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Sample records for borosilicate glasses rich

  1. Structure, thermal stability and resistance under external irradiation of rare earths and molybdenum-rich alumino-borosilicate glasses

    International Nuclear Information System (INIS)

    In France, the highly radioactive nuclear liquid wastes arising from spent nuclear fuel reprocessing (fission products + minor actinides (FPA)) are currently immobilized in an alumino-borosilicate glass called 'R7T7'. In the future, the opportunity of using new alumino-borosilicate glass compositions (HTC glasses) is considered in order to increase the waste loading in glasses and thus significantly decrease the number of glass canisters. However, the increase of the concentration of FPA could lead to the crystallization of rare-earth-rich phases (Ca2RE8(SiO4)6O2) or molybdenum-rich phases (CaMoO4, Na2MoO4) during melt cooling, which can modify the confinement properties of the glass (chemical durability, self-irradiation resistance..), particularly if they can incorporate radionuclides α or β in their structure. This thesis can be divided into two parts: The first part deals with studying the relationship that can occur between the composition, the structure and the crystallization tendency of simplified seven oxides glasses, belonging to the SiO2-B2O3-Al2O3-Na2O-CaO-MoO3-Nd2O3 system and derived from the composition of the HTC glass at 22,5 wt. % in FPA. The impact of the presence of platinoid elements (RuO2 in our case) on the crystallization of the different phases is also studied. The second part deals with the effect of actinides α decays and more particularly of nuclear interactions essentially coming from recoil nuclei (simulated here by heavy ions external irradiations) on the behaviour under irradiation of an alumino-borosilicate glass containing apatite Ca2Nd8(SiO4)6O2 crystals, that can incorporate actinides in their structure. Two samples containing apatite crystals with different size are studied, in order to understand the impact of microstructure on the irradiation resistance of this kind of material. (author)

  2. Dolomite effect on borosilicate glass alteration

    International Nuclear Information System (INIS)

    Highlights: ► Dolomite is a common mineral of clayey formations considered for radioactive waste disposals. ► Borosilicate glass/dolomite interaction have been studied by batch tests and solid analysis. ► Mg provided by dolomite combines with Si from glass to yield secondary Mg–silicates. ► This precipitation increases glass alteration, though in a moderate manner. ► Geochemical modeling allows to quantify the alteration mechanisms involved. - Abstract: Dolomite (CaMg(CO3)2) is one of the common rock-forming minerals in many geological media, in particular in clayey layers that are currently considered as potential host formations for a deep radioactive waste disposal facility. Magnesium in solution is one of the elements known to potentially enhance the alteration of nuclear glasses. The alteration of borosilicate glasses with dolomite as a Mg-bearing mineral source was investigated for 8 months in batch tests at 90 °C. Glass composition effects were investigated through two compositions (SiBNaAlCaZrO and SiBNaAlZrO) differing in their Ca content. The Ca-rich glass alteration is slightly enhanced in the presence of dolomite compared to the alteration observed in pure water. This greater alteration is explained by the precipitation of Mg silicate phases on the dolomite and glass surfaces. In contrast, the Ca-free glass alteration decreases in the presence of dolomite compared to the alteration observed in pure water. This behavior is explained by Ca incorporation in the amorphous layer (formed during glass alteration) coming from dolomite dissolution. Calcium acts as a layer reorganizer and limits glass alteration by reducing the diffusion of reactive species through the altered layer. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC geochemical code to discriminate and interpret the mechanisms involved in glass/dolomite interactions. Magnesium released by dolomite dissolution reacts with silica provided by glass

  3. Borosilicate glass alteration driven by magnesium carbonates

    International Nuclear Information System (INIS)

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

  4. Topological Principles of Borosilicate Glass Chemistry

    DEFF Research Database (Denmark)

    Smedskjær, Morten Mattrup; Mauro, J. C.; Youngman, R. E.;

    2011-01-01

    and laboratory glassware to high-tech applications such as liquid crystal displays. In this paper, we investigate the topological principles of borosilicate glass chemistry covering the extremes from pure borate to pure silicate end members. Based on NMR measurements, we present a two-state statistical...

  5. Photoluminescent properties of nanocrystallized zinc borosilicate glasses

    Czech Academy of Sciences Publication Activity Database

    Chen, G.; Nikl, Martin; Solovieva, Natalia; Beitlerová, Alena; Rao, J.; Yang, Y.; Zhang, Y.; Jiang, X.; Zhu, C.

    2004-01-01

    Roč. 38, - (2004), s. 771-774. ISSN 1350-4487 R&D Projects: GA MŠk(CZ) 1P04ME716 Institutional research plan: CEZ:AV0Z1010914 Keywords : zinc borosilicate glass * scintillating material * luminescence * nanosized crystals Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.664, year: 2004

  6. The mechanism of borosilicate glass corrosion revisited

    Science.gov (United States)

    Geisler, Thorsten; Nagel, Thorsten; Kilburn, Matt R.; Janssen, Arne; Icenhower, Jonathan P.; Fonseca, Raúl O. C.; Grange, Marion; Nemchin, Alexander A.

    2015-06-01

    Currently accepted mechanistic models describing aqueous corrosion of borosilicate glasses are based on diffusion-controlled hydrolysis, hydration, ion exchange reactions, and subsequent re-condensation of the hydrolyzed glass network, leaving behind a residual hydrated glass or gel layer. Here, we report results of novel oxygen and silicon isotope tracer experiments with ternary Na borosilicate glasses that can be better explained by a process that involves the congruent dissolution of the glass, which is spatially and temporally coupled to the precipitation and growth of an amorphous silica layer at an inwardly moving reaction interface. Such a process is thermodynamically driven by the solubility difference between the glass and amorphous silica, and kinetically controlled by glass dissolution reactions at the reaction front, which, in turn, are controlled by the transport of water and solute elements through the growing corrosion zone. Understanding the coupling of these reactions is the key to understand the formation of laminar or more complex structural and chemical patterns observed in natural corrosion zones of ancient glasses. We suggest that these coupled processes also have to be considered to realistically model the long-term performance of silicate glasses in aqueous environments.

  7. Effect of boron oxide addition on the Nd3+ environment in a Nd-rich soda-lime alumino-borosilicate glass

    International Nuclear Information System (INIS)

    The environment of Nd3+ ions has been studied using optical absorption spectroscopy and EXAFS at the Nd-L3-edge, in a series of soda lime alumino-borosilicate glasses with increasing B2O3 content. The proportion of BO4 units has been determined by 11B MAS NMR in an equivalent glass series with La3+ ions replacing the majority of Nd3+ ions, and complementary information has been obtained by measuring the Nd3+ decay fluorescence times in these latter glasses. In these glasses with low Al2O3 content, the R' ratio, with R' = [Na2O(exc)]/[B2O3] and [Na2O(exc)] = [Na2O] - [Al2O3] - [ZrO2], plays a key role in controlling the structural organization and crystallization resistance, in a similar way as the R ratio in the Dell and Bray model of sodium borosilicate glasses. At R'≥ 0.5, the Nd3+ ions are located in a mixed silicate-borate environment and, by slow cooling of the melt, they tend to crystallize within a silicate apatite phase close to the Ca2Nd8(SiO4)6O2 composition. At R' ≤ 0.5, the structural results are compatible with Nd3+ ions located in a borate-type environment (not excluding Si neighbors), and, by slow cooling of the melt, they segregate with Ca2+ ions within a Si-depleted separated borosilicate phase. (authors)

  8. Irradiation effects on borosilicate waste glasses

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, F.P.

