been extracted that agrees very well with compiled results from different experimental techniques directly accessing such relaxation time. We show that a unique temperature dependence governs both, the Q → 0 and Q → ∞ asymptotic characteristic times. The generalized model also gives account for the modulation of the apparent activation energy of the collective times with the static structure factor. It mainly results from changes of the short-range order at inter-molecular length scales

  8. PREFACE: Dynamic crossover phenomena in water and other glass-forming liquids Dynamic crossover phenomena in water and other glass-forming liquids

    Science.gov (United States)

    Chen, Sow-Hsin; Baglioni, Piero

    2012-02-01

    This special section has been inspired by the workshop on Dynamic Crossover Phenomena in Water and Other Glass-Forming Liquids, held during November 11-13, 2010 at Pensione Bencistà, Fiesole, Italy, a well-preserved 14th century Italian villa tucked high in the hills overlooking Florence. The meeting, an assembly of world renowned scientists, was organized as a special occasion to celebrate the 75th birthday of Professor Sow-Hsin Chen of MIT, a pioneer in several aspects of complex fluids and soft matter physics. The workshop covered a large variety of experimental and theoretical research topics of current interest related to dynamic crossover phenomena in water and, more generally, in other glass-forming liquids. The 30 invited speakers/lecturers and approximately 60 participants were a select group of prominent physicists and chemists from the USA, Europe, Asia and Mexico, who are actively working in the field. Some highlights of this special issue include the following works. Professor Yamaguchi's group and their collaborators present a neutron spin echo study of the coherent intermediate scattering function of heavy water confined in cylindrical pores of MCM-41-C10 silica material in the temperature range 190-298 K. They clearly show that a fragile-to-strong (FTS) dynamic crossover occurs at about 225 K. They attribute the FTS dynamic crossover to the formation of a tetrahedral-like structure, which is preserved in the bulk-like water confined to the central part of the cylindrical pores. Mamontov and Kolesnikov et al study the collective excitations in an aqueous solution of lithium chloride over a temperature range of 205-270 K using neutron and x-ray Rayleigh-Brillouin (coherent) scattering. They detect both the low-frequency and the high-frequency sounds known to exist in pure bulk water above the melting temperature. They also perform neutron (incoherent) and x-ray (coherent) elastic intensity scan measurements. Clear evidence of the crossover in the

  9. Cation coordination in oxychloride glasses

    International Nuclear Information System (INIS)

    Johnson, J A; Holland, D; Bland, J; Johnson, C E; Thomas, M F

    2003-01-01

    Glasses containing mixtures of cations and anions of nominal compositions [Sb 2 O 3 ] x - [ZnCl 2 ] 1-x where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb) 2 (OZn)] and [Zn(ClZn) 2 (OSb) 2

  10. Icosahedral binary clusters of glass-forming Lennard-Jones binary alloy

    International Nuclear Information System (INIS)

    Iwamatsu, Masao

    2007-01-01

    It is widely believed that the local icosahedral structure is related to the formation of bulk metallic glasses (BMGs). Specifically the existence of 13-atom icosahedral cluster in undercooled liquid is imagined to play a key role to initiate the glass formation as the seed of amorphous structure or to block the nucleation of regular crystal as the impurity. The existence of 13-atom icosahedral clusters in one-component liquids was predicted more than half a century ago by Frank from his total energy calculation for isolated clusters. In BMG alloys, however, the situation is less clear. In this report, we present the lowest-energy structures of 13-atom Lennard-Jones binary cluster calculated from the modified space-fixed genetic algorithm. We study, in particular, the artificial Lennard-Jones potential designed by Kob and Andersen [W. Kob, H.C. Andersen, Phys. Rev. E 51 (1995) 4626] that is known to form BMG. Curiously, the lowest-energy structures of 13-atom cluster are non-icosahedral for almost all compositions. Our result suggests that the existence of the icosahedral cluster is not a necessary condition but only a sufficient condition for glass formation

  11. Correlation between microstructure and mechanical properties of stable mixtures formed by austenite and martensite

    International Nuclear Information System (INIS)

    Eckstein, C.B.

    1982-03-01

    The influence of martensite in mechanical properties of stable mixtures formed by austenite and martensite was studied by varying the amount of martensite in the mixtures. Microstructural parameters were determined by Optical Quantitative Metallography and used to establish the correlation between the mechanical response of the mixtures in tension and their microstructures. The 'in situ' deformation of each phase in mixtures was determined experimentally in terms of the rule of mixtures. It is shown that the partitioning of the deformation depends on the amount of martensite in the mixture and that it tends to a condition of isostrain at higher martensite volume fractions. Optical observation of fractured specimens showed that the beginning of the fracture process may related to regions of the austenite grain boundaries where they meet martensite plates. (Author) [pt

  12. Glass forming ability of Al–Ni–La alloys with Si addition

    International Nuclear Information System (INIS)

    Yi, J.J.; Xiong, X.Z.; Inoue, A.; Kong, L.T.; Li, J.F.

    2015-01-01

    (Al_8_5_._5Ni_9_._5La_5)_1_0_0_−_xSi_x, (Al_8_6Ni_9La_5)_1_0_0_−_xSi_x, (Al_8_6Ni_9_._5La_4_._5)_1_0_0_−_xSi_x, (Al_8_6Ni_1_0La_4)_1_0_0_−_xSi_x and (Al_8_6Ni_1_0_._5La_3_._5)_1_0_0_−_xSi_x alloys, where x = 0.0, 0.2, 0.5, 1.0, 1.5 and 2.0, were cast under the same suction casting conditions into a wedge-shaped copper mold for investigating the effect of Si addition on the glass-forming ability (GFA). The GFA of the Al–Ni–La base alloys, except for the optimal glass former (Al_8_5_._5Ni_9_._5La_5), is enhanced when a proper content of Si is added. The largest content of Si up to which GFA can be enhanced changes in the following order of the base alloys: Al_8_6Ni_9La_5, Al_8_6Ni_9_._5La_4_._5, Al_8_6Ni_1_0La_4 and Al_8_6Ni_1_0_._5La_3_._5. The enhancement of GFA due to Si addition becomes more significant as the La content decreases. This is presumably because more free Al atoms are present in the base alloy. - Highlights: • 0.2–2.0 at. % Si was added to each ternary base alloy. • Wedge-shaped samples were suction cast to obtain the glass-forming ability (GFA). • The GFA of the ternary non-optimal glass formers can be enhanced by Si addition. • The number of free-Al atoms dominates the best Si addition.

  13. Investigation of structural transformations in surface layer of phosphate glasses incorporating radiactive wastes

    International Nuclear Information System (INIS)

    Aloj, A.S.; Kolycheva, T.I.; Trofimenko, A.V.; Shashukov, E.A.

    1985-01-01

    The objective of the paper was to clarify possibilities of detection of structural transformations initial stages on the surface of phosphate glasses using the method of infrared reflection spectroscopy. Phase composition of crystalline compounds formed in surface glass layer is determined by the method of X-ray diffraction. All experiments were performed using sodium alumophosphate glass comprising the model mixture of fission product of the following compostion (mass%): Na 2 O-22.0, Al 2 O 3 -14.0, P 2 O 5 -50.0, Fe 2 O 3 -3.5, Cs 2 O-3.5, SrO-3.0, Ln 2 O 3 -4.0, where Ln 2 O 3 is a mixture of cerium, lanthanum and europium oxides. Sample preparation were carried out by molten glass deposition on platinum forms 15mm in diameter and 4mm thick. Glasses were treated within the 600-400deg.C temperature range. Fixing of processes accompanied by structural transformations was accomplished the method of rapid cooling. It has been shown that phase transformations, taking place in investigated phosphate glasses under the action of heat, result in deterioration of chemical properties. Analysis of IR spectra has revealed that emergence of structural transformations in surface layer of investigated glasses results in variation of a ratio of 1060 and 1140cm - 1 reflection band intensities. Experimental dependences of the time of beginning of variation of 1060 and 1140cm - 1 bands relative intensity on temperature are presented. Insemilogarithmic coordinates this dependence has a straight line form within the 600-400 deg C temperature range and is desc ribed by the following formular: lg r=-7.41+5.70x10 3 x1/T, where r is the time of process beginning, h. Extrapolation of established to the region of low temperature is shown. Competence of such extrapolation may be confirmed in the course of further experiments

  14. Colorimeter determination of Fe(II)/Fe(III) ratio in glass

    International Nuclear Information System (INIS)

    Baumann, E.W.; Coleman, C.J.; Karraker, D.G.; Scott, W.H.

    1987-01-01

    A colorimetric method has been developed to determine the Fe(II)/Fe(III) ratio in glass containing nuclear waste. Fe(II) is stabilized with pentavalent vanadium during dissolution in sulfuric and hydrofluoric acids. The chromogen is FerroZine (Hach Chemical Company), which forms a magenta complex with Fe(II). The two-step color development consists of determining the Fe(II) by adding FerroZine, followed by determining total Fe after the Fe(III) present is reduced with ascorbic acid. The method was validated by analyzing mixtures of ferrous/ferric solutions and nonferrous glass frit, and by comparison with Moessbauer spectroscopy. The effect of gamma radiation was established. The procedure is generally applicable to nonradioactive materials such as minerals and other glasses

  15. Glass forming in La2O3-TiO2-ZrO2 ternary system by containerless processing

    Science.gov (United States)

    Kaneko, Masashi; Kentei Yu, Yu; Kumar, Vijaya; Masuno, Atsunobu; Inoue, Hiroyuki; Odawara, Osamu; Yoda, Shinichi

    The containerless processing is an appropriate method to create new glasses, because it sup-presses nucleation at the boundary between liquid and crucible during solidification and it enables molten samples to be solidified without crystallization. Recently, we have succeeded in forming BaTi2 O5 glass in the bulk state by using an aerodynamic levitation furnace. BaTi2 O5 glass includes no traditional glass network former and it possesses high electric permittivity [1, 2]. From the point of view of optical application, BaTi2 O5 glass has high refractive indices over 2.1. BaTi2 O5 glass, however, vitrify only in a small sphere, and it crystallize when its diameter exceed 1.5 mm. In order to synthesize new titanate oxide glasses which possess higher refractive indices and larger diameter than BaTi2 O5 , La and Zr can be used as substitutive components. When Ba is replaced with La, refractive indices are expected to increase because of the heavier element. The addition of a third element is thought to be effective for enhance-ment of glass formation ability and Zr can be a candidate because Ti and Zr are homologous. In this research, we have succeeded in forming new bulk glass in La2 O3 -TiO2 -ZrO2 ternary system by means of the aerodynamic levitation furnace. We investigated the glass forming region, thermal properties and optical properties of La2 O3 -TiO2 -ZrO2 glass. Glass transition temperature, crystallization temperature, density, refractive indices and transmittance spectra were varied depending on the chemical composition. Reference [1] J. Yu et al, "Fabrication of BaTi2O5 Glass-Ceramics with Unusual Dielectric Properties during Crystallization", Chem-istry of Materials, 18 (2006) 2169-2173. [2] J. Yu et al., "Comprehensive Structural Study of Glassy and Metastable Crystalline BaTi2O5", Chemistry of Materials, 21 (2009) 259-263.

  16. Consolidated waste forms: glass marbles and ceramic pellets

    International Nuclear Information System (INIS)

    Treat, R.L.; Rusin, J.M.

    1982-05-01

    Glass marbles and ceramic pellets have been developed at Pacific Northwest Laboratory as part of the multibarrier concept for immobilizing high-level radioactive waste. These consolidated waste forms served as substrates for the application of various inert coatings and as ideal-sized particles for encapsulation in protective matrices. Marble and pellet formulations were based on existing defense wastes at Savannah River Plant and proposed commercial wastes. To produce marbles, glass is poured from a melter in a continuous stream into a marble-making device. Marbles were produced at PNL on a vibratory marble machine at rates as high as 60 kg/h. Other marble-making concepts were also investigated. The marble process, including a lead-encapsulation step, was judged as one of the more feasible processes for immobilizing high-level wastes. To produce ceramic pellets, a series of processing steps are required, which include: spray calcining - to dry liquid wastes to a powder; disc pelletizing - to convert waste powders to spherical pellets; sintering - to densify pellets and cause desired crystal formation. These processing steps are quite complex, and thereby render the ceramic pellet process as one of the least feasible processes for immobilizing high-level wastes

  17. Preparation and use of viscous-elastic clay-polymer mixtures in drilling

    Energy Technology Data Exchange (ETDEWEB)

    Davydov, V K; Tyurin, I P

    1979-01-01

    A highly viscous-elastic mixture (VUS) has been widely used as a buffer liquid. It consists of a weakly concentrated aqueous polyacrylamide solute with additives of small quantities of an aqueous hexaresorcin tar and formalin solution. Laboratory tests have shown that when this mixture is prepared, a bentonite suspension is required with a pH 7, containing minimum 10% solid phase and an aqueous polyacrylamide solution with concentration of no less than 1%. Tests have shown that the effect of this formula varies according to proportions in the mixture. Temperature and selection of the formula must be made on an individual basis.

  18. The utilization of a pressurized-graphite/water/oxygen mixture for irradiated graphite incineration

    International Nuclear Information System (INIS)

    Antonini, G.; Perotin, J.P.; Charlot, P.

    1992-01-01

    The authors demonstrate the interest of the utilization of a pressurized-graphite/water/oxygen mixture in the incineration of irradiated graphite. The aqueous phase comes in the form of a three-dimensional system that traps pressurized oxygen, the pulverulent solid being dispersed at the liquid/gas interfaces. These three-phasic formulations give the following advantages: reduction of the apparent viscosity of the mixture in comparison with a solid/liquid mixture at the same solid concentration; reduction of the solid/liquid interactions; self-pulverizability. thus promoting reduction of the flame length utilization of conventional burners; reduction of the flue gas flow rate; complete thermal destruction of graphite. (author)

  19. Development and testing of a glass waste form for the immobilization of plutonium

    International Nuclear Information System (INIS)

    Chamberlain, D.B.; Hanchar, J.M.; Emery, J.W.; Hoh, J.C.; Wolf, S.F.; Finch, R.J.; Bates, J.K.; Ellison, A.J.G.; Dingwell, D.B.

    1996-01-01

    The United States has declared about 50 metric tons of weapons-grade Pu surplus to national security needs. The President has directed that this Pu be placed in a form that provides a high degree of proliferation resistance in which the surplus Pu is both unattractive and inaccessible for use by others [I]. Three alternatives are being evaluated for the disposal 2048 of this material: (1) use of the Pu as a fuel source for commercial reactors; (2) immobilization, where Pu is fixed in a glass or ceramic matrix that also contains or is surrounded by highly radioactive material; and (3) deep bore hole, where Pu is emplaced at depths of several kilometers. The immobilization alternative is being directed by the staff at Lawrence Livermore National Laboratory (LLNL). The staff at ANL are assisting by developing a glass for the immobilization of Pu and in the corrosion testing of glass and ceramic material prepared both at ANL and at other DOE laboratories. As part of this program, we have developed an ATS glass into which 5-7 wt percent Pu has been dissolved. The ATS glass was engineered to accommodate high Pu loading and to be durable under conditions likely to accelerate glass reactions in the geological environment during long-term storage

  20. Conversion of plutonium scrap and residue to boroilicate glass using the GMODS process

    International Nuclear Information System (INIS)

    Forsberg, C.W.; Beahm, E.C.; Parker, G.W.; Rudolph, J.; Elam, K.R.; Ferrada, J.J.

    1995-01-01

    Plutonium scrap and residue represent major national and international concerns because (1) significant environmental, safety, and health (ES ampersand H) problems have been identified with their storage; (2) all plutonium recovered from the black market in Europe has been from this category; (3) storage costs are high; and (4) safeguards are difficult. It is proposed to address these problems by conversion of plutonium scrap and residue to a CRACHIP (CRiticality, Aerosol, and CHemically Inert Plutonium) glass using the Glass Material Oxidation and Dissolution System (GMODS). CRACHIP refers to a set of requirements for plutonium storage forms that minimize ES ampersand H concerns. The concept is several decades old. Conversion of plutonium from complex chemical mixtures and variable geometries into a certified, qualified, homogeneous CRACHIP glass creates a stable chemical form that minimizes ES ampersand H risks, simplifies safeguards and security, provides an easy-to-store form, decreases storage costs, and allows for future disposition options. GMODS is a new process to directly convert metals, ceramics, and amorphous solids to glass; oxidize organics with the residue converted to glass; and convert chlorides to borosilicate glass and a secondary sodium chloride stream. Laboratory work has demonstrated the conversion of cerium (a plutonium surrogate), uranium (a plutonium surrogate), Zircaloy, stainless steel, and other materials to glass. GMODS is an enabling technology that creates new options. Conventional glassmaking processes require conversion of feeds to oxide-like forms before final conversion to glass. Such chemical conversion and separation processes are often complex and expensive

  1. Effects of fibers on expansive shotcrete mixtures consisting of calcium sulfoaluminate cement, ordinary Portland cement, and calcium sulfate

    Directory of Open Access Journals (Sweden)

    H. Yu

    2018-04-01

    Full Text Available The mining industry often uses shotcrete for ground stabilization. However, cracking within shotcrete is commonly observed, which delays production schedules and increases maintenance costs. A possible crack reduction method is using expansive shotcrete mixture consisting of calcium sulfoaluminate cement (CSA, ordinary Portland cement (OPC, and calcium sulfate (CS to reduce shrinkage. Furthermore, fibers can be added to the mixture to restrain expansion and impede cracking. The objective of this paper is to study the effects of nylon fiber, glass fiber, and steel fiber on an expansive shotcrete mixture that can better resist cracking. In this study, parameters such as density, water absorption, volume of permeable voids, unconfined compressive strength (UCS, splitting tensile strength (STS, and volume change of fiber-added expansive mixtures were determined at different time periods (i.e. the strengths on the 28th day, and the volume changes on the 1st, 7th, 14th, 21st, and 28th days. The results show that addition of fibers can improve mixture durability, in the form of decreased water absorption and reduced permeable pore space content. Moreover, the expansion of the CSA-OPC-CS mixture was restrained up to 50% by glass fiber, up to 43% by nylon fiber, and up to 28% by steel fiber. The results show that the STS was improved by 57% with glass fiber addition, 43% with steel fiber addition, and 38% with nylon fiber addition. The UCS was also increased by 31% after steel fiber addition, 26% after nylon fiber addition, and 16% after glass fiber addition. These results suggest that fiber additions to the expansive shotcrete mixtures can improve durability and strengths while controlling expansion. Keywords: Shotcrete, Restrained expansion, Fibers, Calcium sulfoaluminate cement (CSA, Ordinary Portland cement (OPC, Calcium sulfate (CS

  2. Attenuation of glass dissolution in the presence of natural additives

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-11-01

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

  3. Local dynamics and deformation of glass-forming polymers : modelling and atomistic simulations

    NARCIS (Netherlands)

    Vorselaars, B.

    2008-01-01

    The research described in the present thesis is about glassy phenomena and mechanical properties in vitrifiable polymer materials. Glasses are solid materials, but, in contrast to crystals, the structure is disordered. Polymers are macromolecular chains formed by covalently linking a very large

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

    International Nuclear Information System (INIS)

    Vandiver, P.B.

    1994-01-01

    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 glassclose 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

  5. Investigating the Properties of Asphalt Concrete Containing Glass Fibers and Nanoclay

    Directory of Open Access Journals (Sweden)

    Hasan Taherkhani

    2016-06-01

    Full Text Available The performance of asphaltic pavements during their service life is highly dependent on the mechanical properties of the asphaltic layers. Therefore, in order to extend their service life, scientists and engineers are constantly trying to improve the mechanical properties of the asphaltic mixtures. One common method of improving the performance of asphaltic mixtures is using different types of additives. This research investigated the effects of reinforcement by randomly distributed glass fibers and the simultaneous addition of nanoclayon some engineering properties of asphalt concrete have been investigated. The properties of a typical asphalt concrete reinforced by different percentages of glass fibers were compared with those containing both the fibers and nanoclay. Engineering properties, including Marshall stability, flow, Marshall quotient, volumetric properties and indirect tensile strength were studied. Glass fibers were used in different percentages of 0.2, 0.4 and 0.6% (by weight of total mixture, and nanoclay was used in 2, 4 and 6% (by the weight of bitumen. It was found that the addition of fibers proved to be more effective than the nanoclay in increasing the indirect tensile strength. However, nanoclay improved the resistance of the mixture against permanent deformation better than the glass fibers. The results also showed that the mixture reinforced by 0.2% of glass fiber and containing 6% nanoclay possessed the highest Marshall quotient, and the mixture containing 0.6% glass fibers and 2% nanoclay possessedthe highest indirect tensile strength.

  6. Long-term behavior of glass-ceramic zirconolite

    International Nuclear Information System (INIS)

    Martin, Ch.