    1980-06-01

    The effects of alpha decay on five borosilicate glasses containing simulated nuclear high-level waste oxides were studied. Irradiations carried out at room temperature were achieved by incorporating 1 to 8 wt % /sup 244/Cm/sub 2/O/sub 3/ in the glasses. Density changes and stored-energy build-up saturated at doses less than 2 x 10/sup 21/ alpha decays/kg. Damage manifested by stored energy was completely annealed at 633/sup 0/K. Positive and negative density changes were observed which never exceeded 1%. Irradiation had very little effect on mechanical strength or on chemical durability as measured by aqueous leach rates. Also, no effects were observed on the microstructure for vitreous waste glasses, although radiation-induced microcracking could be achieved on specimens that had been devitrified prior to irradiation.

  9. Surface chemistry and durability of borosilicate glass

    International Nuclear Information System (INIS)

    Important glass-water interactions are poorly understood for borosilicate glass radioactive waste forms. Preliminary results show that glass durability is dependent on reactions occurring at the glass-solution interface. CSG glass (18.2 wt. % Na2O, 5.97 wt. % CaO, 11.68 wt. % Al2O3, 8.43 wt. % B2O3, and 55.73 wt. % SiO2) dissolution and net surface H+ and OH- adsorption are minimal at near neutral pH. In the acid and alkaline pH regions, CSG glass dissolution rates are proportional to [H+]adsorbed2 and [OH-]adsorbed0.8, respectively. In contrast, silica gel dissolution and net H+ and OH- adsorption are minimal and independent of pH in acid to neutral solutions. In the alkaline pH region, silica gel dissolution is proportional to [OH-]adsorbed0.9adsorbed. Although Na adsorption is significant for CSG glass and silica gel in the alkaline pH regions, it is not clear if it enhances dissolution, or is an artifact of depolymerization of the framework bonds

  10. Antagonist effects of calcium on borosilicate glass alteration

    Energy Technology Data Exchange (ETDEWEB)

    Mercado-Depierre, S. [CEA Marcoule, DTCD SPDE LCLT, 30207 Bagnols sur Cèze (France); Angeli, F., E-mail: frederic.angeli@cea.fr [CEA Marcoule, DTCD SPDE LCLT, 30207 Bagnols sur Cèze (France); Frizon, F. [CEA Marcoule, DTCD SECM LP2C, 30207 Bagnols sur Cèze (France); Gin, S. [CEA Marcoule, DTCD SPDE LCLT, 30207 Bagnols sur Cèze (France)

    2013-10-15

    Graphical abstract: Display Omitted -- Highlights: •Kinetic study of glass alteration is investigated in calcium-enriched solutions. •New insights into silicon–calcium interactions in glass/cement systems are proposed. •Glass alteration is controlled by pH, Ca concentration and reaction progress. •Evidence of antagonist effects according to the importance of these parameters. -- Abstract: Numerous studies have been conducted on glass and cement durability in contact with water, but very little work to date has focused directly on interactions between the two materials. These interactions are mostly controlled by silicon–calcium reactivity. However, the physical and chemical processes involved remain insufficiently understood to predict the evolution of coupled glass–cement systems used in several industrial applications. Results are reported from borosilicate glass alteration in calcium-rich solutions. Our data show that four distinct behaviors can be expected according to the relative importance of three key parameters: the pH, the reaction progress (short- or long-term alteration) and the calcium concentration. Glass alteration is thus controlled by specific mechanisms depending on the solution chemistry: calcium complexation at the glass surface, precipitation of calcium silicate hydrates (C–S–H) or calcium incorporation in the altered layer. These findings highlight the impact of silicon–calcium interactions on glass durability and open the way for a better understanding of glass–cement mixing in civil engineering applications as well as in nuclear waste storage.

  11. Potassium borosilicate glasses: Phase separation and structon types

    International Nuclear Information System (INIS)

    The dc electrical resistivity of potassium borosilicate glasses was measured in the temperature range from 323 to 623K. The conduction mechanism was of ionic type. The composition and heat treatment effects on the conduction mechanism were studied. The results obtained were interpreted in terms of a previously proposed phase separation model. The possible different structon types of potassium borosilicate glasses were postulated according to the Huggins structon theory. (author)

  12. Direct conversion of halogen-containing wastes to borosilicate glass

    International Nuclear Information System (INIS)

    Glass has become a preferred waste form worldwide for radioactive wastes: however, there are limitations. Halogen-containing wastes can not be converted to glass because halogens form poor-quality waste glasses. Furthermore, halides in glass melters often form second phases that create operating problems. A new waste vitrification process, the Glass Material Oxidation and dissolution System (GMODS), removes these limitations by converting halogen-containing wastes into borosilicate glass and a secondary, clean, sodium-halide stream

  13. Magnetic Glass Ceramics by Sintering of Borosilicate Glass and Inorganic Waste

    Directory of Open Access Journals (Sweden)

    Inès M. M. M. Ponsot

    2014-07-01

    Full Text Available Ceramics and glass ceramics based on industrial waste have been widely recognized as competitive products for building applications; however, there is a great potential for such materials with novel functionalities. In this paper, we discuss the development of magnetic sintered glass ceramics based on two iron-rich slags, coming from non-ferrous metallurgy and recycled borosilicate glass. The substantial viscous flow of the glass led to dense products for rapid treatments at relatively low temperatures (900–1000 °C, whereas glass/slag interactions resulted in the formation of magnetite crystals, providing ferrimagnetism. Such behavior could be exploited for applying the obtained glass ceramics as induction heating plates, according to preliminary tests (showing the rapid heating of selected samples, even above 200 °C. The chemical durability and safety of the obtained glass ceramics were assessed by both leaching tests and cytotoxicity tests.

  14. Er3+-Yb3+ codoped borosilicate glass for optical thermometry

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Infrared to green up-conversion emissions centered at the wavelengths of about 524 and 550 nm of the Er3+-Yb3+ codoped borosilicate glass are recorded,using a 978 nm semiconductor laser diode(LD) as an excitation source.The fluorescence intensity ratio(FIR) of the green up-conversion emissions at about 524 and 550 nm in the Er3+-Yb3+ codoped borosilicate glass has been studied as a function of temperature over the temperature range of 295-873 K.The maximum sensitivity and the temperature resolution derived from the FIR of the green up-conversion emissions are approximately 0.0038 K-1 and 0.2 K,respectively.It is demonstrated that the prototype optical temperature sensor based on the FIR technique from the green up-conversion emissions in the Er3+-Yb3+ codoped borosilicate glass plays a major role in temperature measurement.

  15. Behavior of sodium borosilicate glasses under compression using molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Kilymis, D. A.; Ispas, S., E-mail: simona.ispas@univ-montp2.fr [Laboratoire Charles Coulomb (L2C), UMR 5221 CNRS-Université de Montpellier, F-34095 Montpellier (France); Delaye, J.-M. [CEA, DEN, DTCD, SECM, F-30207 Bagnols-sur-Cèze (France)

    2015-09-07

    We have performed classical molecular dynamics simulations in order to study the changes under compression in the local and medium range structural properties of three sodium borosilicate glasses with varying sodium content. These glasses have been isostatically compressed up to 20 GPa and then decompressed in order to analyze the different mechanisms that affect densification, alongside with the permanent modifications of the structure after a full compression/decompression cycle. The results show that the atomic packing is the prominent characteristic that governs the amount of densification in the glass, as well as the setup of the permanent densification. During compression, the bulk modulus increases linearly up to approximately 15 GPa and more rapidly for higher pressures, a behavior which is reflected on the rate of increase of the average coordination for B and Na. Radial distribution functions at different pressures during the cycle help to quantify the amount of distortions in the elementary structural units, with a pronounced shortening of the Na–Na and Na–O bond lengths during compression. A subsequent decomposition of the glassy matrix into elementary Voronoi volumes verifies the high compressibility of Na-rich regions.