    2003-01-01

    This work is a part of the investigation of new containment matrices considered for specific conditioning of radionuclides after separation. The aim was to demonstrate the long-term aqueous corrosion resistance of the glass-ceramic zirconolite considered for the conditioning of plutonium and the minor actinides. This material is composed of crystals of zirconolite (CaZrTi 2 O 7 ) dispersed in a residual vitreous phase. It appears that glass-ceramic zirconolite presents a better kinetic behavior than the nuclear glass R 7T7. This is mainly due to a more important rate decrease that occurs more rapidly, that induces a quantity of glass altered at least 10 times as small as for R 7T7 glass. This high 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 demonstrated that the rate decrease was controlled as for the R7T7 glass by the amorphous phase of the alteration film forming a diffusion barrier for reactive species. It seems that the porosity is not the single parameter that explains the protective effect of the gel. The main differences compared with R7T7 glass are that silicon does not control the alteration of the material and that the gel is composed of two distinct phases. We have in particular identified a dense phase enriched in titanium and neodymium that probably influences deeply the kinetics. (author)

  7. Simple radiosensitizing of hypoxic tumor tissues by N2O/Br(-) mixture.

    Science.gov (United States)

    Billik, P

    2015-07-01

    The radiosensitization model of hypoxic tumor tissues based on the N2O/Br(-) mixture is described. The well-documented radiolysis of water in the presence of N2O and Br(-) ions at a low concentration supports this model. An aqueous solution saturated with N2O gas during the radiolysis generates OH radicals in a large extent. In N2O/Br- media at pHBr2 is formed. Br2 hydrolyzes in an aqueous solution to form a very reactive hypobromous (HOBr) acid. Such process is described by the following chemical reaction: H2O + Br(-) + N2O + ionizing radiation (IR) --> HOBr + OH(-). In vivo formed HOBr as a long-lived product with a high biological activity induces the hypoxic tumor cell damage via many unique mechanisms. A local application or inhalation of an N2O-O2 mixture before or during the radiotherapy to enhance the saturation of tissues with N2O is a key prerequisite. Since the extracellular concentration of Br(-) ions is very low (0.02-0.05 mM), an oral or local application of NaBr should be used to shift the extracellular concentration of Br(-) ions to the mM region. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Effect of Yttrium Addition on Glass-Forming Ability and Magnetic Properties of Fe–Co–B–Si–Nb Bulk Metallic Glass

    Directory of Open Access Journals (Sweden)

    Teruo Bitoh

    2015-06-01

    Full Text Available The glass-forming ability (GFA and the magnetic properties of the [(Fe0.5Co0.50.75B0.20Si0.05]96Nb4−xYx bulk metallic glasses (BMGs have been studied. The partial replacement of Nb by Y improves the thermal stability of the glass against crystallization. The saturation mass magnetization (σs exhibits a maximum around 2 at. % Y, and the value of σs of the alloy with 2 at. % Y is 6.5% larger than that of the Y-free alloy. The coercivity shows a tendency to decrease with increasing Y content. These results indicate that the partial replacement of Nb by Y in the Fe–Co–B–Si–Nb BMGs is useful to simultaneous achievement of high GFA, high σs, and good soft magnetic properties.

  9. Chemical modification of glass surface with a monolayer of nonchromophoric and chromophoric methacrylate terpolymer

    Energy Technology Data Exchange (ETDEWEB)

    Janik, Ryszard [Department of Polymer Engineering and Technology, Wroclaw University of Technology, 50-370 Wroclaw (Poland); Kucharski, Stanislaw, E-mail: stanislaw.kucharski@pwr.wroc.pl [Department of Polymer Engineering and Technology, Wroclaw University of Technology, 50-370 Wroclaw (Poland); Sobolewska, Anna [Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology, 50-370 Wroclaw (Poland); Barille, Regis [Institut des Sciences et Techniques Moleculaires d' Angers ' Moltech Anjou' , CNRS UMR 6200, 49045 Angers (France)

    2010-11-15

    The methacrylate terpolymers, a nonchromophoric and chromophoric one, containing 2-hydroxyethyl groups were reacted with 3-isocyanatopropyltriethoxysilane to obtain reactive polymers able to form covalent bonding with -SiOH groups of the glass surface via triethoxysilane group condensation. Chemical modification of the Corning 2949 glass plates treated in this way resulted in increase of wetting angle from 11{sup o} to ca. 70-73{sup o}. Determination of ellipsometric parameters revealed low value of the substrate refractive index as compared with that of bulk Corning 2949 glass suggesting roughness of the surface. The AFM image of the bare glass surface and that modified with terpolymer monolayer confirmed this phenomenon. Modification of the glass with the terpolymer monolayer made it possible to create the substrate surface well suited for deposition of familiar chromophore film by spin-coating. The chromophore polymer film deposited onto the modified glass surface was found to be resistant to come unstuck in aqueous solution.

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

    International Nuclear Information System (INIS)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ku-Herrera, J.J., E-mail: jesuskuh@live.com.mx [Centro de Investigación Científica de Yucatán A.C., Unidad de Materiales, Calle 43 No.130, Col. Chuburná de Hidalgo. C.P., 97200 Mérida, Yucatán (Mexico); Avilés, F., E-mail: faviles@cicy.mx [Centro de Investigación Científica de Yucatán A.C., Unidad de Materiales, Calle 43 No.130, Col. Chuburná de Hidalgo. C.P., 97200 Mérida, Yucatán (Mexico); Nistal, A. [Instituto de Cerámica y Vidrio (ICV-CSIC), Kelsen 5, 28049 Madrid (Spain); Cauich-Rodríguez, J.V. [Centro de Investigación Científica de Yucatán A.C., Unidad de Materiales, Calle 43 No.130, Col. Chuburná de Hidalgo. C.P., 97200 Mérida, Yucatán (Mexico); Rubio, F.; Rubio, J. [Instituto de Cerámica y Vidrio (ICV-CSIC), Kelsen 5, 28049 Madrid (Spain); Bartolo-Pérez, P. [Departamento de Física Aplicada, Cinvestav, Unidad Mérida, C.P., 97310 Mérida, Yucatán (Mexico)

    2015-03-01

    Graphical abstract: - Highlights: • Oxidized multiwall carbon nanotubes (MWCNTs) were deposited onto E-glass fibers. • The role of the fiber coating on the deposition of MWCNTs on the fibers is studied. • A rather homogeneous deposition of MWCNTs is achieved if the coating is maintained. • Multiple oxygen-containing groups were found in the analysis of the fiber coating. • Evidence of chemical interaction between MWCNTs and the fiber coating was found. - Abstract: 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.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    Graphical abstract: - Highlights: • Oxidized multiwall carbon nanotubes (MWCNTs) were deposited onto E-glass fibers. • The role of the fiber coating on the deposition of MWCNTs on the fibers is studied. • A rather homogeneous deposition of MWCNTs is achieved if the coating is maintained. • Multiple oxygen-containing groups were found in the analysis of the fiber coating. • Evidence of chemical interaction between MWCNTs and the fiber coating was found. - Abstract: 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

  14. The effect of atom mismatch on the fragility of supercooled Lennard-Jones binary mixtures

    International Nuclear Information System (INIS)

    Sun Minhua; Sun Yongli; Wang Aiping; Ma Congxiao; Li Jiayun; Cheng Weidong; Liu Fang

    2006-01-01

    The shear viscosity of the well-known binary Lennard-Jones mixture is simulated under constant temperature and constant volume conditions (NVT) by a molecular-dynamics (MD) method. The effect of atomic size mismatch on the fragility parameter and glass-forming ability is studied. The fragility parameters calculated from shear viscosity data decrease with the increment of the atomic size mismatch. The value of the fragility changes from 168.963 to 22.976 when the mismatch changes from 0.023 to 0.25. It is shown that the fragility parameter is sensitive to the atomic size mismatch. The calculated pair distribution functions and mean square displacements indicate that the glass-forming ability increases with the atomic size mismatch

  15. Effect of irradiation on the evolution of alteration layer formed during nuclear glass leaching

    International Nuclear Information System (INIS)

    Mougnaud, Sarah

    2016-01-01

    High-level radioactive waste (HLW) remaining after spent nuclear fuel reprocessing is immobilized within a glass matrix, eventually destined for geological disposal. Water intrusion into the repository is expected after several thousand years. The alteration of a non-radioactive surrogate for nuclear glass has been extensively studied and it has been determined that successive leaching mechanisms lead to the formation of a 'passivating' alteration layer and to the establishment of a residual rate regime in the long term. However, glass packages are submitted to the radioactivity of confined radioelements. This work focuses on the influence of irradiation on the alteration layer formed during the residual rate regime, in a structural and mechanistic point of view. Three focal areas have been selected. Non-radioactive simple glasses have been leached and externally irradiated in order to determine modifications induced by electronic effects (irradiations with electrons and alpha particles). The same type of glass samples have been previously irradiated with heavy ions and their leaching behavior have been studied in order to assess the impact of ballistic dose cumulated by the glass before water intrusion. Leaching behavior of a complex radioactive glass, doped with an alpha-emitter, has been studied to consider a more realistic situation. (author) [fr

  16. Uptake of vaporized molybdenum and cesium tracers by molten oxide mixtures as function of free oxygen ion activity

    International Nuclear Information System (INIS)

    Carmon, B.

    1975-11-01

    Molten mixtures of oxides containing Ca, Fe, Al, Na and Si were exposed to vaporized Mo-99 and Cs-137 tracers at 1100 and 1300 deg C. Uptake values at 1300 deg C were extrapolated to short heating times. The obtained ''attachment coefficients'' for that temperature are shown to have the relationship (Mo) approximately equal to (Cs)sup(-1/2). The chemical composition of the melts and their oxygen to metal ratio found to affect the uptake of both tracers. This is associated with the cationic field strengths and the free oxygen ion activities in the mixtures. Molybdenum and cesium apparently behave like glass-network forming and glass-network modifying species, respectively. (author)

  17. Laboratory testing of waste glass aqueous corrosion; effects of experimental parameters

    International Nuclear Information System (INIS)

    Ebert, W.L.; Mazer, J.J.

    1993-01-01

    A literature survey has been performed to assess the effects of the temperature, glass surface area/leachate volume ratio, leachant composition, leachant flow rate, and glass composition (actual radioactive vs. simulated glass) used in laboratory tests on the measured glass reaction rate. The effects of these parameters must be accounted for in mechanistic models used to project glass durability over long times. Test parameters can also be utilized to highlight particular processes in laboratory tests. Waste glass corrosion results as water diffusion, ion-exchange, and hydrolysis reactions occur simultaneously to devitrify the glass and release soluble glass components into solution. The rates of these processes are interrelated by the affects of the solution chemistry and glass alteration phases on each process, and the dominant (fastest) process may change as the reaction progresses. Transport of components from the release sites into solution may also affect the observed corrosion rate. The reaction temperature will affect the rate of each process, while other parameters will affect the solution chemistry and which processes are observed during the test. The early stages of corrosion will be observed under test conditions which maintain dilute leachates and the later stages will be observed under conditions that generate more concentrated leachate solutions. Typically, water diffusion and ion-exchange reactions dominate the observed glass corrosion in dilute solutions while hydrolysis reactions dominant in more concentrated solutions. Which process(es) controls the long-term glass corrosion is not fully understood, and the long-term corrosion rate may be either transport- or reaction-limited

  18. Solubility effects in waste-glass/demineralized-water systems

    International Nuclear Information System (INIS)

    Fullam, H.T.

    1981-06-01

    Aqueous systems involving demineralized water and four glass compositions (including standins for actinides and fission products) at temperatures of up to 150 0 C were studied. Two methods were used to measure the solubility of glass components in demineralized water. One method involved approaching equilibrium from subsaturation, while the second method involved approaching equilibrium from supersaturation. The aqueous solutions were analyzed by induction-coupled plasma spectrometry (ICP). Uranium was determined using a Scintrex U-A3 uranium analyzer and zinc and cesium were determined by atomic absorption. The system that results when a waste glass is contacted with demineralized water is a complex one. The two methods used to determine the solubility limits gave very different results, with the supersaturation method yielding much higher solution concentrations than the subsaturation method for most of the elements present in the waste glasses. The results show that it is impossible to assign solubility limits to the various glass components without thoroughly describing the glass-water systems. This includes not only defining the glass type and solution temperature, but also the glass surface area-to-water volume ratio (S/V) of the system and the complete thermal history of the system. 21 figures, 22 tables

  19. 75 FR 36306 - Chemical Mixtures Containing Listed Forms of Phosphorus and Change in Application Process

    Science.gov (United States)

    2010-06-25

    ... have large industrial uses. Regulated chemical mixtures are not items having common household uses... and others from exposure to the toxic chemicals left behind. Executive Order 12988 This regulation... 1117-AA66 Chemical Mixtures Containing Listed Forms of Phosphorus and Change in Application Process...

  20. Application of Genetic Algorithm (GA) Assisted Partial Least Square (PLS) Analysis on Trilinear and Non-trilinear Fluorescence Data Sets to Quantify the Fluorophores in Multifluorophoric Mixtures: Improving Quantification Accuracy of Fluorimetric Estimations of Dilute Aqueous Mixtures.

    Science.gov (United States)

    Kumar, Keshav

    2018-03-29

    Excitation-emission matrix fluorescence (EEMF) and total synchronous fluorescence spectroscopy (TSFS) are the 2 fluorescence techniques that are commonly used for the analysis of multifluorophoric mixtures. These 2 fluorescence techniques are conceptually different and provide certain advantages over each other. The manual analysis of such highly correlated large volume of EEMF and TSFS towards developing a calibration model is difficult. Partial least square (PLS) analysis can analyze the large volume of EEMF and TSFS data sets by finding important factors that maximize the correlation between the spectral and concentration information for each fluorophore. However, often the application of PLS analysis on entire data sets does not provide a robust calibration model and requires application of suitable pre-processing step. The present work evaluates the application of genetic algorithm (GA) analysis prior to PLS analysis on EEMF and TSFS data sets towards improving the precision and accuracy of the calibration model. The GA algorithm essentially combines the advantages provided by stochastic methods with those provided by deterministic approaches and can find the set of EEMF and TSFS variables that perfectly correlate well with the concentration of each of the fluorophores present in the multifluorophoric mixtures. The utility of the GA assisted PLS analysis is successfully validated using (i) EEMF data sets acquired for dilute aqueous mixture of four biomolecules and (ii) TSFS data sets acquired for dilute aqueous mixtures of four carcinogenic polycyclic aromatic hydrocarbons (PAHs) mixtures. In the present work, it is shown that by using the GA it is possible to significantly improve the accuracy and precision of the PLS calibration model developed for both EEMF and TSFS data set. Hence, GA must be considered as a useful pre-processing technique while developing an EEMF and TSFS calibration model.

  1. Evaluation of La-Doped Mesoporous Bioactive Glass as Adsorbent and Photocatalyst for Removal of Methylene Blue from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Liying Li

    2015-01-01

    Full Text Available A series of La-doped mesoporous bioactive glass (BG-La materials with excellent biosafety and hypotoxicity have been prepared and tested as adsorbent. The study was aimed to evaluate the possibility of utilizing BG-La for the adsorptive removal of methylene blue (MB from aqueous solution and test the adsorption and desorption behavior of this new material. The process parameters affecting adsorption behaviors such as pH, contact time, and initial concentration and the photocatalytic degradation of MB were systematically investigated. The result showed that BG-La had excellent removal rate (R of MB, and BG-La showed better photocatalytic effect than undoped mesoporous bioactive glass (BG. Furthermore, the MB loaded BG-La was easily desorbed with acid solution due to its electronegativity and mesoporous structure. The result indicated that these materials can be employed as candidates for removal of dye pollutant owing to their high removal rate, excellent photocatalytic effect, desorption performance, and their reusability.

  2. Analysis of glass fibre sizing

    DEFF Research Database (Denmark)

    Petersen, Helga Nørgaard; Kusano, Yukihiro; Brøndsted, Povl

    2014-01-01

    Glass fibre reinforced polymer composites are widely used for industrial and engineering applications which include construction, aerospace, automotive and wind energy industry. During the manufacturing glass fibres, they are surface-treated with an aqueous solution. This process and the treated...... surfaces are called sizing. The sizing influences the properties of the interface between fibres and a matrix, and subsequently affects mechanical properties of composites. In this work the sizing of commercially available glass fibres was analysed so as to study the composition and chemical structures....... Soxhlet extraction was used to extract components of the sizing from the glass fibres. The glass fibres, their extracts and coated glass plates were analysed by Thermo-Gravimetric Analysis combined with a mass spectrometer (TGA-MS), and Attenuated Total Reflectance Fourier Transform Infrared (ATR...

  3. Casting of organic glass by radiation-induced polymerization of glass-forming monomers at low temperature. II. Optical strain of remaining stress type

    International Nuclear Information System (INIS)

    Okubo, H.; Yoshii, F.; Kaetsu, I.; Honda, S.

    1978-01-01

    Previously it was found that casting could be carried out efficiently without strain formation by radiation-induced polymerization of glass-forming monomers. Two types of strain were observed in casting: thermal stream type, which was studied previously, and remained stress type. In this report, the effect of various factors on the formation of remaining stress-type strain in radiation-induced casting polymerization was studied. It was found that the molecular weight of prepolymer did not affect strain formation, while prepolymer concentration and viscosity of the system had a serious influence on strain formation. It could be deduced that this type of strain formed as a result of remaining inner stress due to poor relaxation of the shrinking stress. It was realized that less volume shrinkage of glass-forming monomers accompanying casting polymerization reduced the strain formation of this type in radiation-induced casting polymerization at low temperatures

  4. Harmonic-anharmonic transition in disaccharides/H{sub 2}O mixtures by EINS

    Energy Technology Data Exchange (ETDEWEB)

    Magazu, S.; Migliardo, F.; Mondelli, C

    2004-07-15

    This work furnishes new experimental findings on glass-forming systems, i.e. homologues disaccharides (trehalose, maltose, sucrose)/H{sub 2}O mixtures obtained by using elastic incoherent neutron scattering. Such a technique allows to characterize the different degree of 'strength' of the investigated systems by means of the analysis of both the elastic intensity and the mean square displacement behaviours as a function of temperature and Q. The better cryptoprotectant effectiveness of trehalose in comparison with the other disaccharides is ascribed to lower fragility of the matrix in which biostructures are immersed, i.e. of the trehalose/water mixture.

  5. [Depyrogenation test regarding inox and glass containers in the preparation of parenteral nutrition mixtures].

    Science.gov (United States)

    Lajoinie, A; Vasselon, P; Tall, M-L; Salmon, D; Bréant, V; Diouf, E; Pivot, C; Pirot, F

    2012-09-01

    The preparation of parenteral nutrition mixture (PNM) in an open chamber requires the use of intermediate containers sterile and non-pyrogenic. A sterilization of containers by moist heat in large autoclaves is the suitable method. However, sterilization by moist heat is not a depyrogenation method. In our study, we report the validation of a sterilization and depyrogenation method for containers by dry heat using a convection oven. Sterilization and depyrogenation of material by dry heat have been audited by the reduction of at least three logarithms of original endotoxin rate. The containers were initially artificially contaminated with a suspension of endotoxin for 16 hours. Contaminated containers were placed in an oven with revolving heat at 250 °C for 1 hour. After treatment with dry heat, the residual endotoxin levels in the containers were determined by a kinetic chromogenic method. After treatment with dry heat, the average log reductions of endotoxin levels were respectively, for glass and steel containers, 4.78 ± 0.07 and 4.87 ± 0.03. The present validation study confirms the effectiveness of treatment with dry heat for sterilization and depyrogenation of glass and steel containers. This method of sterilization and depyrogenation meets the microbiological quality requirements for the preparation of MNP. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  6. DURABILITY TESTING OF FLUIDIZED BED STEAM REFORMER (FBSR) WASTE FORMS

    International Nuclear Information System (INIS)

    Jantzen, C

    2006-01-01

    Fluidized Bed Steam Reforming (FBSR) is being considered as a potential technology for the immobilization of a wide variety of high sodium aqueous radioactive wastes. The addition of clay and a catalyst as co-reactants converts high sodium aqueous low activity wastes (LAW) such as those existing at the Hanford and Idaho DOE sites to a granular ''mineralized'' waste form that may be made into a monolith form if necessary. Simulant Hanford and Idaho high sodium wastes were processed in a pilot scale FBSR at Science Applications International Corporation (SAIC) Science and Technology Applications Research (STAR) facility in Idaho Falls, ID. Granular mineral waste forms were made from (1) a basic Hanford Envelope A low-activity waste (LAW) simulant and (2) an acidic INL simulant commonly referred to as sodium-bearing waste (SBW). The FBSR waste forms were characterized and the durability tested via ASTM C1285 (Product Consistency Test), the Environmental Protection Agency (EPA) Toxic Characteristic Leaching Procedure (TCLP), and the Single Pass Flow Through (SPFT) test. The durability of the FBSR waste form products was tested in order to compare the measured durability to previous FBSR waste form testing on Hanford Envelope C waste forms that were made by THOR Treatment Technologies (TTT) and to compare the FBSR durability to vitreous LAW waste forms, specifically the Hanford low activity waste (LAW) glass known as the Low-activity Reference Material (LRM). The durability of the FBSR waste form is comparable to that of the LRM glass for the test responses studied

  7. Glassy slag: A complementary waste form to homogeneous glass for the implementation of MAWS in treating DOE low level/mixed wastes

    International Nuclear Information System (INIS)

    Feng, X.; Ordaz, G.; Krumrine, P.

    1994-01-01

    Glassy slag waste forms are being developed to complement glass waste forms in implementing the Minimum Additive Waste Stabilization (MAWS) Program for supporting DOE's environmental restoration efforts. These glassy slags are composed of various metal oxide crystalline phases embedded in an alumino-silicate glass phase. The slags are appropriate final waste forms for waste streams that contain large amounts of scrap metals and elements with low solubilities in glass, and that have low-flux contents. Homogeneous glass waste forms are appropriate for wastes with sufficient fluxes and low metal contents. Therefore, utilization of both glass and glassy slag waste forms will make vitrification technology applicable to the treatment of a much larger range of radioactive and mixed wastes. The MAWS approach was a plied to glassy slags by blending multiple waste streams to produce the final waste form, minimizing overall waste form volume and reducing costs. The crystalline oxide phases formed in the glassy slags can be specially formulated so that they are very durable and contain hazardous and radioactive elements in their lattice structures. The Structural Bond Strength (SBS) Model was used to predict the chemical durability of the product from the slag composition so that optimized slag compositions could be obtain with a limited number of crucible melts and testing

  8. Solvent dynamics in a glass-forming liquid from 300 K to 3 K : What photon echoes can teach us

    NARCIS (Netherlands)

    Lazonder, Kees; Pshenichnikov, Maxim S.

    2007-01-01

    The temperature dependence of the optical non-linear response of dye molecules dissolved in a glass-forming liquid over a temperature range that includes the glass transition is investigated. Cooling down to temperatures below the glass transition dramatically slows the diffusive motion of the

  9. Solution exchange corrosion testing with the glass-zeolite ceramic waste form in demineralized water at 900C

    International Nuclear Information System (INIS)

    Simpson, L. J.

    1998-01-01

    A ceramic waste form of glass-bonded zeolite is being developed for the long-term disposition of fission products and transuranic elements in wastes from the U.S. Department of Energy's spent nuclear fuel conditioning activities. Solution exchange corrosion tests were performed on the ceramic waste form and its potential base constituents of glass, zeolite 5A, and sodalite as part of an effort to qualify the ceramic waste form for acceptance into the Civilian Radioactive Waste Management System. Solution exchange tests were performed at 90 C by replacing 80 to 90% of the leachate with fresh demineralized water after set time intervals. The results from these tests provide information about corrosion mechanisms and the ability of the ceramic waste form and its constituent materials to retain waste components. The results from solution exchange tests indicate that radionuclides will be preferentially retained in the zeolites without the glass matrix and in the ceramic waste form, with respect to cations like Li, K, and Na. Release results have been compared for simulated waste from candidate ceramic waste forms with zeolite 5A and its constituent materials to determine the corrosion behavior of each component

  10. Electrical resistivities of glass melts containing simulated SRP waste sludges

    International Nuclear Information System (INIS)

    Wiley, J.R.

    1978-08-01

    One option for the long-term management of radioactive waste at the Savannah River Plant is to solidify the waste in borosilicate glass by using a continuous, joule-heated, ceramic melter. Electrical resistivities that are needed for melter design were measured for melts of two borosilicate, glass-forming mixtures, each of which was combined with various amounts of several simulated-waste sludges. The simulated sludge spanned the composition range of actual sludges sampled from SRP waste tanks. Resistivities ranged from 6 to 10 ohm-cm at 500 0 C. Melt composition and temperature were correlated with resistivity. Resistivity was not a simple function of viscosity. 15 figures, 4 tables

  11. Cation coordination in oxychloride glasses

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, J A [Energy Technology Division, Argonne National Laboratory, Argonne, IL (United States); Holland, D [Physics Department, Warwick University, Coventry (United Kingdom); Bland, J [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom); Johnson, C E [Physics Department, Northern Illinois University, DeKalb, IL (United States); Thomas, M F [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom)

    2003-02-19

    Glasses containing mixtures of cations and anions of nominal compositions [Sb{sub 2}O{sub 3}]{sub x} - [ZnCl{sub 2}]{sub 1-x} where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb){sub 2}(OZn)] and [Zn(ClZn){sub 2}(OSb){sub 2}].

  12. Glass forming ability of Al–Ni–La alloys with Si addition

    Energy Technology Data Exchange (ETDEWEB)

    Yi, J.J.; Xiong, X.Z. [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Inoue, A. [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); WPI-Advanced Institute for Material Research, Tohoku University, Sendai 980-8577 (Japan); Kong, L.T. [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Li, J.F., E-mail: jfli@sjtu.edu.cn [State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China)

    2015-11-25

    (Al{sub 85.5}Ni{sub 9.5}La{sub 5}){sub 100−x}Si{sub x}, (Al{sub 86}Ni{sub 9}La{sub 5}){sub 100−x}Si{sub x}, (Al{sub 86}Ni{sub 9.5}La{sub 4.5}){sub 100−x}Si{sub x}, (Al{sub 86}Ni{sub 10}La{sub 4}){sub 100−x}Si{sub x} and (Al{sub 86}Ni{sub 10.5}La{sub 3.5}){sub 100−x}Si{sub x} alloys, where x = 0.0, 0.2, 0.5, 1.0, 1.5 and 2.0, were cast under the same suction casting conditions into a wedge-shaped copper mold for investigating the effect of Si addition on the glass-forming ability (GFA). The GFA of the Al–Ni–La base alloys, except for the optimal glass former (Al{sub 85.5}Ni{sub 9.5}La{sub 5}), is enhanced when a proper content of Si is added. The largest content of Si up to which GFA can be enhanced changes in the following order of the base alloys: Al{sub 86}Ni{sub 9}La{sub 5}, Al{sub 86}Ni{sub 9.5}La{sub 4.5}, Al{sub 86}Ni{sub 10}La{sub 4} and Al{sub 86}Ni{sub 10.5}La{sub 3.5}. The enhancement of GFA due to Si addition becomes more significant as the La content decreases. This is presumably because more free Al atoms are present in the base alloy. - Highlights: • 0.2–2.0 at. % Si was added to each ternary base alloy. • Wedge-shaped samples were suction cast to obtain the glass-forming ability (GFA). • The GFA of the ternary non-optimal glass formers can be enhanced by Si addition. • The number of free-Al atoms dominates the best Si addition.

  13. Plutonium recovery from spent glass fiber paper fine air filter

    International Nuclear Information System (INIS)

    Rovnyj, S.I.; Guzhavin, V.I.; Pyatin, N.P.; Evlanov, D.S.

    2002-01-01

    Investigations into the realizing technology of plutonium recovery from waste glass paper filters of fine purification were conducted. Two process schemes involving the nitro-fluoro-acid treatment of glass paper in the mixture of nitric and hydrofluoric acids and the previous alkali treatment of glass paper with the following nitro-fluoro-acid leaching of plutonium from pulp by the mixture of nitric and hydrofluoric acids were developed. Alkali, nitrate solutions and insoluble precipitants were analyzed for plutonium content [ru

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

    International Nuclear Information System (INIS)

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

    1995-01-01

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

  15. Synergic effects in the extraction of paracetamol from aqueous NaCl solution by the binary mixtures of diethyl ether and low molecular weight primary alcohols

    Science.gov (United States)

    Nikolić, G. M.; Živković, J. V.; Atanasković, D. S.; Nikolić, M. G.

    2013-12-01

    Liquid-liquid extraction of paracetamol from aqueous NaCl solutions was performed with diethyl ether, 1-propanol, 1-butanol, isobutanol, 1-pentanol, and binary mixtures diethyl ether/1-propanol, diethyl ether/1-butanol, and diethyl ether/isobutanol. Among the pure solvents investigated in this study best extraction efficacy was obtained with 1-butanol. Synergic effects in the extraction with binary mixtures was investigated and compared with some other systems used for the extraction of poorly extractable compounds. Results obtained in this study may be of both fundamental and practical importance.

  16. Glass forming tendencies of chalcogenides of the system (As2Se3)sub(1-x):(T12Se)sub(x)

    International Nuclear Information System (INIS)

    Majid, C.A.

    1982-07-01

    In this paper glass forming capabilities of chalcogenide glasses based on As 2 Se 3 with T1 2 Se concentrations are discussed. The studies were made using the differential thermal analysis (DTA) technique. These studies show that the glass forming tendency of As 2 Se 3 decreases as the concentrations of T1 2 Se molecules are increased. Also these studies show that with addition of T1 2 Se, the glass transition temperature Tsub(g) of As 2 Se 3 decreases, suggesting a tendency for weaker bonding and hence less stability of T1-rich compositions. (author)

  17. Radiation effects in silicate glasses

    International Nuclear Information System (INIS)

    Bibler, N.E.; Howitt, D.G.

    1988-01-01

    The study of radiation effects in complex silicate glasses has received renewed attention because of their use in special applications such as high level nuclear waste immobilization and fiber optics. Radiation changes the properties of these glasses by altering their electronic and atomic configurations. These alterations or defects may cause dilatations or microscopic phase changes along with absorption centers that limit the optical application of the glasses. Atomic displacements induced in the already disordered structure of the glasses may affect their use where heavy irradiating particles such as alpha particles, alpha recoils, fission fragments, or accelerated ions are present. Large changes (up to 1%) in density may result. In some cases the radiation damage may be severe enough to affect the durability of the glass in aqueous solutions. In the paper, the authors review the literature concerning radiation effects on density, durability, stored energy, microstructure and optical properties of silicate glasses. Both simple glasses and complex glasses used for immobilization of nuclear waste are considered

  18. Glass forms for immobilization of Hanford wastes

    International Nuclear Information System (INIS)

    Schulz, W.W.; Dressen, A.L.; Hobbick, C.W.; Babad, H.

    1975-03-01

    Approximately 140 million liters of solid salt cake (mainly NaNO 3 ), produced by evaporation of aged alkaline high-level liquid wastes, will be stored in underground tanks when the present Hanford Waste Management Program is completed in the early 1980's. At this time also, large volumes of various other solid radioactive wastes (sludges, excavated Pu-contaminated soil, and doubly encapsulated 137 CsCl and 90 SrF 2 ) will be stored on the Hanford Reservation. All these solid wastes can be converted to immobile silicate and aluminosilicate glasses of low water leachability by melting them at 1100 0 to 1400 0 C with appropriate amounts of basalt (or sand) and other glass-formers such as B 2 O 3 or CaO. Reviewed in this paper are formulations and other melt conditions used successfully in batch tests to make glasses from actual and synthetic wastes; leachability and other properties of these glasses show them to be satisfactory vehicles for immobilization of the Hanford wastes. (U.S.)

  19. Class B Fire-Extinguishing Performance Evaluation of a Compressed Air Foam System at Different Air-to-Aqueous Foam Solution Mixing Ratios

    Directory of Open Access Journals (Sweden)

    Dong-Ho Rie

    2016-06-01

    Full Text Available The purpose of this research is to evaluate the fire-extinguishing performance of a compressed air foam system at different mixing ratios of pressurized air. In this system, compressed air is injected into an aqueous solution of foam and then discharged. The experimental device uses an exclusive fire-extinguishing technology with compressed air foam that is produced based on the Canada National Laboratory and UL (Underwriters Laboratories 162 standards, with a 20-unit oil fire model (Class B applied as the fire extinguisher. Compressed air is injected through the air mixture, and results with different air-to-aqueous solution foam ratios of 1:4, 1:7, and 1:10 are studied. In addition, comparison experiments between synthetic surfactant foam and a foam type which forms an aqueous film are carried out at an air-to-aqueous solution foam ratio of 1:4. From the experimental results, at identical discharging flows, it was found that the fire-extinguishing effect of the aqueous film-forming foam is greatest at an air-to-aqueous solution foam ratio of 1:7 and weakest at 1:10. Moreover, the fire-extinguishing effect of the aqueous film-forming foam in the comparison experiments between the aqueous film-forming foam and the synthetic surfactant foam is greatest.

  20. Facing slag glass and slag glass ceramic produced from thermal power plant ash

    Energy Technology Data Exchange (ETDEWEB)

    Buruchenko, A.E.; Kolesnikov, A.A.; Lukoyanov, A.G.

    1990-10-01

    Evaluates properties of fly ash and slags from the Krasnoyarsk coal-fired power plants and their utilization for glass and ceramic glass production. Composition of a mixture of fly ash and slag was: silica 40-55%, aluminium oxides 10-40%, ferric trioxide 6-14%, calcium oxides 20-35%, magnesium oxides 3-6%, potassium oxides 0.3-1.5%, sodium oxides 0.2-05%, sulfur trioxide 0.9-5.0%. The analyzed fly ash and slags from the Krasnoyarsk plant were an economic waste material for glass production. Properties of sand, clay and other materials used in glass production and properties of glass and ceramic glass produced on the basis of fly ash and slags are analyzed. Economic aspects of fly ash and slag utilization are also evaluated. 3 refs.

  1. Structural and interactional behaviour of aqueous mixture of room temperature ionic liquid; 2-hydroxyethyl-trimethylammonium L-lactate

    International Nuclear Information System (INIS)

    Chaudhary, Ganga Ram; Bansal, Shafila; Mehta, S.K.; Ahluwalia, A.S.

    2014-01-01

    Highlights: • Thermophysical and spectroscopic properties of aqueous mixtures 2-[HE3MA]LAC have been measured. • Effect of temperature on thermophysical properties has also been studied. • Stronger intermolecular have been observed between [HE3MA]LAC and H 2 O. • Magnitude of interactions decreases with the rise in temperature. • Spectroscopic studies shows interactions between -N + -(CH 3 ) 3 with -OH - group and COO − with -H + of IL and H 2 O. - Abstract: In order to understand the molecular interactions between the green solvent system, (water + lactate based ionic liquid); 2-hydroxyethyl-trimethylammonium L-lactate ([(C 2 H 4 OH)(CH 3 ) 3 N][Lactate]), the thermophysical properties viz. density ρ, speed of sound u, specific conductivity κ, refractive index n D and spectroscopic properties viz. IR, 1 H and 13 C NMR have been investigated over the whole composition range at atmospheric pressure with temperature varied from (293.15 to 323.15) K. To gain more insight of intermolecular interactions occurring in the aqueous mixture of [(C 2 H 4 OH)(CH 3 ) 3 N][Lactate], intermolecular free length L f , acoustic impedance Z, relative association R A , excess molar volume V E , deviations in isentropic compressibility ΔK S , partial molar excess volume V i E , partial molar deviations in isentropic compressibility ΔK S,i , deviation in specific conductivity Δκ and deviation in refractive index Δn D have been predicted as a function of IL concentration over the whole composition range. These results have been fitted to the Redlich–Kister polynomial. A large deviation from ideality has been observed on mixing water and [(C 2 H 4 OH)(CH 3 ) 3 N][Lactate] which are due to the formation of strong intermolecular hydrogen bonding between the two molecules. Also, it has been noticed that the mixture of water and [(C 2 H 4 OH)(CH 3 ) 3 N][Lactate] became warm that indicates mixing of these two components is exothermic. Thermodynamic and spectroscopic data

  2. Measurement of Solute Diffusion Behavior in Fractured Waste Glass Media

    International Nuclear Information System (INIS)

    Saripalli, Kanaka P.; Lindberg, Michael J.; Meyer, Philip D.

    2008-01-01

    Determination of aqueous phase diffusion coefficients of solutes through fractured media is essential for understanding and modeling contaminants transport at many hazardous waste disposal sites. No methods for earlier measurements are available for the characterization of diffusion in fractured glass blocks. We report here the use of time-lag diffusion experimental method to assess the diffusion behavior of three different solutes (Cs, Sr and Pentafluoro Benzoic Acid or PFBA) in fractured, immobilized low activity waste (ILAW) glass forms. A fractured media time-lag diffusion experimental apparatus that allows the measurement of diffusion coefficients has been designed and built for this purpose. Use of time-lag diffusion method, a considerably easier experimental method than the other available methods, was not previously demonstrated for measuring diffusion in any fractured media. Hydraulic conductivity, porosity and diffusion coefficients of a solute were experimentally measured in fractured glass blocks using this method for the first time. Results agree with the range of properties reported for similar rock media earlier, indicating that the time-lag experimental method can effectively characterize the diffusion coefficients of fractured ILAW glass media

  3. Fragility of superheated melts and glass-forming ability in Pr-based alloys

    International Nuclear Information System (INIS)

    Meng, Q.G.; Zhou, J.K.; Zheng, H.X.; Li, J.G.

    2006-01-01

    The kinetic viscosity (η) of superheated melts, thermal properties (T x , T m , T L ) and X-ray diffraction analysis on the Pr-based bulk metallic glasses (BMG) are reported and discussed. A new refined concept, the superheated fragility defined as M' = E S δ x /k B , has been developed based on common solidification theory and the Arrhenius equation. The interrelationship between this kind of fragility and the glass-forming ability (GFA) is elaborated on and evaluated in Pr-based BMG and Al-based amorphous ribbon alloys. Using viscosity data of superheated melts, it is shown, theoretically and experimentally, that the fragility parameter M' may be used as a GFA indicator for metallic alloys

  4. Low-temperature behaviour of the Kob-Andersen binary mixture

    International Nuclear Information System (INIS)

    Ashwin S S; Sastry, Srikanth

    2003-01-01

    The dynamical behaviours of glass-forming liquids have been analysed extensively via computer simulations of model liquids, among which the Kob-Andersen binary Lennard-Jones mixture has been a widely studied system. Typically, studies of this model have been restricted to temperatures above the mode coupling temperature. Preliminary results concerning the dynamics of the Kob-Andersen binary mixture are presented at temperatures that extend below the mode coupling temperature, along with properties of the local energy minima sampled. These results show that a crossover in the dynamics occurs alongside changes in the properties of the inherent structures sampled. Furthermore, a crossover is observed from non-Arrhenius behaviour of the diffusivity above the mode coupling temperature to Arrhenius behaviour at lower temperatures

  5. Structural disorder in metallic glass-forming liquids.

    Science.gov (United States)

    Pan, Shao-Peng; Feng, Shi-Dong; Wang, Li-Min; Qiao, Jun-Wei; Niu, Xiao-Feng; Dong, Bang-Shao; Wang, Wei-Min; Qin, Jing-Yu

    2016-06-09

    We investigated structural disorder by a new structural parameter, quasi-nearest atom (QNA), in atomistic configurations of eight metallic glass-forming systems generated through molecular dynamics simulations at various temperatures. Structural analysis reveals that the scaled distribution of the number of QNA appears to be an universal property of metallic liquids and the spatial distribution of the number of QNA displays to be clearly heterogeneous. Furthermore, the new parameter can be directly correlated with potential energy and structural relaxation at the atomic level. Some straightforward relationships between QNA and other properties (per-atom potential energy and α-relaxation time) are introduced to reflect structure-property relationship in metallic liquids. We believe that the new structural parameter can well reflect structure disorder in metallic liquids and play an important role in understanding various properties in metallic liquids.

  6. Removal of toxicity the pharmaceutical propranolol and your mixture with fluoxetine hydrochloride in aqueous solution using radiation with electron beam

    International Nuclear Information System (INIS)

    Boiani, Nathalia Fonseca

    2016-01-01

    Environmental health has been damage due to incorrect disposal of products and by-products. Among emerging pollutants it is possible to account with several pharmaceuticals, causing those problems when disposed in the environment by effluents. Conventional processing techniques are insufficient in removal of the pharmaceuticals, for having resistant waste and low biodegradability. Thus the advanced oxidation processes have been studied as an alternative for the treatment of different types of effluents. The objective of this study was to apply the process of irradiation with electron beam in order to reduce the toxic effects of propranolol, and the mixture with fluoxetine hydrochloride in aqueous solution. Ecotoxicological tests conducted with propranolol, and the mixture with fluoxetine hydrochloride, for Daphnia similis microcrustacean, and the Vibrio fischeri bacterium. It was observed that D. similis was more sensitive to propranolol drug and to the mixture, when compared to bacterium V.fischeri. After being subjected to the treatment with ionizing radiation, all applied doses to the propranolol and the mixture, showed significant reduction of toxicity, for D. similis. Different were the results for V. fischeri, when only 5.0 kGy reduced toxicity to propranolol. The mixture of pharmaceuticals required 2.5 and 5.0 kGy for reducing toxicity. 5.0 kGy showed the best removal efficiency for toxicity: 79.94 % for D. similis and 15.64 % for V. fischeri, when exposed to propranolol. The mixture reduction efficacy were 81.59% and 26.93 % for D.similis and V.fischeri, respectively. (author)

  7. Application of Neem Gum for Aqueous Film Coating of Ciprofloxacin Tablets

    OpenAIRE

    A P Kulkarni; Y R Shaikh; MH GR Dehghan

    2013-01-01

    Summary. At present the pharmaceutical industry and academia are focusing on the use of natural materials and resources for development of pharmaceutical product. In previous study, neem gum (NG), obtained from Azadirachata indica plant revealed satisfactory film forming ability. The present study evaluates the application potential of neem gum, as an aqueous film coating material, using ciprofloxacin hydrchloride (drug) as a model drug. Initial study of physical mixture indicated absence of ...