  16. Using of borosilicate glass waste as a cement additive

    Science.gov (United States)

    Han, Weiwei; Sun, Tao; Li, Xinping; Sun, Mian; Lu, Yani

    2016-08-01

    Borosilicate glass waste is investigated as a cement additive in this paper to improve the properties of cement and concrete, such as setting time, compressive strength and radiation shielding. The results demonstrate that borosilicate glass is an effective additive, which not only improves the radiation shielding properties of cement paste, but also shows the irradiation effect on the mechanical and optical properties: borosilicate glass can increase the compressive strength and at the same time it makes a minor impact on the setting time and main mineralogical compositions of hydrated cement mixtures; and when the natural river sand in the mortar is replaced by borosilicate glass sand (in amounts from 0% to 22.2%), the compressive strength and the linear attenuation coefficient firstly increase and then decrease. When the glass waste content is 14.8%, the compressive strength is 43.2 MPa after 28 d and the linear attenuation coefficient is 0.2457 cm-1 after 28 d, which is beneficial for the preparation of radiation shielding concrete with high performances.

  17. Utilization of borosilicate glass for transuranic waste immobilization

    International Nuclear Information System (INIS)

    Incinerated transuranic waste and other low-level residues have been successfully vitrified by mixing with boric acid and sodium carbonate and heating to 10500C in a bench-scale continuous melter. The resulting borosilicate glass demonstrates excellent mechanical durability and chemical stability

  18. Ultrafast laser fabrication of submicrometer pores in borosilicate glass

    OpenAIRE

    An, Ran; Uram, Jeffrey D.; Yusko, Erik C.; Ke, Kevin; Mayer, Michael; Hunt, Alan J.

    2008-01-01

    We demonstrate rapid fabrication of submicrometer-diameter pores in borosilicate glass using femtosecond laser machining and subsequent wet-etch techniques. This approach allows direct and repeatable fabrication of high-quality pores with diameters of 400–800 nm. Such small pores coupled with the desirable electrical and chemical properties of glass enable sensitive resistive-pulse analysis to determine the size and concentration of macromolecules and nanoparticles. Plasma-enhanced chemical v...

  19. Ultrashort laser pulse induced nanogratings in borosilicate glass

    International Nuclear Information System (INIS)

    We report on nanogratings inscribed by repetitive femtosecond laser pulses into the bulk of borosilicate glass. The irradiation produces small nanopores (10–20 nm thick) which start to self-organize in gratings as well as elongated sheets of up to 400 nm length. A quantitative description of the grating structure and its development are obtained by a combination of focused ion beam milling, scanning electron microscopy, and small angle X-ray scattering (SAXS). The SAXS partial invariant of the thin sheets is found to correlate well with the measured optical retardance. Compared to fused silica nanogratings borosilicate glass shows a much smaller retardance due to re-annealing of pores. In addition, the nanograting period strongly deviates from the well-known λ/2n prediction. We could observe periods down to 60 nm (at an inscribing wavelength of 800 nm). This has not been observed yet in other glasses.

  20. Low Velocity Sphere Impact of a Borosilicate Glass

    Energy Technology Data Exchange (ETDEWEB)

    Morrissey, Timothy G [ORNL; Ferber, Mattison K [ORNL; Wereszczak, Andrew A [ORNL; Fox, Ethan E [ORNL

    2012-05-01

    This report summarizes US Army TARDEC sponsored work at Oak Ridge National Laboratory (ORNL) involving low velocity (< 30 m/s or < 65 mph) ball impact testing of Borofloat borosilicate glass, and is a follow-up to a similar study completed by the authors on Starphire soda-lime silicate glass last year. The response of the borosilicate glass to impact testing at different angles was also studied. The Borofloat glass was supplied by the US Army Research Laboratory and its tin-side was impacted or indented. The intent was to better understand low velocity impact response in the Borofloat. Seven sphere materials were used whose densities bracket that of rock: borosilicate glass, soda-lime silicate glass, silicon nitride, aluminum oxide, zirconium oxide, carbon steel, and a chrome steel. A gas gun or a ball-drop test setup was used to produce controlled velocity delivery of the spheres against the glass tile targets. Minimum impact velocities to initiate fracture in the Borofloat were measured and interpreted in context to the kinetic energy of impact and the elastic property mismatch between the seven sphere-Borofloat-target combinations. The primary observations from this low velocity (< 30 m/s or < 65 mph) testing were: (1) BS glass responded similarly to soda-lime silicate glass when spherically indented but quite differently under sphere impact conditions; (2) Frictional effects contributed to fracture initiation in BS glass when it spherically indented. This effect was also observed with soda-lime silicate glass; (3) The force necessary to initiate fracture in BS glass under spherical impact decreases with increasing elastic modulus of the sphere material. This trend is opposite to what was observed with soda-lime silicate glass. Friction cannot explain this trend and the authors do not have a legitimate explanation for it yet; (4) The force necessary to initiate contact-induced fracture is higher under dynamic conditions than under quasi-static conditions. That

  1. Topological Principles of Borosilicate Glass Chemistry - An Invited Talk

    DEFF Research Database (Denmark)

    Mauro, J.C.; Smedskjær, Morten Mattrup; Youngman, R. E.;

    measurements, we present a two-state statistical mechanical model of boron speciation in which addition of network modifiers leads to a competition between the formation of nonbridging oxygen and the conversion of boron from trigonal to tetrahedral configuration. Using this model, we derive a detailed...... topological representation of alkali-alkaline earth-borosilicate glasses that enables the accurate prediction of properties such as glass transition temperature, liquid fragility, hardness, and configurational heat capacity. The implications of the glass topology are discussed in terms of both the temperature...

  2. Moessbauer spectroscopic study of potassium borosilicate glasses at low temperatures

    International Nuclear Information System (INIS)

    The Moessbauer technique at the liquid nitrogen temperature (78 K) was applied to the estimation of nonbridging oxygens in FeO4, BO4, and SiO4 units in potassium borosilicate glasses. Moessbauer spectra consist of a quadrupole doublet and a hyperfine structure due to Fe3+ ions with tetrahedral symmetry. The hyperfine structure is attributed to a relaxation effect because magnetic susceptibility measurements revealed the glasses to be paramagnetic in the temperature range 78 - 295 K. A linear decrease in the absorption area and a similar decrease in the internal magnetic field for the hyperfine structure were observed with an increase in the alkali content of glasses. The decrease is ascribed to a formation of non-bridging oxygen at the site adjacent to iron, because the mean life-time of the internal magnetic field produced by 3d-electrons of iron is considered to decrease with increasing thermal vibration of the iron and neighboring oxygens. Fractions of non-bridging oxygens obtained from the reduction rate of the absorption area of hyperfine structure are in good agreement with earlier results for borate glasses with the same K2O/B2O3 ratios, in the alkali region of 8 - 20 mol% where the borosilicate glasses are essentially considered to be borate glasses diluted with SiO2. (author)