  8. Electron spin-lattice relaxation mechanisms of radiation produced trapped electrons and hydrogen atoms in aqueous and organic glassy matrices. Modulation of electron nuclear dipolar interaction by tunnelling modes in a glassy matrix. [. gamma. rays

    Energy Technology Data Exchange (ETDEWEB)

    Bowman, M K; Kevan, L [Wayne State Univ., Detroit, Mich. (USA). Dept. of Chemistry

    1977-01-01

    The spin lattice relaxation of trapped electrons in aqueous and organic glasses and trapped hydrogen atoms in phosphoric acid glass has been directly studied as a function of temperature by the saturation recovery method. Below 50 to 100 K, the major spin lattice relaxation mechanism involves modulation of the electron nuclear dipolar (END) interaction with nuclei in the radical's environment by tunnelling of those nuclei between two or more positions. This relaxation mechanism occurs with high efficiency and has a characteristic linear temperature dependence. The tunnelling nuclei around trapped electrons do not seem to involve the nearest neighbor nuclei which are oriented by the electron in the process of solvation. Instead the tunnelling nuclei typically appear to be next nearest neighbors to the trapped electron. The identities of the tunnelling nuclei have been deduced by isotopic substitution and are attributed to: Na in 10 mol dm/sup -3/ NaOH aqueous glass, ethyl protons in ethanol glass, methyl protons in methanol glass and methyl protons in MTHF glass. For trapped hydrogen atoms in phosphoric acid, the phosphorus nuclei appear to be the effective tunnelling nuclei. Below approximately 10 K the spin lattice relaxation is dominated by a temperature independent cross relaxation term for H atoms in phosphoric acid glass and for electrons in 10 mol dm/sup -3/ NaOH aqueous glass, but not for electrons in organic glasses. This is compared with recent electron-electron double resonance studies of cross relaxation in these glasses. The spin lattice relaxation of O/sup -/ formed in 10 mol dm/sup -3/ NaOH aqueous glass was also studied and found to be mainly dominated by a Raman process with an effective Debye temperature of about 100 K.

  9. Using 20-million-year-old amber to test the super-Arrhenius behaviour of glass-forming systems

    Science.gov (United States)

    Zhao, Jing; Simon, Sindee L.; McKenna, Gregory B.

    2013-04-01

    Fossil amber offers the opportunity to investigate the dynamics of glass-forming materials far below the nominal glass transition temperature. This is important in the context of classical theory, as well as some new theories that challenge the idea of an ‘ideal’ glass transition. Here we report results from calorimetric and stress relaxation experiments using a 20-million-year-old Dominican amber. By performing the stress relaxation experiments in a step-wise fashion, we measured the relaxation time at each temperature and, above the fictive temperature of this 20-million-year-old glass, this is an upper bound to the equilibrium relaxation time. The results deviate dramatically from the expectation of classical theory and are consistent with some modern ideas, in which the diverging timescale signature of complex fluids disappears below the glass transition temperature.

  10. Beyond packing of hard spheres: The effects of core softness, non-additivity, intermediate-range repulsion, and many-body interactions on the glass-forming ability of bulk metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai; Fan, Meng; Liu, Yanhui; Schroers, Jan [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Center for Research on Interface Structures and Phenomena, Yale University, New Haven, Connecticut 06520 (United States); Shattuck, Mark D. [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Department of Physics and Benjamin Levich Institute, The City College of the City University of New York, New York, New York 10031 (United States); O’Hern, Corey S. [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Center for Research on Interface Structures and Phenomena, Yale University, New Haven, Connecticut 06520 (United States); Department of Physics, Yale University, New Haven, Connecticut 06520 (United States); Department of Applied Physics, Yale University, New Haven, Connecticut 06520 (United States)

    2015-11-14

    When a liquid is cooled well below its melting temperature at a rate that exceeds the critical cooling rate R{sub c}, the crystalline state is bypassed and a metastable, amorphous glassy state forms instead. R{sub c} (or the corresponding critical casting thickness d{sub c}) characterizes the glass-forming ability (GFA) of each material. While silica is an excellent glass-former with small R{sub c} < 10{sup −2} K/s, pure metals and most alloys are typically poor glass-formers with large R{sub c} > 10{sup 10} K/s. Only in the past thirty years have bulk metallic glasses (BMGs) been identified with R{sub c} approaching that for silica. Recent simulations have shown that simple, hard-sphere models are able to identify the atomic size ratio and number fraction regime where BMGs exist with critical cooling rates more than 13 orders of magnitude smaller than those for pure metals. However, there are a number of other features of interatomic potentials beyond hard-core interactions. How do these other features affect the glass-forming ability of BMGs? In this manuscript, we perform molecular dynamics simulations to determine how variations in the softness and non-additivity of the repulsive core and form of the interatomic pair potential at intermediate distances affect the GFA of binary alloys. These variations in the interatomic pair potential allow us to introduce geometric frustration and change the crystal phases that compete with glass formation. We also investigate the effect of tuning the strength of the many-body interactions from zero to the full embedded atom model on the GFA for pure metals. We then employ the full embedded atom model for binary BMGs and show that hard-core interactions play the dominant role in setting the GFA of alloys, while other features of the interatomic potential only change the GFA by one to two orders of magnitude. Despite their perturbative effect, understanding the detailed form of the intermetallic potential is important for

  11. Preparation of SnO_2-Glass Composite Containing Cu Particles Reduced from Copper Ions in Glass Matrix : Effect of Glass Particle Size on Microstructure and Electrical Property

    OpenAIRE

    Haruhisa, SHIOMI; Kaori, UMEHARA; Faculty of Engineering and Design, Kyoto Institute of Technology; Faculty of Engineering and Design, Kyoto Institute of Technology

    2000-01-01

    An attempt was made to improve the electrical properties of SnO_2-glass composites by dispersing Cu particles with low resistivity and positive temperature coefficient of resistance(TCR)in the glass matrix. Cu metal particles were precipitated by reducing Cu_2O previously dissolved into the matrix glass by adding LaB_6 as a reducing agent. The effect of the glass particle size, which influences the homogeneity of LaB_6 dispersion in the powder mixture before firing, on the Cu precipitation in...

  12. Operating Range for High Temperature Borosilicate Waste Glasses: (Simulated Hanford Enveloped)

    International Nuclear Information System (INIS)

    Mohammad, J.; Ramsey, W. G.; Toghiani, R. K.

    2003-01-01

    The following results are a part of an independent thesis study conducted at Diagnostic Instrumentation and Analysis Laboratory-Mississippi State University. A series of small-scale borosilicate glass melts from high-level waste simulant were produced with waste loadings ranging from 20% to 55% (by mass). Crushed glass was allowed to react in an aqueous environment under static conditions for 7 days. The data obtained from the chemical analysis of the leachate solutions were used to test the durability of the resulting glasses. Studies were performed to determine the qualitative effects of increasing the B2O3 content on the overall waste glass leaching behavior. Structural changes in a glass arising due to B2O3 were detected indirectly by its chemical durability, which is a strong function of composition and structure. Modeling was performed to predict glass durability quantitatively in an aqueous environment as a direct function of oxide composition

  13. PREPARATION OF ZEOLITE X COATINGS ON SODA-LIME TYPE GLASS PLATES

    Directory of Open Access Journals (Sweden)

    M. Tatlier

    Full Text Available Abstract The dissolution of glass in highly alkaline reaction mixtures and the impact of this phenomenon on zeolite coating formation were investigated. Coating samples were prepared and characterized by X-ray diffraction (XRD, field emission gun scanning electron microscopy (FEGSEM and thermogravimetry (TG. It was demonstrated that zeolite X coatings might be prepared on soda-lime glass. Glass dissolved to some degree, up to 2% of its original mass, in the reaction mixtures for the conditions investigated. This dissolution affected the zeolite synthesis taking place on the glass surface, resulting in phases different from those obtained on inert metal surfaces in some cases, especially for the use of reaction mixtures with relatively high Si/Al ratios. The percentage of dissolution of glass plates increased with their decreasing thickness, indicating a surface phenomenon for the dissolution. The stabilities of the coatings, which varied with the synthesis conditions, benefited from the addition of extra thin layers of polyacrylic acid.

  14. Exploring the Origin of Fragile-to-Strong Transition in Some Glass-Forming Liquids

    DEFF Research Database (Denmark)

    Yue, Yuanzheng; Hu, L. N.

    2014-01-01

    , topological and thermodynamic changes causing this transition. The theory for describing the transition has not been fully established. In this paper, we summarize our current understanding of the fragile-to-strong transition in some glass-forming liquids basedon our two published papers and recent...

  15. Fabrication of Radiation Shielding Glass

    International Nuclear Information System (INIS)

    Tavichai, Nattaya; Pormsean, Suriyont; Dararutana, Pisutti; Sirikulrat, Narin

    2003-06-01

    In this work, lead glass doped with 50%, 55%,60%, 65%, and 70% w/w Pb 3 O 4 . After that, glass mixtures were melt at 1,250οC with 4 hours soaking time. Molten glass was shaped by mould casting technique then annealed at 700οC and cooled down to room temperature. It was found that the glass with 60%w/w Pb 3 O 4 show maximum absorption coefficient of about 0.383 cm -1 with I-131 at energy 364 keV. The observed refractive indices of the samples range between 1.5908 to 1.5922

  16. Controlling the Release of Indomethacin from Glass Solutions Layered with a Rate Controlling Membrane Using Fluid-Bed Processing. Part 1: Surface and Cross-Sectional Chemical Analysis.

    Science.gov (United States)

    Dereymaker, Aswin; Scurr, David J; Steer, Elisabeth D; Roberts, Clive J; Van den Mooter, Guy

    2017-04-03

    Fluid bed coating has been shown to be a suitable manufacturing technique to formulate poorly soluble drugs in glass solutions. Layering inert carriers with a drug-polymer mixture enables these beads to be immediately filled into capsules, thus avoiding additional, potentially destabilizing, downstream processing. In this study, fluid bed coating is proposed for the production of controlled release dosage forms of glass solutions by applying a second, rate controlling membrane on top of the glass solution. Adding a second coating layer adds to the physical and chemical complexity of the drug delivery system, so a thorough understanding of the physical structure and phase behavior of the different coating layers is needed. This study aimed to investigate the surface and cross-sectional characteristics (employing scanning electron microscopy (SEM) and time of flight secondary ion mass spectrometry (ToF-SIMS)) of an indomethacin-polyvinylpyrrolidone (PVP) glass solution, top-coated with a release rate controlling membrane consisting of either ethyl cellulose or Eudragit RL. The implications of the addition of a pore former (PVP) and the coating medium (ethanol or water) were also considered. In addition, polymer miscibility and the phase analysis of the underlying glass solution were investigated. Significant differences in surface and cross-sectional topography of the different rate controlling membranes or the way they are applied (solution vs dispersion) were observed. These observations can be linked to the polymer miscibility differences. The presence of PVP was observed in all rate controlling membranes, even if it is not part of the coating solution. This could be attributed to residual powder presence in the coating chamber. The distribution of PVP among the sample surfaces depends on the concentration and the rate controlling polymer used. Differences can again be linked to polymer miscibility. Finally, it was shown that the underlying glass solution layer

  17. Aqueous corrosion of borosilicate glasses: experiments, modeling and Monte-Carlo simulations

    International Nuclear Information System (INIS)

    Ledieu, A.

    2004-10-01

    This work is concerned with the corrosion of borosilicate glasses with variable oxide contents. The originality of this study is the complementary use of experiments and numerical simulations. This study is expected to contribute to a better understanding of the corrosion of nuclear waste confinement glasses. First, the corrosion of glasses containing only silicon, boron and sodium oxides has been studied. The kinetics of leaching show that the rate of leaching and the final degree of corrosion sharply depend on the boron content through a percolation mechanism. For some glass contents and some conditions of leaching, the layer which appears at the glass surface stops the release of soluble species (boron and sodium). This altered layer (also called the gel layer) has been characterized with nuclear magnetic resonance (NMR) and small angle X-ray scattering (SAXS) techniques. Second, additional elements have been included in the glass composition. It appears that calcium, zirconium or aluminum oxides strongly modify the final degree of corrosion so that the percolation properties of the boron sub-network is no more a sufficient explanation to account for the behavior of these glasses. Meanwhile, we have developed a theoretical model, based on the dissolution and the reprecipitation of the silicon. Kinetic Monte Carlo simulations have been used in order to test several concepts such as the boron percolation, the local reactivity of weakly soluble elements and the restructuring of the gel layer. This model has been fully validated by comparison with the results on the three oxide glasses. Then, it has been used as a comprehensive tool to investigate the paradoxical behavior of the aluminum and zirconium glasses: although these elements slow down the corrosion kinetics, they lead to a deeper final degree of corrosion. The main contribution of this work is that the final degree of corrosion of borosilicate glasses results from the competition of two opposite mechanisms

  18. Reference document on the long life behavior of nuclear glasses

    International Nuclear Information System (INIS)

    Godon, N.

    2004-01-01

    This document exposes the scientific analysis of the operational modelizations concerning the behavior of glasses (C wastes) for the long time storage and for the retrieval or ultimate underground disposal. The scientific approach adopted to establish the behavior of glasses uses a methodology, a strategy and defined approaches, described in this document. The containment glasses specifications, the glass behavior dry or in non saturated open environment, the glass behavior in aqueous environment, predictions models of glasses alteration and elements of validation are also presented. (A.L.B.)

  19. Long-term stability of high-level waste forms

    International Nuclear Information System (INIS)

    Vernaz, E.; Loida, A.; Malow, G.; Marples, J.A.C.; Matzke, H.J.

    1990-01-01

    The long-term stability of HLW forms is reviewed with regard to temperature, irradiation and aqueous corrosion in a geological environment. The paper focuses on borosilicate glasses, but the radiation stability results are compared with some HLW ceramics. Thermal stability: most nuclear waste glass compositions have been adjusted to ensure a low final crystallized fraction. The crystallization of highly active Pamela glass samples was similar to that of nonradioactive glass. Radiation stability: No adverse effect of irradiation damage was found in glasses doped with short-lived actinides: volume changes were small, no significant change in the leach rate was observed, and the fracture toughness increased. For most ceramics investigated, volume changes of up to 9%, amorphization and higher leach rates were observed as a consequence of high α decay doses. For the KAB 78 ceramic, however, none of these effects were detected since the matrix was not subject to α recoil damage. Chemical stability: It has been demonstrated that alteration by water depends largely on the repository conditions. Most clay act as silica sinks, and increase the glass corrosion rate. It is possible, however, to specify realistic temperature, pressure and environmental conditions to ensure glass integrity for more than 10 000 years

  20. Solid-state characterization of paracetamol metastable polymorphs formed in binary mixtures with hydroxypropylmethylcellulose

    International Nuclear Information System (INIS)

    Rossi, Alessandra; Savioli, Alessandra; Bini, Marcella; Capsoni, Doretta; Massarotti, Vincenzo; Bettini, Ruggero; Gazzaniga, Andrea; Sangalli, Maria Edvige; Giordano, Ferdinando

    2003-01-01

    Two metastable polymorphs of paracetamol (forms II and III) were prepared by appropriate thermal methods from binary mixtures containing 10% (w/w) of hydroxypropylmethylcellulose. By controlling the reheating step, it was possible to address the recrystallization of the drug either into form II or III. Moreover, it was observed that form III transforms either into form II or I depending on the preparation method. The physical characterization of the polymorphs was performed by means of micro-Fourier transform infrared spectroscopy (MFTIR) and powder X-ray diffractometry (PXRD), both temperature controlled

  1. Solid-state characterization of paracetamol metastable polymorphs formed in binary mixtures with hydroxypropylmethylcellulose

    Energy Technology Data Exchange (ETDEWEB)

    Rossi, Alessandra; Savioli, Alessandra; Bini, Marcella; Capsoni, Doretta; Massarotti, Vincenzo; Bettini, Ruggero; Gazzaniga, Andrea; Sangalli, Maria Edvige; Giordano, Ferdinando

    2003-11-28

    Two metastable polymorphs of paracetamol (forms II and III) were prepared by appropriate thermal methods from binary mixtures containing 10% (w/w) of hydroxypropylmethylcellulose. By controlling the reheating step, it was possible to address the recrystallization of the drug either into form II or III. Moreover, it was observed that form III transforms either into form II or I depending on the preparation method. The physical characterization of the polymorphs was performed by means of micro-Fourier transform infrared spectroscopy (MFTIR) and powder X-ray diffractometry (PXRD), both temperature controlled.

  2. Chemical behaviors of tritium formed in a LiF-BeF2 mixture and its removal from a molten mixture

    International Nuclear Information System (INIS)

    Oishi, J.; Moriyama, H.; Maeda, S.; Ohmura, T.; Moritani, K.

    1987-01-01

    Chemical behaviors of tritium formed in a LiF-BeF 2 mixture were studied using a radiometric method. Most of tritium was found to be present in the T + and T - states under no thermal treatment. The distribution of tritium in chemical states was explained by considering hot atom reactions and radiation chemical reactions. Tritium behaviors in a molten LiF-BeF 2 mixture were also studied at 873 K. In the presence of hydrogen, the isotopic exchange reaction which is TF + H 2 → HT + HF was observed to occur probably in the salt phase. The removal of tritium in a molten LiF-BeF 2 mixture was tried by sparging a gas in a melt for tritium purge, and the effects of the composition of purge gas and of the construction material of crucibles containing the melt on the removal rate were observed. (author)

  3. UV–vis spectroscopic study of room temperature ionic liquid–water mixtures: N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate

    International Nuclear Information System (INIS)

    Aono, Masami; Imai, Yusuke; Abe, Hiroshi; Matsumoto, Hitoshi; Yoshimura, Yukihiro

    2012-01-01

    Highlights: ► Number of absorption peaks in [DEME][BF 4 ]-H 2 O depends on H 2 O concentrations. ► At 90–96 mol% H 2 O, low optical transmittance shows on UV-visible region. ► Relatively soft glass appears only 90–96 mol% region by slow cooling. - Abstract: N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate, [DEME][BF 4 ], and H 2 O mixtures were investigated in optical properties by UV–visible spectroscopy. The concentration region of H 2 O in the mixtures was 0–100 mol%. At room temperature, the mixtures of H 2 O exhibit absorption peaks at around 280 nm and 750 nm, which depend on H 2 O concentrations. At 90–95 mol% H 2 O, the optical transmittance decreased over the whole region of UV–visible light. In X-ray diffraction, correlation over the medium-range such as network-forming materials develops at 90–95 mol%. Also, in quenched glass, low glass transition temperature appeared at these H 2 O concentrations. The specific glass is induced by different molecular aggregation in liquid. Therefore, an optical anomaly is connected with the specific water network over the medium-range order.

  4. Calorimetric study of water's two glass transitions in the presence of LiCl

    Science.gov (United States)

    Ruiz, Guadalupe N.; Amann-Winkel, Katrin; Bove, Livia E.; Corti, Horacio R.

    2018-01-01

    A DSC study of dilute glassy LiCl aqueous solutions in the water-dominated regime provides direct evidence of a glass-to-liquid transition in expanded high density amorphous (eHDA)-type solutions. Similarly, low density amorphous ice (LDA) exhibits a glass transition prior to crystallization to ice Ic. Both glass transition temperatures are independent of the salt concentration, whereas the magnitude of the heat capacity increase differs. By contrast to pure water, the glass transition endpoint for LDA can be accessed in LiCl aqueous solutions above 0.01 mole fraction. Furthermore, we also reveal the endpoint for HDA's glass transition, solving the question on the width of both glass transitions. This suggests that both equilibrated HDL and LDL can be accessed in dilute LiCl solutions, supporting the liquid–liquid transition scenario to understand water's anomalies. PMID:29442107

  5. Probing the limit of magnesium uptake by β-tricalcium phosphate in biphasic mixtures formed from calcium deficient apatites

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, P. Nandha; Mishra, Sandeep K.; Kannan, S., E-mail: para_kanna@yahoo.com

    2015-11-15

    A series of magnesium doped non-stoichiometric calcium deficient apatites were synthesized through an aqueous precipitation route. The resultant structural changes during heat treatment were investigated by X-ray diffraction, Raman and FT-IR spectroscopy and Rietveld refinement. The results confirmed the formation of biphasic mixtures comprising Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} and β-Ca{sub 3}(PO{sub 4}){sub 2} after heat treatment at 1000 °C with the preferential occupancy of Mg{sup 2+} at the crystal lattice of β-Ca{sub 3}(PO{sub 4}){sub 2}. The concentration of Mg{sup 2+} uptake in β-Ca{sub 3}(PO{sub 4}){sub 2} is limited till reaching the stoichiometric ratio of (Ca+Mg)/P=1.67 and beyond this stoichiometric value [(Ca+Mg)/P>1.67], Mg{sup 2+} precipitates as Mg(OH){sub 2} and thereafter gets converted to MgO during heat treatment. Any kind of Mg{sup 2+} uptake in the crystal lattice of Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} is discarded from the investigation. - Highlights: • Aqueous co-precipitation of calcium deficient apatites with excess magnesium (Mg{sup 2+}) additions. • Heat treatments beyond 800 °C results in the formation of biphasic apatite mixtures. • Mg{sup 2+} gets accommodated at the β-Ca{sub 3}(PO{sub 4}){sub 2} lattice of biphasic mixtures. • Mg{sup 2+} additions exceeding stoichiometric value (Ca/P>1.67) results in its formation as MgO. • Mg{sup 2+} occupancy at β-Ca{sub 3}(PO{sub 4}){sub 2} lattice delays its allotropic conversion α-Ca{sub 3}(PO{sub 4}){sub 2} till 1350 °C.

  6. Vertical sorting in bed forms - flume experiments with a natural and a tri-modal sediment mixture

    NARCIS (Netherlands)

    Blom, Astrid; Ribberink, Jan S.; de Vriend, Huib J.

    2003-01-01

    Two sets of flume experiments were conducted to examine grain size selective transport and vertical sorting in conditions with migrating bed forms and bed load transport. In the two sets of experiments we used a sediment mixture from the river Rhine and a trimodal mixture, respectively. The vertical

  7. Therapeutic effect of aqueous extracts of three dietary spices and their mixture on lipid metabolism and oxidative stress in a rat model of chronic alcohol consumption.

    Science.gov (United States)

    Otunola, Gloria Aderonke; Afolayan, Anthony Jide

    2016-07-01

    The protective effect of aqueous extracts of three dietary spices, garlic, (Allium sativum), ginger (Zingiber officinale) and pepper (Capsicum frutescens) singly and combined was investigated using a rat model of chronic alcohol intake. Rats were given 30% ethanol, with or without aqueous extracts of garlic, ginger, pepper or mixture of the three administered at 200mg/kg body weight by oral gavage for 28 days. Lipid profile, lipid peroxidation, oxidative and antioxidative profiles of serum, faecal, liver, kidney, heart and brain tissues of the rats were analyzed. Alcohol treatment significantly elevated liver enzymes, lipid peroxidation, depleted antioxidant system and induced histopathological changes in the liver. These alterations were markedly ameliorated by treatment with aqueous extracts of the three spices singly or mixed at 200mg/kg body weight. These results suggest that aqueous extracts of garlic, ginger, pepper or a blend of the three protects against alcohol- induced hypercholesterolemia, lipid peroxidation, oxidative stress and liver damage.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-12-31

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

  9. Low temperature irradiation of vitrifiable mixtures of unsaturated monomers

    International Nuclear Information System (INIS)

    Kaetsu, I.; Ito, A.; Hayashi, K.

    1975-01-01

    A specific mixture containing at least one polymerizable unsaturated monomer which is not vitrifiable by itself can advantageously be polymerized by irradiating the mixture at a temperature not higher than 100 0 C above glass transition temperature of the mixture with an ionizing radiation and/or a light. 12 claims, 6 drawings, figures

  10. A Method to Produce Foam Glasses

    DEFF Research Database (Denmark)

    2016-01-01

    The present invention relates to a production process of foam glass from a mixture of glass cullet or slag or fly ash with a foaming agent and an oxidizing agent and heating to below 1100 C under low oxygen atmosphere. The invention relates more particularly to a process wherein pure carbon or a ...

  11. Fatigue crack initiation in hybrid boron/glass/aluminum fiber metal laminates

    International Nuclear Information System (INIS)

    Chang, P.-Y.; Yeh, P.-C.; Yang, J.-M.

    2008-01-01

    The fatigue crack initiation behavior of a high modulus and hybrid boron/glass/aluminum fiber/metal laminate (FML) was investigated experimentally and analytically. Two types of hybrid boron/glass/aluminum FMLs were fabricated and studied, which consisted of aluminum alloy sheets as the metal layers and a mixture of boron fibers and glass fibers as the composite layers. For the first type, the boron fiber/prepreg and the glass fiber/prepreg were used separately in the composite layers, and for the second type, the boron fibers and the glass fibers were mingled together to form a hybrid boron/glass/prepreg composite layer. These hybrid FMLs were consolidated using an autoclave curing process. The incorporation of the boron fibers improved the Young's modulus of the composite layer in FMLs, which in turn, would improve the fatigue crack initiation life of the Al sheet. The experimental results clearly showed that the fatigue crack initiation lives for both types of hybrid boron/glass/aluminum FMLs were superior to the monolithic aluminum alloy under the same loading condition. An analytical approach was proposed to calculate the fatigue crack initiation lives of hybrid boron/glass/aluminum FMLs based on the classical laminate theory and the small-crack theory. A good correlation was obtained between the predictions and the experimental results

  12. Glass forming ability of amorphous drugs investigated by continuous cooling- and isothermal transformation

    DEFF Research Database (Denmark)

    Blaabjerg, Lasse Ingerslev; Lindenberg, Eleanor; Löbmann, Korbinian

    2016-01-01

    /min). Thus, the glass forming ability can be predicted by the use of TTT diagrams. In contrast to TTT diagrams, CCT diagrams may not be suitable for small organic molecules due to poor separation of exothermic events, which makes it difficult to determine the zone of recrystallization. In conclusion...

  13. Structural evolution during fragile-to-strong transition in CuZr(Al) glass-forming liquids

    DEFF Research Database (Denmark)

    Zhou, C.; Hu, L.N.; Sun, Q.J.

    2015-01-01

    In the present work, we show experimental evidence for the dynamic fragile-to-strong (F-S) transition in a series of CuZr(Al) glass-forming liquids (GFLs). A detailed analysis of the dynamics of 98 glass-forming liquids indicates that the F-S transition occurs around Tf-s ≈ 1.36 Tg. Using...... the hyperquenching-annealing-x-ray scattering approach, we have observed a three-stage evolution pattern of medium-range ordering (MRO) structures during the F-S transition, indicating a dramatic change of the MRO clusters around Tf-s upon cooling. The F-S transition in CuZr(Al) GFLs is attributed to the competition...... among the MRO clusters composed of different locally ordering configurations. A phenomenological scenario has been proposed to explain the structural evolution from the fragile to the strong phase in the CuZr(Al) GFLs....

  14. Predictions of glass transition temperature for hydrogen bonding biomaterials.

    Science.gov (United States)

    van der Sman, R G M

    2013-12-19

    We show that the glass transition of a multitude of mixtures containing hydrogen bonding materials correlates strongly with the effective number of hydroxyl groups per molecule, which are available for intermolecular hydrogen bonding. This correlation is in compliance with the topological constraint theory, wherein the intermolecular hydrogen bonds constrain the mobility of the hydrogen bonded network. The finding that the glass transition relates to hydrogen bonding rather than free volume agrees with our recent finding that there is little difference in free volume among carbohydrates and polysaccharides. For binary and ternary mixtures of sugars, polyols, or biopolymers with water, our correlation states that the glass transition temperature is linear with the inverse of the number of effective hydroxyl groups per molecule. Only for dry biopolymer/sugar or sugar/polyol mixtures do we find deviations due to nonideal mixing, imposed by microheterogeneity.

  15. Partitioning of the rare earths and actinides between R7T7 nuclear glass alteration products and solution according to disposal conditions

    International Nuclear Information System (INIS)

    Menard, O.

    1995-01-01

    The alteration of nuclear glass by water is liable to release radionuclides into the environment. Determining the release kinetics of these elements and their aqueous chemical forms are therefore essential steps in establishing the safety of a geological repository site. Leach tests were conducted with a nonradioactive specimen of the French ''R7T7'' light water containment glass spiked with U and Th, and with two R7T7 specimens spiked with 237 Np and 239 Pu, respectively. The alteration solution compositions were representative of deep groundwater and contained carbonate, sulfate, phosphate, fluorine and chlorine ions. The release of U, Th, Np and Pu, as well as of the rare earths La, Ce and Nd were monitored by ICP mass spectrometry and by α spectrometry. Scanning and transmission electron microscopic examination of the nonradioactive altered glass surfaces was also performed to assess the partitioning balance for the rare earths, U and Th between the glass alteration products and solution. The mobility of these elements depends on two competing mechanisms. The rare earths and thorium are incorporated in the alteration products (gel); the retention process is assumed to involve chemisorption or coprecipitation, enhanced in the gel layer by the presence of phosphate ions in particular. Conversely, the aqueous species in the alteration solutions (mainly anions) form complexes with the actinides and rare earths; this phenomenon is particularly evident with U and Np. The presence of carbonate ions favors this mobility. Plutonium differs from U and Np in that it is adsorbed mainly on colloids formed by glass dissolution, the principal factors governing its chemical evolution in solution. (author). refs., 122 figs., 185 tabs

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

    International Nuclear Information System (INIS)

    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

  17. Phenomenological description of internal friction spectra in glass-forming and glassy systems

    International Nuclear Information System (INIS)

    Lomovskij, V.A.

    1999-01-01

    Dissipative events in different by chemical nature glass-forming systems, including B 2 O 3 , are studied. It is established from the spectra of internal friction of these systems that the maxima of the energy dissipation of the external power impact are positioned both in the area of viscous flow metastable structural liquid state and in the area of solid elastic state

  18. Hydrothermal reaction of albite and a sodium aluminosilicate glass: A solid-state NMR study

    Science.gov (United States)

    Yang, Wang-hong Alex; Kirkpatrick, R. James

    1989-04-01

    We present here a solid-state NMR study of the structure and chemical composition of the products and mechanisms of the reaction of crystalline low albite and a glass of nearly albite composition with aqueous solutions of pH from 1 to 11 at 250°C. For the crystalline albite, there are no detectable bulk or surface structural changes due to aqueous attack, consistent with the idea that both cation exchange and disruption of the aluminosilicate framework occur only near the mineral/solution interface and that the hydrated surface layer, if it exists, is not more than about 30 Å thick. This reaction occurs by solution/reprecipitation, and its rate decreases with increasing solution pH, supporting the idea that the dissolution of feldspar is initiated by cation-exchange. For the glass, the reaction proceeds by cation exchange of protons for Na +, incorporation of molecular water into the bulk glass, and a small amount of depolymerization of the aluminosilicate framework in the interior of the glass. Cation exchange becomes less important with increasing solution pH. The incorporation of molecular water and cation-exchange cause structural changes in the glass via solidstate adjustment without dissolution/reprecipitation. The large cations in the hydrated glass (Na and K) probably have a shell of water molecules around them, with a maximum average coordination number of six. The secondary phases formed from both albite and the glass are often amorphous and can be well characterized by NMR. The compositional and structural variations of the amorphous phases are important factors in these reactions and cannot be ignored in theoretical models of aluminosilicate dissolution. As expected, the aluminum coordination in the secondary phases changes from six-fold to four-fold as the solution pH increases.

  19. Inelastic neutron scattering from glass formers

    International Nuclear Information System (INIS)

    Buchenau, U.

    1997-01-01

    Neutron spectra below and above the glass transition temperature show a pronounced difference between strong and fragile glass formers in Angell's fragility scheme. The strong anharmonic increase of the inelastic scattering with increasing temperature in fragile substances is absent in the strongest glass former SiO 2 . That difference is reflected in the temperature dependence of Brillouin sound velocities above the glass transition. Coherent inelastic neutron scattering data indicate a mixture of sound waves and local modes at the low frequency boson peak. A relation between the fragility and the temperature dependence of the transverse hypersound velocity at the glass temperature is derived. (author)

  20. Solvatochromism of naringenin in aqueous alcoholic mixtures

    Directory of Open Access Journals (Sweden)

    Faraji Mohammad

    2016-01-01

    Full Text Available The spectral change of naringenin was studied by Uv-vis spectrophotometric method in binary mixtures of water with methanol, ethanol and 1-propanol at 25°C. The effect of solvent was investigated by analysis of electron transition energy at the maximum absorption wavelength as a function of Kamlet and Taft parameters of mixtures by means of linear solvation energy relationships. The nonlinear response of solvatochromism was explained based on solute-solvent and solvent-solvent interactions. The possible preferential solvation of naringenin by each of solvents was studied through a modified preferential solvation model which considers the hydrogen bonding interactions between the prior solvents due to solvent-solvent interactions. The preferential solvation parameters and local mole fraction distribution around the solute were calculated. Results indicate that naringenin prefers to be more solvated by the complex solvating species and organic solvents than water.

  1. Mineralogical textural and compositional data on the alteration of basaltic glass from Kilauea, Hawaii to 300 degrees C: Insights to the corrosion of a borosilicate glass waste-form

    International Nuclear Information System (INIS)

    Smith, D.K.

    1990-01-01

    Mineralogical, textural and compositional data accompanying greenschist facies metamorphism (to 300 degrees C) of basalts of the East Rift Zone (ERZ), Kilauea, Hawaii may be evaluated relative to published and experimental results for the surface corrosion of borosilicate glass. The ERZ alteration sequence is dominated by intermittent palagonite, interlayered smectite-chlorite, chlorite, and actinolite-epidote-anhydrite. Alteration is best developed in fractures and vesicles where surface reaction layers root on the glass matrix forming rinds in excess of 100 microns thick. Fractures control fluid circulation and the alteration sequence. Proximal to the glass surface, palagonite, Fe-Ti oxides and clays replace fresh glass as the surface reaction layer migrates inwards; away from the surface, amphibole, anhydrite, quartz and calcite crystallize from hydrothermal fluids in contact with the glass. The texture and composition of basaltic glass surfaces are similar to those of a SRL-165 glass leached statically for sixty days at 150 degrees C. While the ERZ reservoir is a complex open system, conservative comparisons between the alteration of ERZ and synthetic borosilicate glass are warranted. 31 refs., 2 figs

  2. Infrared and x-ray photoelectron spectroscopic studies on sodium borosilicate glass interacted with thermally oxidized aluminides formed on alloy 690

    International Nuclear Information System (INIS)

    Yusufali, C.; Dutta, R.S.; Dey, G.K.; Kshirsagar, R.J.; Jagannath; Mishra, R.K.

    2012-01-01

    Thermally oxidized aluminides formed on Ni-Cr-Fe based superalloy 690 substrates were subjected to interaction with sodium borosilicate melt (used as matrices for immobilization of high-level radioactive liquid waste) at 1248 K for 192 hours. After the interaction, Fourier-transform infrared (FT-IR) spectroscopy analysis of glass samples indicated the incorporation of Al in the glass network. X-ray photoelectron spectroscopy (XPS) of glass specimens revealed modified glass structure. (author)

  3. Insight on the glass-forming ability of Al–Y–Ni–Ce bulk metallic glass

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Shih-Fan, E-mail: sfchen@ntut.edu.tw [Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei 106, Taiwan (China); Chen, Chih-Yuan, E-mail: chen6563@gmail.com [Department of Energy Engineering, National United University, Miaoli 36003, Taiwan (China); Lin, Chia-Hung [Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei 106, Taiwan (China)

    2015-07-15

    Highlights: • Adding 1 at.% cerium to Al{sub 87}Y{sub 8}Ni{sub 5} alloy causes glass transition. • A large ΔT{sub x} indicates that (Al{sub 87}Y{sub 8}Ni{sub 5}){sub 99}Ce{sub 1} is possibly a ductile amorphous alloy. • Ce is effective in improving the thermal stability of the Al–Y–Ni amorphous alloy. • The hardness of the crystallized cerium-bearing alloy was as high as 593 Hv. - Abstract: In the present study, the role of Ce in the thermal stability and glass forming ability (GFA) of (Al{sub 87}Y{sub 8}Ni{sub 5}){sub 99}Ce{sub 1} alloy ribbons produced by a single roller melt-spinning process has been investigated in an attempt to understand the influences of multiple RE elements in an Al–TM–RE (TM: transition metal, RE: rear earth metal) alloy system. Only the (Al{sub 87}Y{sub 8}Ni{sub 5}){sub 99}Ce{sub 1} alloy ribbon showed a glass transition temperature (T{sub g}) at 483.2 K, and its ΔT{sub x} value was 41.3 K. Crystallization occurred in the temperature range of 500–750 K in three exothermic reaction stages. The peak temperature for these reactions shifted toward higher temperatures at higher heating rates. XRD and SEM analysis of annealed samples revealed that nano-sized Al particles precipitated within the amorphous matrix during the first exothermic reaction. The maximum hardness was obtained for both non-cerium and cerium addition alloys after crystallization in the 550–660 K region due to numerous nano-sized precipitates randomly and homogeneously distributed in the amorphous matrix. Moreover, from observation of the fracture surface, it is found that the fracture mode transforms from ductile to brittle when the sample is annealed at a higher crystallization temperature, at which brittle intermetallic compounds appear.

  4. Probing heterogeneous dynamics from spatial density correlation in glass-forming liquids.

    Science.gov (United States)

    Li, Yan-Wei; Zhu, You-Liang; Sun, Zhao-Yan

    2016-12-01

    We numerically investigate the connection between spatial density correlation and dynamical heterogeneity in glass-forming liquids. We demonstrate that the cluster size defined by the spatial aggregation of densely packed particles (DPPs) can better capture the difference between the dynamics of the Lennard-Jones glass model and the Weeks-Chandler-Andersen truncation model than the commonly used pair correlation functions. More interestingly, we compare the mobility of DPPs and loosely packed particles, and we find that high local density correlates well with slow dynamics in systems with relatively hard repulsive interactions but links to mobile ones in the system with soft repulsive interactions at one relaxation time scale. Our results show clear evidence that the above model dependence behavior stems from the hopping motion of DPPs at the end of the caging stage due to the compressive nature of soft repulsive spheres, which activates the dynamics of DPPs in the α relaxation stage.

  5. Settling of Spinel in A High-Level Waste Glass Melter

    International Nuclear Information System (INIS)

    Pavel Hrma; Pert Schill; Lubomir Nemec

    2002-01-01

    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 call melters to which the waste is charged together with glass-forming additives. The mixture is electrically heated to a temperature as high as 1150 degree C (or even higher in advanced melters) to create a melt that becomes glass on cooling. This process is slow and expensive. Moreover, the melters that are currently in use or are going to be used in the U.S. are sensitive to clogging and thus cannot process melt in which solid particles are suspended. These particles settle and gradually accumulate on the melter bottom. Such particles, most often small crystals of spinel ( a mineral containing iron, nickel, chromium, and other minor oxides), inevitably occurred in the melt when the content of the waste in the glass (called waste loading) increases above a certain limit. To avoid the presence of solid particles in the melter, the waste loading is kept rather low, in average 15% lower than in glass formulated for more robust melters

  6. Synthesis and Properties of Nanoparticle Forms Saponite Clay, Cancrinite Zeolite and Phase Mixtures Thereof.

    Science.gov (United States)

    Shao, Hua; Pinnavaia, Thomas J

    2010-09-01

    The low-temperature synthesis (90°C) of nanoparticle forms of a pure phase smectic clay (saponite) and zeolite (cancrinite) is reported, along with phase mixtures thereof. A synthesis gel corresponding to the Si:Al:Mg unit cell composition of saponite (3.6:0.40:3.0) and a NaOH/Si ratio of 1.39 affords the pure phase clay with disordered nanolayer stacking. Progressive increases in the NaOH/Si ratio up to a value of 8.33 results in the co-crystallization of first garronite and then cancrinite zeolites with nanolath morphology. The resulting phase mixtures exhibit a compound particulate structure of intertwined saponite nanolayers and cancrinite nanolaths that cannot be formed through physical mixing of the pure phase end members. Under magnesium-free conditions, pure phase cancrinite nanocrystals are formed. The Si/Al ratio of the reaction mixture affects the particle morphology as well as the chemical composition of the cancrinite zeolite. Ordinarily, cancrinite crystallizes with a Si/Al ratio of 1.0, but a silicon-rich form of the zeolite (Si/Al=1.25) is crystallized at low temperature from a silica rich synthesis gel, as evidenced by (29)Si NMR spectroscopy and XEDS-TEM. Owing to the exceptionally high external surface areas of the pure phase clay (875 m(2)/g) and zeolite end members (8.9 - 40 m(2)/g), as well as their unique mixed phase composites (124 - 329 m(2)/g), these synthetic derivatives are promising model nanoparticles for studies of the bioavailability of poly-aromatic hydrocarbons immobilized in silicate bearing sediments and soils.