  3. Modeling and simulation of the cooling process of borosilicate glass

    International Nuclear Information System (INIS)

    For a better understanding of the thermomechanical behavior of glasses used for nuclear waste vitrification, the cooling process of a bulk borosilicate glass is modeled using the finite element code Abaqus. During this process, the thermal gradients may have an impact on the solidification process. To evaluate this impact, the simulation was based on thermal experimental data from an inactive nuclear waste package. The thermal calculations were made within a parametric window using different boundary conditions to evaluate the variations of temperature distributions for each case. The temperature differences throughout the thickness of solidified glass were found to be significantly non-uniform throughout the package. The temperature evolution in the bulk glass was highly responsive to the external cooling rates applied; thus emphasizing the role of the thermal inertia for this bulky glass cast. (authors)

  4. Sulphate Incorporation in Borosilicate Glasses and Melts: a Kinetic Approach

    International Nuclear Information System (INIS)

    The kinetics of sulphate departure in a sodium borosilicate melt were studied using in situ Raman spectroscopy. This technique allows the quantification of the amount of sulphate dissolved in a borosilicate glass as a function of heating time by comparison with measurements obtained by microprobe wavelength dispersive spectrometry. To quantify the sulphate content obtained with Raman spectroscopy, the integrated intensity of the sulphate band at 990 cm-1 was scaled to the sum of the integrated bands between 800 and 1200 cm-1, bands that are assigned to Qn silica units on the basis of previous literature. Calibration curves were then determined for two different samples. An evaluation of the kinetics of departure of sulphate could thus be made as a function of the viscosity of the borosilicate glass, showing that the kinetics were controlled by the diffusion of sulphate and its volatilization from the melt. This experimental method allows in situ measurements of sulphate content at high temperature which cannot be obtained by any other simple technique. (authors)

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

    International Nuclear Information System (INIS)

    Borosilicate glasses loaded with ∼10 wt % plutonium were found to produce plutonium-silicate alteration phases upon aqueous corrosion under a range of conditions. The phases observed were generally rich in lanthanide (Ln) elements and were related to the lanthanide orthosilicate phases of the monoclinic Ln2SiO5 type. The composition of the phases was variable regarding [Ln]/[Pu] ratio, depending upon type of corrosion test and on the location within the alteration layer. The formation of these phases likely has implications for the incorporation of plutonium into silicate alteration phases during corrosion of titanate ceramics, high-level waste glasses, and spent nuclear fuel

  6. Study on leaching mechanism of sodium borosilicate glass microspheres

    International Nuclear Information System (INIS)

    Sodium borosilicate glasses find applications in heavy water plants, in nuclear waste immobilization, glass to metal sealing and various others fields. These glasses are found to be durable in corrosive ambient. Aim of the present work is to see the initial leaching mechanism/kinetics on sodium borosilicate glass microspheres. For this, glass with composition (mol%) 16.6Na2O-17.4 B2O3-66.0SiO2 was synthesized by melt-quench method. The studies were carried out at accelerated conditions of 120°C at different exposure hours, maximum upto 55 hrs in distilled water (DW). Studies on accelerated conditions helps in predicting long-term durability of the glass. The glass was taken in the form of micro spheres of 75 - 125 micron range. Glass microspheres were selected for the study as they have the advantage of maximum surface area. Their weight loss and surface study using SEM and SAXS were carried out intermittently. The weight loss observed was negligible even after 55 hrs of exposure at 120°C in DW. The interesting phenomenon of leaching were observed by SEM and SAXS studies. Initially few pore formation on the surface of spheres which grew in size and numerals followed by layer removal were observed by SAXS. On the removal of outer layer, inner exposed surface were leached in a similar pattern with pore formation. Initially only a few spheres were leached and gradually the intensity of leached spheres increased which was observed by SEM studies. The elemental analysis of the surface of leached and unleached spheres were carried out. The analysis showed the decrease in concentration of sodium on the leached layer. (author)

  7. Determination of the free enthalpies of formation of borosilicate glasses

    International Nuclear Information System (INIS)

    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)

  8. Commercial Ion Exchange Resin Vitrification in Borosilicate Glass

    International Nuclear Information System (INIS)

    Bench-scale studies were performed to determine the feasibility of vitrification treatment of six resins representative of those used in the commercial nuclear industry. Each resin was successfully immobilized using the same proprietary borosilicate glass formulation. Waste loadings varied from 38 to 70 g of resin/100 g of glass produced depending on the particular resin, with volume reductions of 28 percent to 68 percent. The bench-scale results were used to perform a melter demonstration with one of the resins at the Clemson Environmental Technologies Laboratory (CETL). The resin used was a weakly acidic meth acrylic cation exchange resin. The vitrification process utilized represented a approximately 64 percent volume reduction. Glass characterization, radionuclide retention, offgas analyses, and system compatibility results will be discussed in this paper

  9. Barium borosilicate glass as a matrix for the uptake of dyes

    International Nuclear Information System (INIS)

    Barium borosilicate (BBS) and sodium borosilicate (SBS) glass samples, prepared by the conventional melt-quench method, were used for the uptake of Rhodamine 6G dye from aqueous solution. The experimental conditions were optimized to get maximum uptake and was found to be 0.4 mg of dye per gram of BBS glass sample. For the same network former to modifier ratio, barium borosilicate glasses are found to have improved extent of uptake for the dye molecules from aqueous solutions compared to sodium borosilicate glasses. Based on 29Si MAS NMR studies on these glasses, it is inferred that significantly higher number of non-bridging oxygen atoms present in barium borosilicate glasses compared to sodium borosilicate glasses is responsible for its improved uptake of Rhodamine 6G dye. 11B MAS NMR studies have confirmed the simultaneous existence of boron in BO3 and BO4 configurations in both barium borosilicate and sodium borosilicate glasses. The luminescence studies have established that the dye molecule is incorporated into the glass matrix through ion exchange mechanism by replacing the exchangeable ions like Na+/Ba2+ attached with the non-bridging oxygen atoms present in the glass.

  10. Leaching of borosilicate glasses incorporating H.L. radioactive wastes

    International Nuclear Information System (INIS)

    The european community commission organized in the period 1983-84 an international round robin test aiming at the evaluation of a method for controlling the high-temperature leaching resistance of borosilicate glasses incorporating high-level radioactive wastes. The radwaste experimental processes laboratory of the COMB/MEPIS Division, in collaboration with the Analytical Chemistry Laboratory of the TIB/CHI Division, partecipated to this round robin test with other 12 european and 2 extra european laboratories. In this paper the main results obtained in thi partecipation are reported

  11. Gadolinium borosilicate glass-bonded Gd-silicate apatite: a glass-ceramic nuclear waste form for actinides

    International Nuclear Information System (INIS)

    A Gd-rich crystalline phase precipitated in a sodium gadolinium alumino-borosilicate glass during synthesis. The glass has a chemical composition of 45.4-31.1 wt% Gd2O3, 28.8-34.0 wt% SiO2,10.8-14.0 wt% Na2O, 4.3-5.9 wt% Al2O3, and 10.8-14.9 wt% B2O3. Backscattered electron images revealed that the crystals are hexagonal, elongated, acicular, prismatic, skeletal or dendritic, tens of μm in size, some reaching 200 μm in length. Electron microprobe analysis confirmed that the crystals are chemically homogeneous and have a formula of NaGd9(SiO4)6O2 with minor B substitution for Si. The X-ray diffraction pattern of this phase is similar to that of lithium gadolinium silicate apatite. Thus, this hexagonal phase is a rare earth silicate with the apatite structure. We suggest that this Gd-silicate apatite in a Gd-borosilicate glass is a potential glass-ceramic nuclear waste form for actinide disposition. Am, Cm and other actinides can easily occupy the Gd-sites. The potential advantages of this glass-ceramic waste form include: 1) both the glass and apatite can be used to immobilize actinides, 2) silicate apatite is thermodynamically more stable than the glass, 3) borosilicate glass-bonded Gd-silicate apatite is easily fabricated, and 4) the Gd is an effective neutron absorber.Copyright (2001) Material Research Society

  12. Boron Speciation in Soda-Lime Borosilicate Glasses Containing Zirconium

    International Nuclear Information System (INIS)

    Boron speciation was investigated in soda-lime borosilicate glass containing zirconium. In such compositions, competition between charge compensators (here, sodium and calcium) can occur for the compensation of tetrahedral boron or octahedral zirconium units. 11B MAS NMR is particularly suitable for obtaining data on preferential compensation behavior that directly affects the boron coordination number. In addition to the classical proportions of tri- and tetrahedral boron, additional data can be obtained on the contributions involved in these two coordination numbers. An approach is described here based on simultaneous MAS spectrum analysis of borosilicate glass with variable Zr/Si and Ca/Na ratios at two magnetic field strengths (11. 7 and 18. 8 T), with constraints arising from MQMAS spectroscopy, detailed analysis of satellite transitions, and spin-echo experiments. New possibilities of 11B NMR were presented for improving the identification and quantification of the different contributions involved in tri- and tetrahedral boron coordination. Both NMR and Raman revealed a trend of decreased tetrahedral boron proportion with the increase of Ca/Na ratio or the Zr/Si ratio. This strongly suggests that zirconium compensation takes preference over boron compensation, and that zirconium and boron are both compensated mainly by sodium rather than calcium. (authors)

  13. Enhancing cerium and plutonium solubility by reduction in borosilicate glass

    Science.gov (United States)

    Cachia, J.-N.; Deschanels, X.; Den Auwer, C.; Pinet, O.; Phalippou, J.; Hennig, C.; Scheinost, A.

    2006-06-01

    High-level radioactive wastes produced by spent fuel reprocessing containing fission and activation products as well as actinides are incorporated in a borosilicate glass. To ensure optimum radionuclide containment, the resulting glass must be as homogeneous as possible. Microscopic heterogeneity can arise from various processes including the excess loading of an element above its solubility limit. The current actinide loading limit is 0.4 wt%. Work is in progress to assess the actinide solubility in these glasses, especially for plutonium. Initially the actinides were simulated by lanthanides and hafnium. The results show that trivalent elements (La, Gd) exhibit greater solubility than tetravalent elements (Pu, Hf). Cerium is an interesting element because its oxidation state varies from IV to III depending on the process conditions, such as the temperature and redox potential of the melt. In order to quantify the solubility increase, cerium-doped glass samples were melted under reducing conditions by adding a reducing agent. The solubility observed at 1473 K increased significantly from 0.95 to 13.00 wt%. Several reducing compounds have been tested. This paper deals with this study and the application to reduce Pu(IV) to Pu(III). The reduction state was characterized by X-ray absorption spectroscopy (XANES) for plutonium and by chemical analysis for cerium. The material homogeneity was verified by optical and scanning electron microscopy. Preliminary findings concerning the reduction of Pu-doped glasses fabricated in hot cells are also discussed.

  14. Borosilicate glass as a matrix for the immobilization of Savannah River Plant waste

    International Nuclear Information System (INIS)

    The reference waste form for immobilization of Savannah River Plant (SRP) waste is borosilicate glass. In the reference process, waste is mixed with glass-forming chemicals and melted in a Joule-heated ceramic melter at 11500C. Waste glass made with actual or simulated waste on a small scale and glass made with simulated waste on a large scale confirm that the current reference process and glass-former composition are able to accommodate all SRP waste compositions and can produce a glass with: high waste loading; low leach rates; good thermal stability; high resistance to radiation effects; and good impact resistance. Borosilicate glass has been studied as a matrix for the immobilization of SRP waste since 1974. This paper reviews the results of extensive characterization and performance testing of the glass product. These results show that borosilicate glass is a very suitable matrix for the immobilization of SRP waste. 18 references, 3 figures, 10 tables

  15. Methanobactin-Promoted Dissolution of Cu-Substituted Borosilicate Glass

    Science.gov (United States)

    Kulczycki, E.; Fowle, D. A.; Knapp, C.; Graham, D. W.; Roberts, J. A.

    2006-12-01

    Mineral weathering processes play a major role in the global cycling of carbon and metals and there is an increasing realization that subsurface microbial activity may be a key factor regulating specific biogeochemical reactions and their rates. Methanobactin (mb) is an extracellular copper-binding compound excreted by methanotrophs who require copper to regulate methane oxidation. Cu that is available to the cell regulates the expression and activity of pMMO versus sMMO (particulate versus soluble methane monooxygenase, respectively), which are key enzymes responsible for methane oxidation. The primary focus of this study is to determine the effect of mb-promoted dissolution of Cu-substituted glass at low temperature and near neutral pH conditions, using batch dissolution experiments with and without the methanotroph, Methylonsinus trichosporium OB3b. Methanobactin promotes the weathering of Cu-substituted borosilicate glasses at rates faster than control experiments without methanobactin. Glasses with lower concentrations of copper (80 ppm) or no copper are dissolved more rapidly than those containing larger amounts of copper (800 ppm). Within the first 2 hours of reactivity, a greater quantity of mb appears to sorb onto the glass surface at higher copper concentrations and may limit mass transfer of Cu to solution. Furthermore gene expression in M. trichosporium OB3b, using real-time RT-PCR techniques, indicate that pmoA expression is influenced by mb in presence of Cu containing solid phases. These findings demonstrate that this methanotroph can directly access mineral-bound Cu and suggests that methane oxidation rates may be directly linked to mineral weathering in near-surface geologic settings.

  16. IR study of Pb–Sr titanate borosilicate glasses

    Indian Academy of Sciences (India)

    C R Gautam; Devendra Kumar; Om Parkash

    2010-04-01

    The infrared spectra (IR) of various glass compositions in the glass system, [(PbSr1–)O.TiO2]– [2SiO2.B2O3]–[BaO.K2O]–[La2O3], were recorded over a continuous spectral range (400–4000 cm-1) to study their structure systematically. IR spectrum of each glass composition shows a number of absorption bands. These bands are strongly influenced by the increasing substitution of SrO for PbO. Various bands shift with composition. Absorption peaks occur due to the vibrational mode of the borate network in these glasses. The vibrational modes of the borate network are seen to be mainly due to the asymmetric stretching relaxation of the B–O bond of trigonal BO3 units. More splitting is observed in strontium-rich composition.