  7. Application of the final flotation waste for obtaining the glass-ceramic materials

    Directory of Open Access Journals (Sweden)

    Cocić Mira

    2017-01-01

    Full Text Available This work describes the investigation of the final flotation waste (FFW, originating from the RTB Bor Company (Serbia, as the main component for the production of glass-ceramic materials. The glass-ceramics was synthesized by the sintering of FFW, mixtures of FFW with basalt (10%, 20%, and 40%, and mixtures of FFW with tuff (20% and 40%. The sintering was conducted at the different temperatures and with the different time duration in order to find the optimal composition and conditions for crystallization. The increase of temperature, from 1100 to 1480°C, and sintering time, from 4 to 6h resulted in a higher content of hematite crystal in the obtained glass-ceramic (up to 44%. The glass-ceramics sintered from pure FFW (1080°C/36h has good mechanical properties, such as high propagation speed (4500 m/s and hardness (10800 MPa, as well as very good thermal stability. The glass-ceramics obtained from mixtures shows weaker mechanical properties compared to that obtained from pure FFW. The mixtures of FFW with tuff have a significantly lower bulk density compared to other obtained glass-ceramics. Our results indicate that FFW can be applied as a basis for obtaining the construction materials. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 176010: Composition, genesis, application, and contribution to the environmental sustainability

  8. Radiation-induced polymerization of glass-forming systems. VII. Polymerization in supercooled state under high pressure

    International Nuclear Information System (INIS)

    Kaetsu, I.; Yoshii, F.; Watanabe, Y.

    1978-01-01

    Radiation-induced polymerization of glass-forming monomers such as 2-hydroxyethyl methacrylate and glycidyl methacrylate under high pressure was studied. The glass transition temperature of these monomers was heightened by increased pressure. The temperature dependence of polymerizability showed a characteristic relation, similar to those in supercooled-phase polymerization under normal pressure, that had a maximum at T/sub ν/ which shifted to higher levels of temperature as well as to T/sub g/ under high pressure. Polymerizability in the supercooled state also increased under increased pressure

  9. A strategy for weapons-grade plutonium disposition

    International Nuclear Information System (INIS)

    Sylvester, K.W.B.

    1994-09-01

    A political as well as technical analysis was performed to determine the feasibility of glassification (vitrification) for weapons grade plutonium (WGPu) disposition. The political analysis provided the criteria necessary to compare alternative storage forms. The technical areas of weapon useability and environmental safety were then computationally and experimentally explored and a vitrification implementation strategy postulated. The Monte Carlo Neutron Photon (MCNP) computer code was used to model the effect of blending WGPu with reactor grade Pu (RGPu). A mixture of 30% RGPu and 70% WGPu more than doubled the surface flux from a bare sphere of the mixture which assumedly correlates to a significantly increased predetonation probability. Rare earth diluents were also examined (using MCNP) for their ability to increase the compressed critical mass of the WGPu mixture. The rare earths (notably Eu) were effective in this regard. As Pu-239 has a 24,100 year half life, reactivity control in the long term is an environmental safety issue. Rare earths were investigated as criticality controllers due to their neutron absorption capabilities and insolubility in aqueous environments. Thorium (a Pu surrogate) and the rare earths Eu, Gd, and Sm were added to two standard frits (ARM-1 and SRL-165) and formed into glass. Aqueous leach tests were performed (using MCC-1P guidelines) to measure rare earth leaching and determine the added elements' effects on glass durability. Europium was much more leach resistant than boron in the glasses tested. The elements had no negative effect on the environmental durability of the glasses tested at 90 C and minimal effect at room temperature. No fission product releases were detected in the ARM-1 compositions (which contained numerous simulated fission products)

  10. A strategy for weapons-grade plutonium disposition

    Energy Technology Data Exchange (ETDEWEB)

    Sylvester, K.W.B. [Iowa State Univ., Ames, IA (United States)

    1994-09-01

    A political as well as technical analysis was performed to determine the feasibility of glassification (vitrification) for weapons grade plutonium (WGPu) disposition. The political analysis provided the criteria necessary to compare alternative storage forms. The technical areas of weapon useability and environmental safety were then computationally and experimentally explored and a vitrification implementation strategy postulated. The Monte Carlo Neutron Photon (MCNP) computer code was used to model the effect of blending WGPu with reactor grade Pu (RGPu). A mixture of 30% RGPu and 70% WGPu more than doubled the surface flux from a bare sphere of the mixture which assumedly correlates to a significantly increased predetonation probability. Rare earth diluents were also examined (using MCNP) for their ability to increase the compressed critical mass of the WGPu mixture. The rare earths (notably Eu) were effective in this regard. As Pu-239 has a 24,100 year half life, reactivity control in the long term is an environmental safety issue. Rare earths were investigated as criticality controllers due to their neutron absorption capabilities and insolubility in aqueous environments. Thorium (a Pu surrogate) and the rare earths Eu, Gd, and Sm were added to two standard frits (ARM-1 and SRL-165) and formed into glass. Aqueous leach tests were performed (using MCC-1P guidelines) to measure rare earth leaching and determine the added elements` effects on glass durability. Europium was much more leach resistant than boron in the glasses tested. The elements had no negative effect on the environmental durability of the glasses tested at 90 C and minimal effect at room temperature. No fission product releases were detected in the ARM-1 compositions (which contained numerous simulated fission products).

  11. Improving the interfacial and mechanical properties of short glass fiber/epoxy composites by coating the glass fibers with cellulose nanocrystals

    Science.gov (United States)

    A. Asadi; M. Miller; Robert Moon; K. Kalaitzidou

    2016-01-01

    In this study, the interfacial and mechanical properties of cellulose nanocrystals (CNC) coated glass fiber/epoxy composites were investigated as a function of the CNC content on the surface of glass fibers (GF). Chopped GF rovings were coated with CNC by immersing the GF in CNC (0–5 wt%) aqueous suspensions. Single fiber fragmentation (SFF) tests showed that the...

  12. The quality study of recycled glass phosphor waste for LED

    Science.gov (United States)

    Tsai, Chun-Chin; Chen, Guan-Hao; Yue, Cheng-Feng; Chen, Cin-Fu; Cheng, Wood-Hi

    2017-02-01

    To study the feasibility and quality of recycled glass phosphor waste for LED packaging, the experiments were conducted to compare optical characteristics between fresh color conversion layer and that made of recycled waste. The fresh color conversion layer was fabricated through sintering pristine mixture of Y.A.G. powder [yellow phosphor (Y3AlO12 : Ce3+). Those recycled waste glass phosphor re-melted to form Secondary Molten Glass Phosphor (S.M.G.P.). The experiments on such low melting temperature glass results showed that transmission rates of S.M.G.P. are 9% higher than those of first-sintered glass phosphor, corresponding to 1.25% greater average bubble size and 36% more bubble coverage area in S.M.G.P. In the recent years, high power LED modules and laser projectors have been requiring higher thermal stability by using glass phosphor materials for light mixing. Nevertheless, phosphor and related materials are too expensive to expand their markets. It seems a right trend and research goal that recycling such waste of high thermal stability and quality materials could be preferably one of feasible cost-down solutions. This technical approach could bring out brighter future for solid lighting and light source module industries.

  13. Structural Origin of the Enhanced Glass-Forming Ability Induced by Microalloying Y in the ZrCuAl Alloy

    Directory of Open Access Journals (Sweden)

    Gu-Qing Guo

    2016-03-01

    Full Text Available In this work, the structural origin of the enhanced glass-forming ability induced by microalloying Y in a ZrCuAl multicomponent system is studied by performing synchrotron radiation experiments combined with simulations. It is revealed that the addition of Y leads to the optimization of local structures, including: (1 more Zr-centered and Y-centered icosahedral-like clusters occur in the microstructure; (2 the atomic packing efficiency inside clusters and the regularity of clusters are both enhanced. These structural optimizations help to stabilize the amorphous structure in the ZrCuAlY system, and lead to a high glass-forming ability (GFA. The present work provides an understanding of GFAs in multicomponent alloys and will shed light on the development of more metallic glasses with high GFAs.

  14. Influence of the glass-calcium carbonate mixture's characteristics on the foaming process and the properties of the foam glass

    DEFF Research Database (Denmark)

    König, Jakob; Petersen, Rasmus Rosenlund; Yue, Yuanzheng

    2014-01-01

    We prepared foam glasses from cathode-ray-tube panel glass and CaCO3 as a foaming agent. We investigated the influences of powder preparation, CaCO3 concentration and foaming temperature and time on the density, porosity and homogeneity of the foam glasses. The results show that the decomposition...

  15. Sorption of a mixture of phenols in aqueous solution with activated carbon; Sorcion de una mezcla de fenoles en solucion acuosa con carbon activado

    Energy Technology Data Exchange (ETDEWEB)

    Mejia M, D.; Lopez M, B.E.; Iturbe G, J.L. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)

    2003-07-01

    The main objective of this work is the sorption of an aqueous mixture of phenol-4 chloro phenol of different concentrations in a molar relationship 1:1 in activated carbon of mineral origin of different nets (10, 20 and 30) and to diminish with it its presence in water. The experimental results show that the removal capacity depends so much of the surface properties of the sorbent like of the physical and chemical properties of the sorbate. In all the cases it was observed that in the aqueous systems of low concentration the 4-chloro phenol are removed in an approximate proportion of 1.2-4 times greater to than phenol, however to concentrations but high both they are removed approximately in the same proportion. (Author)

  16. Enhanced HLW glass formulations for the waste treatment and immobilization plant

    Energy Technology Data Exchange (ETDEWEB)

    Kruger, Albert A. [DOE-WTP Project Office, US Department of Energy, Richland, Washington (United States)

    2013-07-01

    Current estimates and glass formulation efforts are conservative vis-a-vis achievable waste loadings. These formulations have been specified to ensure that glasses are homogenous, contain essentially no crystalline phases, are processable in joule-heated, ceramic-lined melters and meet WTP Contract terms. The WTP's overall mission will require the immobilization of tank waste compositions that are dominated by mixtures of aluminum, chromium, bismuth, iron, phosphorous, zirconium, and sulfur compounds as waste-limiting components. Glass compositions for these waste mixtures have been developed based upon previous experience and current glass property models. DOE has a testing program to develop and characterize HLW glasses with higher waste loadings. This work has demonstrated the feasibility of increases in waste loading from 25 wt% to 33-50 wt% (based on oxide loading) in the glass depending on the waste stream. It is expected these higher waste loading glasses will reduce the HLW canister production requirement by 25% or more. (authors)

  17. Crossover to potential energy landscape dominated dynamics in a model glass-forming liquid

    DEFF Research Database (Denmark)

    Schrøder, Thomas; Sastry, S.; Dyre, Jeppe

    2000-01-01

    An equilibrated model glass-forming liquid is studied by mapping successive configurations produced by molecular dynamics simulation onto a time series of inherent structures (local minima in the potential energy). Using this "inherent dynamics" approach we find direct numerical evidence for the ......An equilibrated model glass-forming liquid is studied by mapping successive configurations produced by molecular dynamics simulation onto a time series of inherent structures (local minima in the potential energy). Using this "inherent dynamics" approach we find direct numerical evidence...... for the long held view that below a crossover temperature, Tx, the liquid's dynamics can be separated into (i) vibrations around inherent structures and (ii) transitions between inherent structures [M. Goldstein, J. Chem. Phys. 51, 3728 (1969)], i.e., the dynamics become "dominated" by the potential energy...... landscape. In agreement with previous proposals, we find that Tx is within the vicinity of the mode-coupling critical temperature Tc. We further find that near Tx, transitions between inherent structures occur via cooperative, stringlike rearrangements of groups of particles moving distances substantially...

  18. In-situ ductile metal/bulk metallic glass matrix composites formed by chemical partitioning

    Science.gov (United States)

    Kim, Choong Paul; Hays, Charles C.; Johnson, William L.

    2004-03-23

    A composite metal object comprises ductile crystalline metal particles in an amorphous metal matrix. An alloy is heated above its liquidus temperature. Upon cooling from the high temperature melt, the alloy chemically partitions, forming dendrites in the melt. Upon cooling the remaining liquid below the glass transition temperature it freezes to the amorphous state, producing a two-phase microstructure containing crystalline particles in an amorphous metal matrix. The ductile metal particles have a size in the range of from 0.1 to 15 micrometers and spacing in the range of from 0.1 to 20 micrometers. Preferably, the particle size is in the range of from 0.5 to 8 micrometers and spacing is in the range of from 1 to 10 micrometers. The volume proportion of particles is in the range of from 5 to 50% and preferably 15 to 35%. Differential cooling can produce oriented dendrites of ductile metal phase in an amorphous matrix. Examples are given in the Zr--Ti--Cu--Ni--Be alloy bulk glass forming system with added niobium.

  19. Novel method for early investigation of bioactivity in different borate bio-glasses

    Science.gov (United States)

    Abdelghany, A. M.

    Some ternary borate glasses were prepared and corrosion behavior of such ternary borate glasses after immersion in aqueous dilute phosphate solution was studied using different immersion times. Fourier transform infrared (FTIR) absorption spectral measurements were done before and after immersion in the mentioned solution for extended times up to 2 days to justify the appearance of the characteristic FTIR bands due to calcium phosphate (hydroxyapatite (HA)) which is considered as the potential indication of bioactivity. Experimental IR data confirm the beginning of the appearance of FTIR bands at about 580 and 620 cm-1 after 3 days and the complete resolution with its characteristic split form after 1 week and more. Deconvolution analysis technique (DAT) of the FTIR spectrum was employed to investigate the bioactivity of such ternary borate system after a short period of immersion. The corrosion behavior of such glasses is explained in relation to a suggested hydrolysis followed by direct dissolution mechanism. The ease of dissolution of all the borate glasses constituents explains the formation of calcium phosphate and conversion to crystalline hydroxyapatite within the borate glass matrix. X-ray diffraction may be used to retrace the structural changes and degree of crystallinity of the prepared glasses.

  20. The chemical durability of alkali aluminosilicate glasses

    International Nuclear Information System (INIS)

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

    1983-09-01

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

  1. Determination of the free enthalpies of formation of borosilicate glasses

    International Nuclear Information System (INIS)

    Linard, Y.

    2000-01-01

    This work contributes to the study of the thermochemical properties of nuclear waste glasses. Results are used to discuss mechanisms and parameters integrated in alteration models of conditioning materials. Glass is a disordered material defined thermodynamically as a non-equilibrium state. Taking into account one order parameter to characterise its configurational state, the metastable equilibrium for the glass was considered and the main thermochemical properties were determined. Calorimetric techniques were used to measure heat capacities and formation enthalpies of borosilicate glasses (from 3 to 8 constitutive oxides). Formation Entropies were measured too, using the entropy theory of relaxation processes proposed by Adam and Gibbs (1965). The configurational entropy contribution were determined from viscosity measurements. This set of data has allowed the calculation of Gibb's free energies of dissolution of glasses in pure water. By comparison with leaching experiments, it has been demonstrated that the decreasing of the dissolution rate at high reaction progress cannot be associated to the approach of an equilibrium between the sound glass and the aqueous solution. The composition changes of the reaction area at the glass surface need to be considered too. To achieve a complete description of the thermodynamic stability, the equilibrium between hydrated de-alkalinized glass and/or the gel layer with the aqueous solution should also be evaluated. (author)

  2. Combined Waste Form Cost Trade Study

    International Nuclear Information System (INIS)

    Gombert, Dirk; Piet, Steve; Trickel, Timothy; Carter, Joe; Vienna, John; Ebert, Bill; Matthern, Gretchen

    2008-01-01

    A new generation of aqueous nuclear fuel reprocessing, now in development under the auspices of the DOE Office of Nuclear Energy (NE), separates fuel into several fractions, thereby partitioning the wastes into groups of common chemistry. This technology advance enables development of waste management strategies that were not conceivable with simple PUREX reprocessing. Conventional wisdom suggests minimizing high level waste (HLW) volume is desirable, but logical extrapolation of this concept suggests that at some point the cost of reducing volume further will reach a point of diminishing return and may cease to be cost-effective. This report summarizes an evaluation considering three groupings of wastes in terms of cost-benefit for the reprocessing system. Internationally, the typical waste form for HLW from the PUREX process is borosilicate glass containing waste elements as oxides. Unfortunately several fission products (primarily Mo and the noble metals Ru, Rh, Pd) have limited solubility in glass, yielding relatively low waste loading, producing more glass, and greater disposal costs. Advanced separations allow matching the waste form to waste stream chemistry, allowing the disposal system to achieve more optimum waste loading with improved performance. Metals can be segregated from oxides and each can be stabilized in forms to minimize the HLW volume for repository disposal. Thus, a more efficient waste management system making the most effective use of advanced waste forms and disposal design for each waste is enabled by advanced separations and how the waste streams are combined. This trade-study was designed to juxtapose a combined waste form baseline waste treatment scheme with two options and to evaluate the cost-benefit using available data from the conceptual design studies supported by DOE-NE

  3. Construction of a 21-Component Layered Mixture Experiment Design

    International Nuclear Information System (INIS)

    Piepel, Gregory F.; Cooley, Scott K.; Jones, Bradley

    2004-01-01

    This paper describes the solution to a unique and challenging mixture experiment design problem involving: (1) 19 and 21 components for two different parts of the design, (2) many single-component and multi-component constraints, (3) augmentation of existing data, (4) a layered design developed in stages, and (5) a no-candidate-point optimal design approach. The problem involved studying the liquidus temperature of spinel crystals as a function of nuclear waste glass composition. The statistical objective was to develop an experimental design by augmenting existing glasses with new nonradioactive and radioactive glasses chosen to cover the designated nonradioactive and radioactive experimental regions. The existing 144 glasses were expressed as 19-component nonradioactive compositions and then augmented with 40 new nonradioactive glasses. These included 8 glasses on the outer layer of the region, 27 glasses on an inner layer, 2 replicate glasses at the centroid, and one replicate each of three existing glasses. Then, the 144 + 40 = 184 glasses were expressed as 21-component radioactive compositions and augmented with 5 radioactive glasses. A D-optimal design algorithm was used to select the new outer layer, inner layer, and radioactive glasses. Several statistical software packages can generate D-optimal experimental designs, but nearly all require a set of candidate points (e.g., vertices) from which to select design points. The large number of components (19 or 21) and many constraints made it impossible to generate the huge number of vertices and other typical candidate points. JMP(R) was used to select design points without candidate points. JMP uses a coordinate-exchange algorithm modified for mixture experiments, which is discussed in the paper

  4. Synthesis of sub-10 nm VO2 nanoparticles films with plasma-treated glass slides by aqueous sol–gel method

    International Nuclear Information System (INIS)

    Lan, Shi-Di; Cheng, Chih-Chia; Huang, Chi-Hsien; Chen, Jem-Kun

    2015-01-01

    Highlights: • Sub-10 nm VO 2 nanoparticles (VNPs) are synthesized on a plasma-treated glass. • Glass slides generate negative charges sites after plasma treatment to attract VO 2 + . • Doping tungsten with 1 wt% in VNPs did not change particle size significantly. • The particle size of VNP can be tuned by the density of negative charge sites. • Sub-10 nm structured VO 2 particle films exhibited high visible transmittance. - Abstract: This paper describes an aqueous sol–gel synthesis of thermochromic thin films consisted of vanadium dioxide nanoparticles (VNPs) on glass slides. The glass slides were treated by argon/oxygen plasma to generate dispersedly negative charge sites on the surface to attract VO 2 + from a sol–gel solution. After heat treatment in a low-pressure carbon monoxide/carbon dioxide (CO/CO 2 ) atmosphere, the VNPs could be generated in sub-10 nm of particle size on the surface. Various levels of doping were achieved by adding small quantities of a water-soluble tungsten compound to the sol; however, the particle size increased slightly with the tungsten doping levels. The change in electrical conductivity with temperature for VNP films were measured and compared to VO 2 crystalline films. VNP films exhibited the lower transition temperature of the semiconductor to metal phase change; at a doping level of 4 wt% the transition temperature was measured at 32.2 ± 1.2 and 24.1 ± 1.2 °C for the VO 2 and VNP films, respectively. The VNP films showed excellent visible transparency and a large change in transmittance at near-infrared (NIR) wavelengths before and after the metal–insulator phase transition (MIT). The current method is a landmark in the development of nanostructured material toward applications in energy-saving smart windows.

  5. Aqueous sulfomethylated melamine gel-forming compositions and methods of use

    Energy Technology Data Exchange (ETDEWEB)

    Meltz, C.N.; Guetzmacher, G.D.; Chang, P.W.

    1989-04-18

    A method is described for the selective modification of the permeability of the strata of a subterranean bydrocarbon-containing reservoir consisting of introducing into a well in, communication with the reservoir; an aqueous gel-forming composition, comprising a 1.0-60.0 weight percent sulfomethylated melamine polymer solution. The solution is prepared with a 1.0 molar equivalent of a malemine, reacted with 3.0-6.7 molar equivalents of formaldehyde or a 2-6 carbon atom containing dialdehyde; 0.25-1.25 molar equivalents of an alkali metal or ammonium salt of surfurous acid; and 0.01-1.5 molar equivalents of a gel-modifying agent.