  17. Speciation of U and Am in sol-gel derived borosilicate glasses by photoluminescence lifetime spectroscopy

    International Nuclear Information System (INIS)

    Borosilicate glasses are intended to be the barrier in between the high level nuclear waste and the geosphere. The oxidation state and the coordination geometry of a particular element in the glass influences its solubility, migration and complexation behavior, which in turn influences its long term leaching behavior. In this context, uranium and americium containing barium borosilicate glasses were prepared by sol-gel route and the speciation studies of U and Am in the glasses were carried out using photoluminescence lifetime spectroscopic technique. It was observed that in the matrix the uranium is stabilised as (UO6)6- and the americium as Am3+. (author)

  18. The Effect of Sm2O3 on the Chemical Stability of Borosilicate Glass and Glass Ceramics

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yongqiang; WANG Mitang; LI Mei; WANG Ming; LIU Quansheng

    2014-01-01

    Sm2O3 containing zinc-borosilicate glass and glass ceramics were prepared by melt quenching method, and the effect of Sm2O3 and micro-crystallization on the chemical stability of borosilicate glass was explored. DTA analysis showed that the endothermic peak and exothermic peak of basic glass changed from 635℃and 834℃to 630℃and 828℃respectively as a result of the doping of Sm2O3. XRD analysis showed the promoting effect of Sm2O3 on crystallization ability of this glass. The cumulative mass loss of base glass, Sm2O3 containing glass, glass ceramic and Sm2O3 containing glass ceramic was 0.289, 0.253, 0.329, 0.269 mg/mm2 respectively after 26 days corrosion in alkali solution, and 1.293, 1.290, 0.999, 1.040 mg/mm2 respectively in acidic erosion medium. Micro-crystallization decreased and improved the alkali and acid resistance of borosilicate glass respectively, the addition of Sm2O3 increased the alkali resistance of base glass and glass ceramics, and the slight effect of Sm2O3 on the acid resistance of borosilicate glass was also observed.

  19. Removal of OH Absorption Bands Due to Pyrohydrolysis Reactions in Fluoride-Containing Borosilicate Glasses

    Science.gov (United States)

    Kobayashi, Keiji

    1997-05-01

    The purpose of this study is to decrease and to remove OH ions and H2O in borosilicate glasses. Fluoride-containing borosilicate glasses followed by dry-air-bubbling showed the significant decrease of OH absorption bands around 3500 cm-1. The decrease of OH absorption bands was elucidated by the use of pyrohydrolysis reactions in these glasses where fluoride ions react with OH ions or H2O during melting. The rates of the decrease of OH absorption bands substantially depend on high valence cations of fluorides. Particularly, the decrease rates of OH absorption coefficients were in the order of ZrF4-containing glass>AlF3-containing glass>ZnF2-containing glass. ZrF4-containing glass treated by dry-air-bubbling showed a good capability to remove OH absorption band. Fluoride-containing glasses showed the low flow point in comparison with fluoride-free glasses.

  20. A kinetic approach of sulphur behaviour in borosilicate glasses and melts: implications for sulphate incorporation in nuclear waste glasses

    International Nuclear Information System (INIS)

    The kinetics of sulphate decomposition in a borosilicate melt were studied using in situ Raman spectroscopy. This technique permits the quantification of the amount of sulphate dissolved in a borosilicate glass as a function of heating time by comparison with measurements obtained by microprobe WDS (Wavelength Dispersive Spectrometry). In order to quantify the content of sulphate obtained by Raman spectroscopy, the integrated intensity of the sulphate band at 985 cm-1 was scaled to the sum of the integrated bands between 800 and 1200 cm-1, bands that are assigned to Qn silica units on the basis of previous literature. Viscosities of some borosilicate glasses are also presented here in order to study the kinetics of sulphate decomposition as a function of the viscosity of the melt. This underlines the importance of variations in viscosity depending on the composition of the melt and thus shows that viscosity is an important parameter governing the kinetics of decomposition of sulphate in borosilicate glasses. (authors)

  1. LIQUIDUS TEMPERATURE OF HIGH-LEVEL WASTE BOROSILICATE GLASSES WITH SPINEL PRIMARY PHASE

    Science.gov (United States)

    Liquidus temperatures (TL) were measured for high-level waste (HLW) borosilicate glasses covering a Savannah River composition region. The primary crystallization phase for most glasses was spinel, a solid solution of trevorite (NiFe2O4) with other oxides (FeO, MnO, and Cr2O3). T...

  2. ORIGEN-S (α,n) neutron source spectra in borosilicate glass containing HLW

    International Nuclear Information System (INIS)

    There is growing interest in the methodology and computational software for evaluating the (α,n) source spectra produced in mixtures of high-level waste (HLW) and borosilicate glass. The need for this development has been seen in previous work involving the analysis of HLW in borosilicate glass. Descriptions and applications of the ORIGEN-S method of computing neutron source spectra by both (α,n) reactions and spontaneous fission of UO2 spent fuel have been reported previously. This summary presents a significant expansion of the ORIGEN-S (α,n) model to include alpha interactions with the light elements of borosilicate glass. The Battelle/Office of Nuclear Waste Isolation requested this model extension. There is an associated interest in the use of Oak Ridge National Lab. shielding codes for analyzing HLW systems

  3. Immobilization of simulated high-level liquid wastes in sintered borosilicate, aluminosilicate and aluminoborosilicate glasses

    International Nuclear Information System (INIS)

    The purpose of this paper is to report on the results obtained with different vitreous materials: a German borosilicate glass (VG98/12), its local counterpart (Simil VG), a natural aluminosilicate volcanic glass (VV), and two German aluminoborosilicate glasses (SG7 and SG8), with incorporated simulated high-level liquid wastes (HLLW), LWR and PHWR types. The optimal conditions for pressure and pressureless sintering are given, as well as the simulation, formulation and preparation of the simulated HLLW type PHWR, as well as the corrosion and thermal behavior of the waste forms obtained. Leaching rates of aluminosilicate (VV) and aluminoborosilicate (SG7) glasses were about 10-2 g m-2 d-1, that is one order of magnitude lower than those for borosilicate glasses. The devitrification of aluminoborosilicate glass (SG7) increased leaching rate by a factor of 3 for Mo. (orig.)

  4. Monte Carlo Simulations of Coupled Diffusion and Surface Reactions during the Aqueous Corrosion of Borosilicate Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Kerisit, Sebastien N.; Pierce, Eric M.; Ryan, Joseph V.

    2015-01-01

    Borosilicate nuclear waste glasses develop complex altered layers as a result of coupled processes such as hydrolysis of network species, condensation of Si species, and diffusion. However, diffusion has often been overlooked in Monte Carlo models of the aqueous corrosion of borosilicate glasses. Therefore, three different models for dissolved Si diffusion in the altered layer were implemented in a Monte Carlo model and evaluated for glasses in the compositional range (75-x) mol% SiO2 (12.5+x/2) mol% B2O3 and (12.5+x/2) mol% Na2O, where 0 ≤ x ≤ 20%, and corroded in static conditions at a surface-to-volume ratio of 1000 m-1. The three models considered instantaneous homogenization (M1), linear concentration gradients (M2), and concentration profiles determined by solving Fick’s 2nd law using a finite difference method (M3). Model M3 revealed that concentration profiles in the altered layer are not linear and show changes in shape and magnitude as corrosion progresses, unlike those assumed in model M2. Furthermore, model M3 showed that, for borosilicate glasses with a high forward dissolution rate compared to the diffusion rate, the gradual polymerization and densification of the altered layer is significantly delayed compared to models M1 and M2. Models M1 and M2 were found to be appropriate models only for glasses with high release rates such as simple borosilicate glasses with low ZrO2 content.

  5. High-level waste glass compendium; what it tells us concerning the durability of borosilicate waste glass

    International Nuclear Information System (INIS)

    Facilities for vitrification of high-level nuclear waste in the United States are scheduled for startup in the next few years. It is, therefore, appropriate to examine the current scientific basis for understanding the corrosion of high-level waste borosilicate glass for the range of service conditions to which the glass products from these facilities may be exposed. To this end, a document has been prepared which compiles worldwide information on borosilicate waste glass corrosion. Based on the content of this document, the acceptability of canistered waste glass for geological disposal is addressed. Waste glass corrosion in a geologic repository may be due to groundwater and/or water vapor contact. The important processes that determine the glass corrosion kinetics under these conditions are discussed based on experimental evidence from laboratory testing. Testing data together with understanding of the long-term corrosion kinetics are used to estimate radionuclide release rates. These rates are discussed in terms of regulatory performance standards

  6. High-level waste borosilicate glass: A compendium of corrosion characteristics. Volume 3

    Energy Technology Data Exchange (ETDEWEB)

    Cunnane, J.C. [comp.; Bates, J.K.; Bradley, C.R. [Argonne National Lab., IL (United States)] [and others

    1994-03-01

    The objective of this document is to summarize scientific information pertinent to evaluating the extent to which high-level waste borosilicate glass corrosion and the associated radionuclide release processes are understood for the range of environmental conditions to which waste glass may be exposed in service. Alteration processes occurring within the bulk of the glass (e.g., devitrification and radiation-induced changes) are discussed insofar as they affect glass corrosion. Volume III contains a bibliography of glass corrosion studies, including studies that are not cited in Volumes I and II.

  7. High-level waste borosilicate glass: A compendium of corrosion characteristics. Volume 3

    International Nuclear Information System (INIS)

    The objective of this document is to summarize scientific information pertinent to evaluating the extent to which high-level waste borosilicate glass corrosion and the associated radionuclide release processes are understood for the range of environmental conditions to which waste glass may be exposed in service. Alteration processes occurring within the bulk of the glass (e.g., devitrification and radiation-induced changes) are discussed insofar as they affect glass corrosion. Volume III contains a bibliography of glass corrosion studies, including studies that are not cited in Volumes I and II

  8. Dielectric behaviour of (Ba,Sr)TiO3 perovskite borosilicate glass ceramics

    International Nuclear Information System (INIS)

    Various perovskite (Ba,Sr)TiO3 borosilicate glasses were prepared by rapid melt-quench technique in the glass system ((Ba1-xSrx).TiO3)-(2SiO2.B2O3)-(K2O)-(La2O3). On the basis of differential thermal analysis results, glasses were converted into glass ceramic samples by regulated heat treatment schedules. The dielectric behaviour of crystallized barium strontium titanate borosilicate glass ceramic samples shows diffuse phase transition. The study depicts the dielectric behaviour of glass ceramic sample BST5K1L0.2S814. The double relaxation was observed in glass ceramic samples corresponding 80/20% Ba/Sr due to change in crystal structure from orthorhombic to tetragonal and tetragonal to cubic with variation of temperature. The highest value of dielectric constant was found to be 48289 for the glass ceramic sample BST5K1L0.2S814. The high value of dielectric constant attributed to space charge polarization between the glassy phase and perovskite phase. Due to very high value of dielectric constant, such glass ceramics are used for high energy storage devices. La2O3 acts as nucleating agent for crystallization of glass to glass ceramics and enhances the dielectric constant and retarded dielectric loss. Such glass ceramics can be used in high energy storage devices such as barrier layer capacitors, multilayer capacitors etc. (author)

  9. High-level waste borosilicate glass a compendium of corrosion characteristics. Volume 1

    International Nuclear Information System (INIS)

    Current plans call for the United States Department of Energy (DOE) to start up facilities for vitrification of high-level radioactive waste (HLW) stored in tanks at the Savannah River Site, Aiken, South Carolina, in 1995; West Valley Demonstration Project, West Valley, New York, in 1996; and at the Hanford Site, Richland, Washington, after the year 2000. The product from these facilities will be canistered HLW borosilicate glass, which will be stored, transported, and eventually disposed of in a geologic repository. The behavior of this glass waste product, under the range of likely service conditions, is the subject of considerable scientific and public interest. Over the past few decades, a large body of scientific information on borosilicate waste glass has been generated worldwide. The intent of this document is to consolidate information pertaining to our current understanding of waste glass corrosion behavior and radionuclide release. The objective, scope, and organization of the document are discussed in Section 1.1, and an overview of borosilicate glass corrosion is provided in Section 1.2. The history of glass as a waste form and the international experience with waste glass are summarized in Sections 1.3 and 1.4, respectively

  10. Influence of (Na2O-Al2O3)/B2O3 on Viscosity and Thermal Properties of Silica-rich Borosilicate Glasses%(Na2O-Al2O3)/B2O3对高硼硅酸盐玻璃粘度和热学性能的影响

    Institute of Scientific and Technical Information of China (English)

    何峰; 平财明; 郑媛媛; 乔勇

    2013-01-01

    采用熔融冷却法制备了不同R’系数的高硼硅酸盐玻璃,其中R’=(Na2O-Al2O3)/B2O3.利用红外光谱、高温旋转粘度计和热膨胀仪等对玻璃的结构和性能进行表征.结果表明:高温段粘度-温度关系符合阿伦尼乌斯定律;R’值的增大导致非桥氧的增加,高温粘度和熔制温度呈显著降低.当R’>0.5时,热膨胀系数近似线性增大,玻璃化转变温度增大至590℃基本维持不变.R’值影响结构中的[BO3]与[BO4]的比例及硅氧网络的完整程度,从而决定高硼硅酸盐玻璃的性能.%Silica-rich sodium borosilicate glasses with varying R' values have been prepared using conventional melt quenching method,where R' represents the ratio of (Na2O-Al2O3) and B2O3.The structure and properties have been investigated by the FTIR spectra,rotating crucible viscometer and thermal expanse dilatometer.The results show that the viscosity dependence of temperature is accord with Arrhenius law in the high temperature range.The non-bridging oxygen increases due to the increase of R',which leads to obvious decease of high temperature viscosity and melting temperature.Thermal expanse coefficient increases linearly with R' when R' exceeds 0.5,and the glass transformation temperature increases to 590 ℃.The fraction of [BO3] and [BO4] and the integrity of Si-O network are controlled mainly by R',then decide properties of borosilicate glasses.