  6. Glass Polyalkenoate Cements Designed for Cranioplasty Applications: An Evaluation of Their Physical and Mechanical Properties

    Directory of Open Access Journals (Sweden)

    Basel A. Khader

    2016-03-01

    Full Text Available Glass polyalkenoate cements (GPCs have potential for skeletal cementation. Unfortunately, commercial GPCs all contain, and subsequently release, aluminum ions, which have been implicated in degenerative brain disease. The purpose of this research was to create a series of aluminum-free GPCs constructed from silicate (SiO2, calcium (CaO, zinc (ZnO and sodium (Na2O-containing glasses mixed with poly-acrylic acid (PAA and to evaluate the potential of these cements for cranioplasty applications. Three glasses were formulated based on the SiO2-CaO-ZnO-Na2O parent glass (KBT01 with 0.03 mol % (KBT02 and 0.06 mol % (KBT03 germanium (GeO2 substituted for ZnO. Each glass was then mixed with 50 wt % of a patented SiO2-CaO-ZnO-strontium (SrO glass composition and the resultant mixtures were subsequently reacted with aqueous PAA (50 wt % addition to produce three GPCs. The incorporation of Ge in the glass phase was found to result in decreased working (142 s to 112 s and setting (807 s to 448 s times for the cements manufactured from them, likely due to the increase in crosslink formation between the Ge-containing glasses and the PAA. Compressive (σc and biaxial flexural (σf strengths of the cements were examined at 1, 7 and 30 days post mixing and were found to increase with both maturation and Ge content. The bonding strength of a titanium cylinder (Ti attached to bone by the cements increased from 0.2 MPa, when placed, to 0.6 MPa, after 14 days maturation. The results of this research indicate that Germano-Silicate based GPCs have suitable handling and mechanical properties for cranioplasty fixation.

  7. Glass dissolution rate measurement and calculation revisited

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-01

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

  8. West Valley high-level nuclear waste glass development: a statistically designed mixture study

    Energy Technology Data Exchange (ETDEWEB)

    Chick, L.A.; Bowen, W.M.; Lokken, R.O.; Wald, J.W.; Bunnell, L.R.; Strachan, D.M.

    1984-10-01

    The first full-scale conversion of high-level commercial nuclear wastes to glass in the United States will be conducted at West Valley, New York, by West Valley Nuclear Services Company, Inc. (WVNS), for the US Department of Energy. Pacific Northwest Laboratory (PNL) is supporting WVNS in the design of the glass-making process and the chemical formulation of the glass. This report describes the statistically designed study performed by PNL to develop the glass composition recommended for use at West Valley. The recommended glass contains 28 wt% waste, as limited by process requirements. The waste loading and the silica content (45 wt%) are similar to those in previously developed waste glasses; however, the new formulation contains more calcium and less boron. A series of tests verified that the increased calcium results in improved chemical durability and does not adversely affect the other modeled properties. The optimization study assessed the effects of seven oxide components on glass properties. Over 100 melts combining the seven components into a wide variety of statistically chosen compositions were tested. Viscosity, electrical conductivity, thermal expansion, crystallinity, and chemical durability were measured and empirically modeled as a function of the glass composition. The mathematical models were then used to predict the optimum formulation. This glass was tested and adjusted to arrive at the final composition recommended for use at West Valley. 56 references, 49 figures, 18 tables.

  9. Non-ergodicity transition and multiple glasses in binary mixtures: on the accuracy of the input static structure in the mode coupling theory

    International Nuclear Information System (INIS)

    Tchangnwa Nya, F; Ayadim, A; Germain, Ph; Amokrane, S

    2012-01-01

    We examine the question of the accuracy of the static correlation functions used as input in the mode coupling theory (MCT) of non-ergodic states in binary mixtures. We first consider hard-sphere mixtures and compute the static pair structure from the Ornstein-Zernike equations with the Percus-Yevick closure and more accurate ones that use bridge functions deduced from Rosenfeld’s fundamental measures functional. The corresponding MCT predictions for the non-ergodicity lines and the transitions between multiple glassy states are determined from the long-time limit of the density autocorrelation functions. We find that while the non-ergodicity transition line is not very sensitive to the input static structure, up to diameter ratios D 2 /D 1 = 10, quantitative differences exist for the transitions between different glasses. The discrepancies with the more accurate closures become even qualitative for sufficiently asymmetric mixtures. They are correlated with the incorrect behavior of the PY structure at high size asymmetry. From the example of ultra-soft potential it is argued that this issue is of general relevance beyond the hard-sphere model. (paper)

  10. Physical properties of aqueous mixtures of the ionic 1-ethl-3-methyl imidazolium octyl sulfate: A new ionic rigid gel

    International Nuclear Information System (INIS)

    Cabeza, O.; Vila, J.; Rilo, E.; Domínguez-Pérez, M.; Otero-Cernadas, L.; López-Lago, E.; Méndez-Morales, T.; Varela, L.M.

    2014-01-01

    Graphical abstract: Phase diagram indicating three transitions temperatures: (liquid + gel) (dot symbols), (liquid + crystal) (square symbols) and (crystal + liquid) (triangle symbols) for the aqueous EMIM-OS mixtures. - Highlights: • We present the phase diagram of the system EMIM-octyl sulfate + water. • We show that a rigid gel phase appears for certain concentrations and temperatures. • That gel presents a smectic-like phase, being really a rigid gel crystal. • The gel is as electrical conductive as the liquid in spite of the viscosity change. • Density does not change at the (liquid + gel) transition. - Abstract: We report the existence of hydrophobically driven lyotropic rigid gel phase in aqueous mixtures of the ionic liquid (IL) 1-ethyl-3-methyl imidazolium octyl sulfate (EMIM-OS), and we characterize the physical properties of the gel phase by means of density, electrical conductivity and viscosity measurements. Also we include polarized microscopy images, showing the existence of a crystalline-like gel phase with the cations and anions (mainly the alkyl chain of this last ones) ordered in a fashion similar to a liquid crystal, which is induced by the presence of the water molecules. As was pointed out briefly in a previous paper, some of the mixtures of that system under goes a (liquid + gel) phase transition only in a quite narrow concentration interval: for ionic liquid molar fraction, x IL , from 0.09 to 0.5. Below x IL = 0.09 and above x IL = 0.5, the mixtures crystallize at low temperature becoming a hard solid crystal. Here we report the complete phase diagram of this binary system, as well as measurements of the temperature behavior of several physical properties around the (liquid + gel) and (liquid + crystal) transitions. Curiously enough, we did not detect any change in the temperature dependence of the measured magnitudes at the (liquid + gel) phase transition, but for viscosity, even in the case of the electrical conductivity

  11. Development and characterization of solidified forms for high-level wastes: 1978. Annual report

    International Nuclear Information System (INIS)

    Ross, W.A.; Mendel, J.E.

    1979-12-01

    Development and characterization of solidified high-level waste forms are directed at determining both process properties and long-term behaviors of various solidified high-level waste forms in aqueous, thermal, and radiation environments. Waste glass properties measured as a function of composition were melt viscosity, melt electrical conductivity, devitrification, and chemical durability. The alkali metals were found to have the greatest effect upon glass properties. Titanium caused a slight decrease in viscosity and a significant increase in chemical durability in acidic solutions (pH-4). Aluminum, nickel and iron were all found to increase the formation of nickel-ferrite spinel crystals in the glass. Four multibarrier advanced waste forms were produced on a one-liter scale with simulated waste and characterized. Glass marbles encapsulated in a vacuum-cast lead alloy provided improved inertness with a minimal increase in technological complexity. Supercalcine spheres exhibited excellent inertness when coated with pyrolytic carbon and alumina and put in a metal matrix, but the processing requirements are quite complex. Tests on simulated and actual high-level waste glasses continue to suggest that thermal devitrification has a relatively small effect upon mechanical and chemical durabilities. Tests on the effects radiation has upon waste forms also continue to show changes to be relatively insignificant. Effects caused by decay of actinides can be estimated to saturate at near 10 19 alpha-events/cm 3 in homogeneous solids. Actually, in solidified waste forms the effects are usually observed around certain crystals as radiation causes amorphization and swelling of th crystals

  12. Physicochemical characterization of in situ drug-polymer nanocomplex formed between zwitterionic drug and ionomeric material in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Salamanca, Constain H., E-mail: chsalamanca@icesi.edu.co [Pharmaceutical physical chemistry laboratory, Department of Pharmacy, Faculty of Natural Sciences, ICESI University, Cali (Colombia); Castillo, Duvan F.; Villada, Juan D. [Pharmaceutical physical chemistry laboratory, Department of Pharmacy, Faculty of Natural Sciences, ICESI University, Cali (Colombia); Rivera, Gustavo R. [SIT Biotech GmbH, BMZ 2 Otto-Hahn-Str. 15, 44227 Dortmund (Germany)

    2017-03-01

    Biocompatible polymeric materials with the potential to form functional structures, in association with different therapeutic molecules, in physiological media, represent a great potential for biological and pharmaceutical applications. Therefore, here the formation of a nano-complex between a synthetic cationic polymer and model drug (ampicillin trihydrate) was studied. The formed complex was characterized by size and zeta potential measurements, using dynamic light scattering and capillary electrophoresis. Moreover, the chemical and thermodynamically stability of these complexes were studied. The ionomeric material, here referred as EuCl, was obtained by equimolar reaction between Eudragit E and HCl. The structural characterization was carried out by potentiometric titration, FTIR spectroscopy, and DSC. The effect of pH, time, polymer concentration and ampicillin/polymer molar ratio over the hydrodynamic diameter and zeta potential were established. The results show that EuCl ionomer in aqueous media presents two different populations of nanoparticles; one of this tends to form flocculated aggregates in high pH and concentrations, by acquiring different conformations in solution by changing from a compact to an extended conformation. Moreover, the formation of an in situ interfacial polymer-drug complex was demonstrated, this could slightly reduce the hydrolytic degradation of the drug while affecting its solubility, mainly under acidic conditions. - Highlights: • The EuCl ionomer in aqueous media presents two different populations of nanoparticle, corresponding to proximally 15 nm and 150 nm. • The EuCl ionomer in aqueous media may form different structure depending on the pH and polymer concentration, which tends to form flocculated aggregates in high pH and concentrations. • The formation of an in situ interfacial polymer-drug complex was demonstrated, which could slightly reduce the hydrolytic degradation of the drug and affecting its solubility in

  13. Characterization of iron phosphate glasses prepared by microwave heating

    International Nuclear Information System (INIS)

    Almeida, Fabio Jesus Moreira de

    2006-01-01

    Phosphate glasses have been investigated since the fifties, because they are relatively easy to prepare, have low melting temperatures (1000 deg C - 1200 deg C and low glass transition. However, these glasses were very sensitive to humidity, showing a very low chemical durability. Iron phosphate glasses have been prepared by melting inorganic precursors in conventional electric furnaces and induction furnaces. By adding iron, phosphate glasses became chemical resistant and were thought to be used as nuclear waste forms or mechanical resistance fibers. The use of microwaves has been investigated because it makes possible a fast and homogeneous heating of the materials. Microwave promotes the self-heating of the material by the interaction of the external electromagnetic field with the molecules and ions of the material. Niobium phosphate glasses was also produced already through the heating of precursors in microwave ovens. Other glasses containing iron in theirs structure was produced by conventional furnaces and they had your structures analyzed. But even so, it was not still published synthesis of iron phosphate glasses starting from the melting of precursors materials in microwave ovens. In the present work mixtures of (NH 4 ) 2 HPO 4 and Fe 3 O 4 or (NH 4 ) 2 HPO 4 and Fe 2 O 3 were exposed to microwave energy with electromagnetic waves of 2,45 GHz. It was proposed that the absorption of this radiation for the material causes the heating from room temperature to melting temperature. The obtained iron phosphate glasses was analyzed by X-ray diffraction, Moessbauer spectroscopy, and Differential Thermal Analysis. Iron phosphate glasses were also produced in electrical furnaces for comparison. (author)

  14. Characterization of iron phosphate glasses prepared by microwave heating

    International Nuclear Information System (INIS)

    Almeida, Fabio Jesus Moreira de

    2006-01-01

    Phosphate glasses have been investigated since the fifties, because they are relatively easy to prepare, have low melting temperatures (1000 deg C - 1200 deg C), and low glass transition. However, these glasses were very sensitive to humidity, showing a very low chemical durability. Iron phosphate glasses have been prepared by melting inorganic precursors in conventional electric furnaces and induction furnaces. By adding iron, phosphate glasses became chemical resistant and were thought to be used as nuclear waste forms or mechanical resistance fibers. The use of microwaves has been investigated because it makes possible a fast and homogeneous heating of the materials. Microwave promotes the self-heating of the material by the interaction of the external electromagnetic field with the molecules and ions of the material. Niobium phosphate glasses was also produced already through the heating of precursors in microwave ovens. Other glasses containing iron in theirs structure was produced by conventional furnaces and they had your structures analyzed. But even so, it was not still published synthesis of iron phosphate glasses starting from the melting of precursors materials in microwave ovens. In the present work mixtures of (NH 4 ) 2 HPO 4 and Fe 3 O 4 or (NH 4 ) 2 HPO 4 and Fe 2 O 3 were exposed to microwave energy with electromagnetic waves of 2,45 GHz. It was proposed that the absorption of this radiation for the material causes the heating from room temperature to melting temperature. The obtained iron phosphate glasses was analyzed by X-ray diffraction, Moessbauer spectroscopy, and Differential Thermal Analysis. Iron phosphate glasses were also produced in electrical furnaces for comparison. (author)

  15. Fragility correlates thermodynamic and kinetic properties of glass forming liquids

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, C.Narayana [Maharani’s Science College for Women, Bangalore 560001 (India); Viswanatha, R.; Chethana, B.K. [Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012 (India); Gowda, V.C.Veeranna [Government First Grade College, Jayanagara, Bangalore 560070 (India); Rao, K.J., E-mail: kalyajrao@yahoo.co.in [Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012 (India)

    2015-03-15

    Graphical abstract: The suggested new fragility parameter correlates viscosity and configurational entropy. - Highlights: • A new fragility function, F=ΔT/ΔC{sub p}×C{sub p}{sup l}/T{sub g} has been proposed. • A three parameter viscosity function using the new F reproduces Angell fragility plot. • A new ΔC{sub p} function is derived which directly relates Adam–Gibbs function with the fragility based viscosity function. - Abstract: In our earlier communication we proposed a simple fragility determining function, ([NBO]/V{sub m}{sup 3}T{sub g}), which we have now used to analyze several glass systems using available thermal data. A comparison with similar fragility determining function, ΔC{sub p}/C{sub p}{sup l}, introduced by Chryssikos et al. in their investigation of lithium borate glasses has also been performed and found to be more convenient quantity for discussing fragilities. We now propose a new function which uses both ΔC{sub p} and ΔT and which gives a numerical fragility parameter, F whose value lies between 0 and 1 for glass forming liquids. F can be calculated through the use of measured thermal parameters ΔC{sub p}, C{sub p}{sup l}, T{sub g} and T{sub m}. Use of the new fragility values in reduced viscosity equation reproduces the whole range of viscosity curves of the Angell plot. The reduced viscosity equation can be directly compared with the Adam–Gibbs viscosity equation and a heat capacity function can be formulated which reproduces satisfactorily the ΔC{sub p} versus ln(T{sub r}) curves and hence the configurational entropy.

  16. Electrochromic Glasses.

    Science.gov (United States)

    1980-07-31

    this glass and that dipole-dipole correlations contribute to the "ferroelectric-like" character of this amorphous system. The TeO2 -W03 glasses can only...shows the dielectric constant and Fig. I(b) glass from pure TeO2 ot pure WO. In addition, glass the tan 8 of the WO glass as a function of temperature... glasses containing WO, in various glass forming nitworks of LifO-B1O0, Na:O-BzO,, and TeO2 were prepared from reagent grade oxides at 800 C - 9SO C in

  17. Structure and aqueous reactivity of silicate glasses high-resolution nuclear magnetic resonance contribution; Structure et reactivite aqueuse des verres silicates apport de la resonance magnetique nucleaire haute-resolution

    Energy Technology Data Exchange (ETDEWEB)

    Angeli, F

    2000-10-25

    This research aims at getting a better understanding of the relations which may exist between the chemical composition of the oxide silicate glasses, the structure and the aqueous reactivity. We study the cations present in most glasses, more particularly the radioactive waste glasses, and those which are more liable to bring information both about structure and reactivity. Among the experimental methods used, the nuclear magnetic resonance of multi-quantum magic-angle spinning (NMR MQ-MAS) has been carried out for the structural characterization of the pristine and altered glasses. In the first part, we discuss the possibility of deducting a type of information from a quantitative approach of the {sup 23}Na, {sup 27}Al and {sup 17}O NMR MQ-MAS. In the second part, we apply this method to glasses containing between two and six oxides. The vitreous compositions studied permit to focus our attention on the influence of sodium, aluminum and calcium on their local structural environment. We point out an evolution of the distributions of bond distances and angles in relation to the glass chemical composition. We show the strong potentiality of the {sup 17}O used to probe the pristine and altered glasses. The influence of the different cations studied on the rate of glass dissolution is debated from the alterations made on short periods. On the basis of all these data, we discuss the importance of the structural effect which may influence the kinetic phenomena of alteration. (author)

  18. Production of lightweight foam glass (invited talk)

    DEFF Research Database (Denmark)

    Petersen, Rasmus Rosenlund; König, Jakob; Yue, Yuanzheng

    The foam glass production allows low cost recycling of postconsumer glass and industrial waste materials as foaming agent or as melt resource. Foam glass is commonly produced by utilising milled glass mixed with a foaming agent. The powder mixture is heat-treated to around 10^3.7 – 10^6 Pa s, which...... result in viscous sintering and subsequent foaming of the glass melt. The porous glass melt is cooled down to room temperature to freeze-in the foam structure. The resulting foam glass is applied in constructions as a light weight material to reduce load bearing capacity and as heat insulating material...... in buildings and industry. We foam panel glass from old televisions with different foaming agents. We discuss the foaming ability and the foaming mechanism of different foaming systems. We compare several studies to define a viscous window for preparing low density foam glass. However, preparing foam glass...

  19. Kissinger method applied to the crystallization of glass-forming liquids: Regimes revealed by ultra-fast-heating calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Orava, J., E-mail: jo316@cam.ac.uk [Department of Materials Science & Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS (United Kingdom); WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Greer, A.L., E-mail: alg13@cam.ac.uk [Department of Materials Science & Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS (United Kingdom); WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan)

    2015-03-10

    Highlights: • Study of ultra-fast DSC applied to the crystallization of glass-forming liquids. • Numerical modeling of DSC traces at heating rates exceeding 10 orders of magnitude. • Identification of three regimes in Kissinger plots. • Elucidation of the effect of liquid fragility on the Kissinger method. • Modeling to study the regime in which crystal growth is thermodynamically limited. - Abstract: Numerical simulation of DSC traces is used to study the validity and limitations of the Kissinger method for determining the temperature dependence of the crystal-growth rate on continuous heating of glasses from the glass transition to the melting temperature. A particular interest is to use the wide range of heating rates accessible with ultra-fast DSC to study systems such as the chalcogenide Ge{sub 2}Sb{sub 2}Te{sub 5} for which fast crystallization is of practical interest in phase-change memory. Kissinger plots are found to show three regimes: (i) at low heating rates the plot is straight, (ii) at medium heating rates the plot is curved as expected from the liquid fragility, and (iii) at the highest heating rates the crystallization rate is thermodynamically limited, and the plot has curvature of the opposite sign. The relative importance of these regimes is identified for different glass-forming systems, considered in terms of the liquid fragility and the reduced glass-transition temperature. The extraction of quantitative information on fundamental crystallization kinetics from Kissinger plots is discussed.

  20. Kissinger method applied to the crystallization of glass-forming liquids: Regimes revealed by ultra-fast-heating calorimetry

    International Nuclear Information System (INIS)

    Orava, J.; Greer, A.L.

    2015-01-01

    Highlights: • Study of ultra-fast DSC applied to the crystallization of glass-forming liquids. • Numerical modeling of DSC traces at heating rates exceeding 10 orders of magnitude. • Identification of three regimes in Kissinger plots. • Elucidation of the effect of liquid fragility on the Kissinger method. • Modeling to study the regime in which crystal growth is thermodynamically limited. - Abstract: Numerical simulation of DSC traces is used to study the validity and limitations of the Kissinger method for determining the temperature dependence of the crystal-growth rate on continuous heating of glasses from the glass transition to the melting temperature. A particular interest is to use the wide range of heating rates accessible with ultra-fast DSC to study systems such as the chalcogenide Ge 2 Sb 2 Te 5 for which fast crystallization is of practical interest in phase-change memory. Kissinger plots are found to show three regimes: (i) at low heating rates the plot is straight, (ii) at medium heating rates the plot is curved as expected from the liquid fragility, and (iii) at the highest heating rates the crystallization rate is thermodynamically limited, and the plot has curvature of the opposite sign. The relative importance of these regimes is identified for different glass-forming systems, considered in terms of the liquid fragility and the reduced glass-transition temperature. The extraction of quantitative information on fundamental crystallization kinetics from Kissinger plots is discussed

  1. Fracture toughness measurements on a glass bonded sodalite high-level waste form

    International Nuclear Information System (INIS)

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

    1999-01-01

    The electrometallurgical treatment of metallic spent nuclear fuel produces two high-level waste streams; cladding hulls and chloride salt. Argonne National Laboratory is developing a glass bonded sodalite waste form to immobilize the salt waste stream. The waste form consists of 75 Vol.% crystalline sodalite (containing the salt) with 25 Vol.% of an ''intergranular'' glassy phase. Microindentation fracture toughness measurements were performed on representative samples of this material using a Vickers indenter. Palmqvist cracking was confirmed by post-indentation polishing of a test sample. Young's modulus was measured by an acoustic technique. Fracture toughness, microhardness, and Young's modulus values are reported, along with results from scanning electron microscopy studies

  2. Radiosensitization of thymidine in deaerated aqueous solution

    International Nuclear Information System (INIS)

    Berger, Maurice.

    1982-09-01

    This work investigates the mode of action of various radiosensitizing agents on the radio-induced degradation of thymidine in deaerated aqueous solution. A special effort was devoted to the separation of addition products formed by one of these substances (a stable nitroxide radical: TAN) with the radio-induced neutral radicals of thymidine. The complex mixture of different diastereoisomers resulting from the covalent addition of the TAN molecule on the thymidine carbons C (5) or C (6) was resolved by HPLC. The structural determination of these adducts (absolute configuration) was achieved by various spectroscopic techniques and specific chemical syntheses. A conformational study has been undertaken [fr

  3. Glass and cellulose acetate fibers-supported boehmite nanosheets for bacteria adsorption

    Directory of Open Access Journals (Sweden)

    N.V. Svarovskaya

    2017-04-01

    Full Text Available In this work, in situ method of producing hybrid fibrous adsorbents in which boehmite nanosheets with high sorption properties formed on the surface of hydrophilic microfibres, such as cellulose acetate and glass fibre, was described. The boehmite nanosheets were fabricated by the reaction of composite AlN/Al nanoparticles with water at 60 °C. The synthesized samples were characterized by X-ray diffractometer, scanning, transmission electron microscopy, Fourier transform infrared spectrometer (FT-IR, zeta-potential and specific surface area analyzers. The introduction of microfibres into a diluted aqueous suspension of nanopowders causes heteroadagulation of the nanoparticles and accelerates their further transformation. This effect is most substantial with the glass microfibre, which is thought to have a higher concentration of surface groups capable of generating hydrogen bonds that act as heteroadagulation and nucleation centres. The experimental results showed that the morphology of the resultant hybrid fibrous adsorbents differed accordingly: the nanosheets were attached on-edge to the glass microfibre surface, while on the surface of the cellulose acetate microfibre, they were secured in the form of spherical “nanoflowers” of agglomerated nanosheets. The effect of the morphology of hybrid fibrous adsorbents on adsorption bacteria Escherichia coli was also investigated.

  4. Molecular environmental science using synchrotron radiation: Chemistry and physics of waste form materials

    International Nuclear Information System (INIS)

    Lindle, Dennis W.; Shuh, David K.

    2005-01-01

    Production of defense-related nuclear materials has generated large volumes of complex chemical wastes containing a mixture of radionuclides. The disposition of these wastes requires conversion of the liquid and solid-phase components into durable, solid forms suitable for long-term immobilization [1]. Specially formulated glass compositions, many of which have been derived from glass developed for commercial purposes, and ceramics such as pyrochlores and apatites, will be the main recipients for these wastes. The performance characteristics of waste-form glasses and ceramics are largely determined by the loading capacity for the waste constituents (radioactive and non-radioactive) and the resultant chemical and radiation resistance of the waste-form package to leaching (durability). There are unique opportunities for the use of near-edge soft-x-ray absorption fine structure (NEXAFS) spectroscopy to investigate speciation of low-Z elements forming the backbone of waste-form glasses and ceramics. Although nuclear magnetic resonance (NMR) is the primary technique employed to obtain speciation information from low-Z elements in waste forms, NMR is incompatible with the metallic impurities contained in real waste and is thus limited to studies of idealized model systems. In contrast, NEXAFS can yield element-specific speciation information from glass constituents without sensitivity to paramagnetic species. Development and use of NEXAFS for eventual studies of real waste glasses has significant implications, especially for the low-Z elements comprising glass matrices [5-7]. The NEXAFS measurements were performed at Beamline 6.3.1, an entrance-slitless bend-magnet beamline operating from 200 eV to 2000 eV with a Hettrick-Underwood varied-line-space (VLS) grating monochromator, of the Advanced Light Source (ALS) at LBNL. Complete characterization and optimization of this beamline was conducted to enable high-performance measurements

  5. Molecular environmental science using synchrotron radiation:Chemistry and physics of waste form materials

    Energy Technology Data Exchange (ETDEWEB)

    Lindle, Dennis W.; Shuh, David K.

    2005-02-28

    Production of defense-related nuclear materials has generated large volumes of complex chemical wastes containing a mixture of radionuclides. The disposition of these wastes requires conversion of the liquid and solid-phase components into durable, solid forms suitable for long-term immobilization [1]. Specially formulated glass compositions, many of which have been derived from glass developed for commercial purposes, and ceramics such as pyrochlores and apatites, will be the main recipients for these wastes. The performance characteristics of waste-form glasses and ceramics are largely determined by the loading capacity for the waste constituents (radioactive and non-radioactive) and the resultant chemical and radiation resistance of the waste-form package to leaching (durability). There are unique opportunities for the use of near-edge soft-x-ray absorption fine structure (NEXAFS) spectroscopy to investigate speciation of low-Z elements forming the backbone of waste-form glasses and ceramics. Although nuclear magnetic resonance (NMR) is the primary technique employed to obtain speciation information from low-Z elements in waste forms, NMR is incompatible with the metallic impurities contained in real waste and is thus limited to studies of idealized model systems. In contrast, NEXAFS can yield element-specific speciation information from glass constituents without sensitivity to paramagnetic species. Development and use of NEXAFS for eventual studies of real waste glasses has significant implications, especially for the low-Z elements comprising glass matrices [5-7]. The NEXAFS measurements were performed at Beamline 6.3.1, an entrance-slitless bend-magnet beamline operating from 200 eV to 2000 eV with a Hettrick-Underwood varied-line-space (VLS) grating monochromator, of the Advanced Light Source (ALS) at LBNL. Complete characterization and optimization of this beamline was conducted to enable high-performance measurements.

  6. Disordered ultracold atomic gases in optical lattices: A case study of Fermi-Bose mixtures

    International Nuclear Information System (INIS)

    Ahufinger, V.; Sanchez-Palencia, L.; Kantian, A.; Sanpera, A.; Lewenstein, M.

    2005-01-01

    We present a review of properties of ultracold atomic Fermi-Bose mixtures in inhomogeneous and random optical lattices. In the strong interacting limit and at very low temperatures, fermions form, together with bosons or bosonic holes, composite fermions. Composite fermions behave as a spinless interacting Fermi gas, and in the presence of local disorder they interact via random couplings and feel effective random local potential. This opens a wide variety of possibilities of realizing various kinds of ultracold quantum disordered systems. In this paper we review these possibilities, discuss the accessible quantum disordered phases, and methods for their detection. The discussed quantum phases include Fermi glasses, quantum spin glasses, 'dirty' superfluids, disordered metallic phases, and phases involving quantum percolation

  7. Local elastic expansion model for viscous-flow activation energies of glass-forming molecular liquids

    DEFF Research Database (Denmark)

    Dyre, Jeppe; Olsen, Niels Boye; Christensen, Tage Emil

    1996-01-01

    A model for the viscosity of glass-forming molecular liquids is proposed in which a "flow event" requires a local volume increase. The activation energy for a flow event is identified with the work done in shoving aside the surrounding liquid; this work is proportional to the high-frequency shear...

  8. Changing the Tendency of Glass-Forming Liquid To Crystallize by Moving Along Different Isolines in the T-p Phase Diagram

    DEFF Research Database (Denmark)

    Adrjanowicz, Karolina; Koperwas, Kajetan; Tarnacka, Magdalena

    2016-01-01

    Controlling crystallization and glass-forming tendencies of molecular liquids is of great scientific and practical importance. In the present work, we show that a lot can be learned regarding this process by introducing temperature and pressure as thermodynamic control variables. For the glass...

  9. Na, Mg, Ni and Cs distribution and speciation after long-term alteration of a simulated nuclear waste glass: A micro-XAS/XRF/XRD and wet chemical study

    Science.gov (United States)

    Curti, Enzo; Dähn, Rainer; Farges, François; Vespa, Marika

    2009-04-01

    Microscopic distribution and speciation of Na, Mg, Ni and Cs in a simulated (inactive) nuclear waste glass were studied using micro X-ray fluorescence (μ-XRF) and micro X-ray absorption spectroscopy (μ-XAS), after aqueous leaching during 12 years at 90 °C. Na and Mg are major constituents of the glass that can be used to determine the progress of the glass corrosion process and the nature of secondary alteration phases. Ni and Cs represent dose determining long-lived radionuclides ( 59Ni, 135Cs) in vitrified nuclear waste. The Na-Mg μ-XRF maps revealed that the core regions of the glass fragments are apparently unaltered and compositionally homogeneous, whereas rims and interstitial spaces are enriched with Mg-rich smectite formed during the leaching process. The micro X-ray absorption near edge structure (μ-XANES) spectra collected at the Mg K-edge in the altered zones show three sharp resonances typical for crystalline Mg-silicates. These resonances are distinctive of Mg occupying undistorted octahedral positions. In contrast, the μ-XANES spectra collected in the core zones of the glass fragments lack this resonance pattern and are identical to the spectra measured on the pristine (unleached) MW glass. Micro extended X-ray absorption fine structure (μ-EXAFS) and μ-XANES analyses at the Ni K-edge revealed three distinct Ni(II) species: (a) Ni uniformly distributed in the glass matrix, (b) micro-inclusions with high Ni concentrations and (c) Ni associated to the Mg-clay. The comparison with reference spectra of unleached MW and other Ni-bearing silicate glasses indicated that species (a) represents the original coordinative environment of Ni in the glass. The μ-EXAFS analyses revealed that species (b) is structural Ni in trevorite (NiFe 2O 4), which probably formed through unmixing processes during the cooling of the glass melt. The μ-EXAFS of species (c) could be successfully modeled assuming specific adsorption or incorporation of Ni into the lattice of

  10. Dropping and semimicrotest glass reactions on beryllium, lenthanum, vanadyl and uranyl cations with synthetic organic dyes and their mutual determination in binary mixtures

    International Nuclear Information System (INIS)

    Shemyakin, F.M.; Novikova, A.A.; Reshetnyak, V.Yu.; Teplyakov, G.K.; Nekrasov, E.L.

    1978-01-01

    Coloured reactions for beryllium, lanthanum, vanadyl and uranyl cations with a number of organic dyes, have been studied. These reactions are used in dropping analysis on papers, impregnated with relevant dyes, and for semimicro-test glass reactions on the above cations. Sensitivity and maximum permissible dilution have been determined for each of the reactions. Mutual determinations of relevant couples of the above cations have been performed. It is shown, that such binary mixtures enable to freely open relevant cations

  11. Effect of solute atoms on glass-forming ability for Fe–Y–B alloy: An ab initio molecular dynamics study

    International Nuclear Information System (INIS)

    Han, J.J.; Wang, W.Y.; Liu, X.J.; Wang, C.P.; Hui, X.D.; Liu, Z.K.

    2014-01-01

    The glass-forming abilities of Fe 78 B 22 , Fe 70 Y 6 B 24 , Fe 72 Y 6 B 22 and Fe 72.5 Y 3.5 B 24 alloys were characterized comprehensively using ab initio molecular dynamics simulations. The calculated results were correlated with the properties and atomic structures. It was found that the Fe 72 Y 6 B 22 alloy consists of both the most stable and the least deformed body centered cubic atomic packing structures in the supercooled liquid and glassy states. It was observed that the local compositions in the Fe 72 Y 6 B 22 alloy significantly deviate from the compositions of stable crystalline phases, indicating that the Fe 72 Y 6 B 22 alloy has the best glass-forming ability among the alloys studied. However, Fe 72 Y 6 B 22 alloy has two flaws in terms of glass-forming ability, i.e. relatively large atomic diffusivity and insufficiently close atomic packing. The best performance in these two aspects is observed in the Fe 72.5 Y 3.5 B 24 alloy. Thus, the theoretical study predicts that the best glass former for the Fe–Y–B system is within the compositional range of 22–24 at.% B and 3.5–6 at.% Y

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

    International Nuclear Information System (INIS)

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

    1999-01-01

    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 3 forms UO 2 and PuCl 3 forms PuO 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 2

  13. Electronic-structure origin of the glass-forming ability and magnetic properties in Fe–RE–B–Nb bulk metallic glasses

    International Nuclear Information System (INIS)

    Li, J.W.; Estévez, D.; Jiang, K.M.; Yang, W.M.; Man, Q.K.; Chang, C.T.; Wang, X.M.

    2014-01-01

    Highlights: • Relation between GFA and electronic structure of RE doped BMGs is investigated. • Tm enhances RE–B bonds and decreases the density of states near the Fermi level. • Magnetic properties of the alloys are related to the electronic structure of RE. - Abstract: (Fe 0.71 RE 0.05 B 0.24 ) 96 Nb 4 (RE = Gd, Tb, Ho, Er, Tm) bulk metallic glasses (BMGs) were found exhibiting excellent glass-forming ability (GFA) with critical diameters ranging from 3.5 to 6.5 mm, and high compressive fracture strength larger than 4300 MPa. Moreover, they displayed good soft-magnetic properties with saturation magnetic flux density of 0.71–0.87 T, coercive force of 1.23–39.76 A/m and effective permeability of 1500–12,740 at 1 kHz. X-ray photoelectron spectroscopy was performed to clarify the origin of the excellent GFA from the viewpoint of electronic structure. It was found that the Tm doped alloy displayed unique electronic structure including the deepest core-level binding energy, the most numerous RE–B bonds and the minimum density of states near the Fermi level, making this alloy the best glass former. The various trends noticed in the magnetic properties were ascribed mainly to the differences in the magnetic anisotropy and magnetic moment of RE elements

  14. The slag from ELCOGAS IGCC thermal power plant as raw material for the synthesis of glass-ceramic materials. Part I: Thermal behavior of the IGCC slag and synthesis of the parent glass.

    Energy Technology Data Exchange (ETDEWEB)

    Aineto, M.; Acosta, A. [University of Castilla La Mancha, Ciudad Real (Spain)

    2005-12-01

    We report here the results of the first phase of investigation on the melting behavior of the IGCC slag, and the use of this slag as raw component to produce glass ceramics. The vitrifying mixture named ECSCP, is composed of 40% slag, 30% glass cullet and 30% precipitated calcium carbonate obtained as a by-product in a sugar refining plant. This mixture was melted at 1450{sup o}C to obtain the ECSCP parent glass, that was then characterized and its crystallization kinetics studied by thermal analysis. The ECSCP glass exhibit a surface mechanism of crystallization, and will be used to produce anorthite/wollastonite glass ceramics in the second part of the investigation.

  15. Effect of glass-forming biopreservatives on head group rotational dynamics in freeze-dried phospholipid bilayers: A 31P NMR study

    Science.gov (United States)

    Jain, P.; Sen, S.; Risbud, S. H.

    2009-07-01

    P31 NMR spectroscopy has been used to elucidate the role of glass-forming sugars in the preservation of dipalmitoylphosphatidylcholine (DPPC) lipid bilayers. P31 wideline NMR spectra of freeze-dried pure DPPC, DPPC/trehalose, DPPC/glucose, and DPPC/hydroxyethyl starch (HES) mixtures collected in the temperature range of 25-80 °C have been simulated to obtain quantitative information about rotational dynamics and orientation of the lipid head groups in these media. In the case of pure DPPC, DPPC/glucose, and DPPC/HES, the gel-to-liquid crystalline phase transition of DPPC bilayer is characterized by a sudden increase in the rate of rotational diffusion of the PO4 head groups near 40 °C. The corresponding rotational jump frequency increases from a few kilohertz in the gel phase to at least several megahertz in the liquid crystalline phase. On the other hand, in the case of DPPC/trehalose mixture the temperature of this onset of rapid head group dynamics is increased by ˜10 °C. Trehalose reduces the lipid head group motions most effectively in the temperature range of T ≤50 °C relevant for biopreservation. Additionally, and possibly more importantly, trehalose is found to strongly restrict any change in the orientation of the diffusion axis of the PO4 head groups during the phase transformation. This unique ability of trehalose to maintain the dynamical and orientational rigidity of lipid head groups is likely to be responsible for its superior ability in biopreservation.

  16. Segregative phase separation in aqueous mixtures of polydisperse biopolymers

    NARCIS (Netherlands)

    Edelman, M.W.

    2003-01-01

    Keywords: biopolymer, gelatine, dextran, PEO, phase separation, polydispersity, molar mass distribution, SEC-MALLS, CSLM The temperature-composition phase diagram of aqueous solutions of gelatine and dextran, which show liquid/liquid phase segregation, were explored at temperatures above the

  17. Rhyolitic glasses as natural analogues of nuclear waste glasses: behaviour of an Icelandic glass upon natural aqueous corrosion

    International Nuclear Information System (INIS)

    Magonthier, M.-C.; Petit, J.-C.; Dran, J.-C.

    1992-01-01

    A detailed study of the altered rims present in narrow fissures of a 52 ka-old Icelandic obsidian reveals the behaviour of transition and heavy elements, as well as the mechanism and kinetics of alteration, during glass/solution interaction. These complex altered rims are alkali depleted and consist of alternating layers of Fe-rich aluminosilicate and aluminium thihydroxide. The elemental partitioning observed on this naturally corroded obsidian is supported by laboratory experiments performed on the same glass, the elemental accumulation being explained by the formation of a hydrosilicate. A good correlation exists between the thickness of the altered rims and that calculated from the amounts of Fe and Ti accumulated locally. Thus, immobile elements can be used reliably as indices of the extent of alteration because only near-equilibrium conditions occur. The good agreement between the experimental hydration rate of obsidians and the progress of natural corrosion, leads to the assumption that ion diffusion is the long-term controlling mechanism of corrosion. Such an assumption is supported by the particular distribution of the immobile elements which is due to ion diffusion and coprecipitation processes (self-organization genesis). These observations have implications for nuclear waste disposal topics and support the validity of obsidians as analogues of nuclear waste glasses with respect to some local environmental constraints induced by waste packaging and disposal. (author)

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

    OpenAIRE

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

    2011-01-01

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

  19. Experimental Design for Hanford Low-Activity Waste Glasses with High Waste Loading

    International Nuclear Information System (INIS)

    Piepel, Gregory F.; Cooley, Scott K.; Vienna, John D.; Crum, Jarrod V.

    2015-01-01

    This report discusses the development of an experimental design for the initial phase of the Hanford low-activity waste (LAW) enhanced glass study. This report is based on a manuscript written for an applied statistics journal. Appendices A, B, and E include additional information relevant to the LAW enhanced glass experimental design that is not included in the journal manuscript. The glass composition experimental region is defined by single-component constraints (SCCs), linear multiple-component constraints (MCCs), and a nonlinear MCC involving 15 LAW glass components. Traditional methods and software for designing constrained mixture experiments with SCCs and linear MCCs are not directly applicable because of the nonlinear MCC. A modification of existing methodology to account for the nonlinear MCC was developed and is described in this report. One of the glass components, SO 3 , has a solubility limit in glass that depends on the composition of the balance of the glass. A goal was to design the experiment so that SO 3 would not exceed its predicted solubility limit for any of the experimental glasses. The SO 3 solubility limit had previously been modeled by a partial quadratic mixture model expressed in the relative proportions of the 14 other components. The partial quadratic mixture model was used to construct a nonlinear MCC in terms of all 15 components. In addition, there were SCCs and linear MCCs. This report describes how a layered design was generated to (i) account for the SCCs, linear MCCs, and nonlinear MCC and (ii) meet the goals of the study. A layered design consists of points on an outer layer, and inner layer, and a center point. There were 18 outer-layer glasses chosen using optimal experimental design software to augment 147 existing glass compositions that were within the LAW glass composition experimental region. Then 13 inner-layer glasses were chosen with the software to augment the existing and outer-layer glasses. The experimental

  20. Flexible, Heat-Resistant, and Flame-Retardant Glass Fiber Nonwoven/Glass Platelet Composite Separator for Lithium-Ion Batteries

    Directory of Open Access Journals (Sweden)

    Ulrich Schadeck

    2018-04-01

    Full Text Available A new type of high-temperature stable and self-supporting composite separator for lithium-ion batteries was developed consisting of custom-made ultrathin micrometer-sized glass platelets embedded in a glass fiber nonwoven together with a water-based sodium alginate binder. The physical and electrochemical properties were investigated and compared to commercial polymer-based separators. Full-cell configuration cycling tests at different current rates were performed using graphite and lithium iron phosphate as electrode materials. The glass separator was high-temperature tested and showed a stability up to at least 600 °C without significant shrinking. Furthermore, it showed an exceptional wettability for non-aqueous electrolytes. The electrochemical performance was excellent compared to commercially available polymer-based separators. The results clearly show that glass platelets integrated into a glass fiber nonwoven performs remarkably well as a separator material in lithium-ion batteries and show high-temperature stability.