  11. Electron irradiation effect on bubble formation and growth in a sodium borosilicate glass

    International Nuclear Information System (INIS)

    In this study, the authors studied simultaneous and intermittent electron irradiation effects on bubble growth in a simple sodium borosilicate glass during Xe ion implantation at 200 C. Simultaneous electron irradiation increases the average bubble size in the glass. This enhanced diffusion is also shown by the migration of Xe from bubbles into the matrix when the sample is irradiated by an electron beam after the Xe implantation

  12. Chemical durability of lead borosilicate glass matrix under simulated geological conditions

    International Nuclear Information System (INIS)

    The lead borosilicate glass has been developed for vitrification of High Level Waste (HLW) stored at Trombay. This waste is contains especially high contents of sodium, uranium sulphate and iron. The glasses containing HLW are to be ultimately disposed into deep geological repositories. Long term leach rates under simulated geological conditions need to be evaluated for glass matrix. Studies were taken up to estimate the lead borosilicate glass WTR-62 matrix for chemical durability in presence of synthetic ground water. The leachant selected was based on composition of ground water sample near proposed repository site. In the first phase of these tests, the experiments were conducted for short duration of one and half month. The leaching experiments were conducted in presence of a) distilled water b) synthetic ground water c) synthetic ground water containing granite, bentonite and ferric oxide and d) synthetic ground water containing humic acid at 1000C. The leachate samples were analysed by pHmetry , ion chromatography and UV -VIS spectrophotometry. The normalised leach rates for lead borosilicate WTR- 62 glass matrix based on silica, boron and sulphate analyses of leachates were of the order of 10-3 to 10-5 gms/cm2/day for 45 days test period in presence of synthetic ground water as well as in presence of other materials likely to be present along with synthetic ground water. These rates are comparable to those of sodium borsilicate glass matrices reported in literature. It is known that the leach rates of glass matrix decrease with longer test durations due to formation of leached layer on its surface. The observed leach rates of lead borosilicate WTR- 62 glass matrix for 45 day tests under simulated geological conditions were found to be sufficiently encouraging to take up long term tests for evaluating its performances under repository conditions. (author)

  13. Structural aspects of barium borosilicate glasses containing thorium and uranium oxides

    International Nuclear Information System (INIS)

    Barium borosilicate glasses incorporated with 15.86 wt% ThO2 and containing different amounts of uranium oxide were prepared by conventional melt quench method. Based on 29Si and 11B magic angle spinning nuclear magnetic resonance (MAS NMR) studies, it has been confirmed that uranium oxide incorporation is associated with distortion of borosilicate network as revealed by the increase in the relative concentration of Q2 structural units of silicon as well as the increase in the quadrupolar coupling constant (C q) of BO3 structural units. The increased number of non-bridging oxygen atoms brought about by the increase in Q2 structural units of silicon facilitates the incorporation of both uranium and thorium ions in the sites created by non-bridging oxygen atoms (network modifying positions) in the glass. Uranium oxide incorporation above 7.5 wt% resulted in the phase separation of ThO2 as revealed by the X-ray diffraction studies. The present study focuses on the structural changes with the borosilicate network of barium borosilicate glasses brought about by the introduction of thorium and uranium ions

  14. PLUTONIUM SOLUBILITY IN HIGH-LEVEL WASTE ALKALI BOROSILICATE GLASS

    Energy Technology Data Exchange (ETDEWEB)

    Marra, J.; Crawford, C.; Fox, K.; Bibler, N.

    2011-01-04

    The solubility of plutonium in a Sludge Batch 6 (SB6) reference glass and the effect of incorporation of Pu in the glass on specific glass properties were evaluated. A Pu loading of 1 wt % in glass was studied. Prior to actual plutonium glass testing, surrogate testing (using Hf as a surrogate for Pu) was conducted to evaluate the homogeneity of significant quantities of Hf (Pu) in the glass, determine the most appropriate methods to evaluate homogeneity for Pu glass testing, and to evaluate the impact of Hf loading in the glass on select glass properties. Surrogate testing was conducted using Hf to represent between 0 and 1 wt % Pu in glass on an equivalent molar basis. A Pu loading of 1 wt % in glass translated to {approx}18 kg Pu per Defense Waste Processing Facility (DWPF) canister, or about 10X the current allowed limit per the Waste Acceptance Product Specifications (2500 g/m{sup 3} of glass or about 1700 g/canister) and about 30X the current allowable concentration based on the fissile material concentration limit referenced in the Yucca Mountain Project License Application (897 g/m{sup 3}3 of glass or about 600 g Pu/canister). Based on historical process throughput data, this level was considered to represent a reasonable upper bound for Pu loading based on the ability to provide Pu containing feed to the DWPF. The task elements included evaluating the distribution of Pu in the glass (e.g. homogeneity), evaluating crystallization within the glass, evaluating select glass properties (with surrogates), and evaluating durability using the Product Consistency Test -- Method A (PCT-A). The behavior of Pu in the melter was evaluated using paper studies and corresponding analyses of DWPF melter pour samples.The results of the testing indicated that at 1 wt % Pu in the glass, the Pu was homogeneously distributed and did not result in any formation of plutonium-containing crystalline phases as long as the glass was prepared under 'well-mixed' conditions

  15. Influence of processing conditions on the glass-crystal transition into borosilicate glasses

    International Nuclear Information System (INIS)

    The precipitation of a crystalline phase in glass is observed when one element exceeds its loading limit (i.e.: solubility limit). In this work we have studied the solubility of different actinides and surrogates (lanthanides and hafnium) in borosilicate glass used for the immobilization of the high-level nuclear waste (HLW glasses). The results obtained show an increase of the solubility limits of these elements with the processing temperature and the redox potential of the melt. The elements at the oxidation state (III) exhibit a higher solubility than the element at oxidation state (IV). In this framework, cerium is an interesting element because its oxidation state tunes from (IV) to (III) as a function of the processing conditions. It is shown that the solubility of cerium can be multiplied by a factor of 20 at 1100 C. degrees. In order to have a better understanding of the mechanisms that underline the evolution of the solubility, XAFS and NMR investigation has been undertaken. Trivalent elements present the characteristics of network-modified cations while tetravalent elements look like network-former cations

  16. Structural and optical properties of barium borosilicate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Vishal; Pandey, O.P. [School of Physics and Materials and Science, Thapar University, Patiala 147004 (India); Singh, K., E-mail: kusingh@thapar.ed [School of Physics and Materials and Science, Thapar University, Patiala 147004 (India)

    2010-01-01

    The 40SiO{sub 2}-30BaO-20B{sub 2}O{sub 3}-10A{sub 2}O{sub 3} (A=Y, La, Al, Cr) glasses were synthesized by melt quenching at 1550 deg. C. Controlled crystallization was carried out to convert these glasses to corresponding glass ceramics. The amorphous nature of as prepared glasses was ascertained from XRD diffraction pattern. Fourier-transform infrared spectroscopy was done to find out the basic structural units in these glasses. The effect of intermediate oxides on optical properties was investigated using UV-Visible spectra.

  17. Structural and optical properties of barium borosilicate glasses

    International Nuclear Information System (INIS)

    The 40SiO2-30BaO-20B2O3-10A2O3 (A=Y, La, Al, Cr) glasses were synthesized by melt quenching at 1550 deg. C. Controlled crystallization was carried out to convert these glasses to corresponding glass ceramics. The amorphous nature of as prepared glasses was ascertained from XRD diffraction pattern. Fourier-transform infrared spectroscopy was done to find out the basic structural units in these glasses. The effect of intermediate oxides on optical properties was investigated using UV-Visible spectra.

  18. Gamma-ray shielding and structural properties of barium-bismuth-borosilicate glasses

    Science.gov (United States)

    Bootjomchai, Cherdsak; Laopaiboon, Jintana; Yenchai, Chadet; Laopaiboon, Raewat

    2012-07-01

    The attenuation coefficients of barium-bismuth-borosilicate glasses have been measured for gamma-ray photon energies of 662, 1173 and 1332 keV using a narrow beam transmission geometry. These coefficients were then used to obtain the values of mass attenuation coefficients, effective atomic number, effective electron density and mean free path. Good agreement has been observed between experimental and theoretical values of these parameters. From the obtained results it is reported here that from the barium-bismuth-borosilicate glasses are better shields to gamma-radiations in comparison to the standard radiation shielding concretes from the shielding point of view. The molar volume, FTIR and acoustic investigations have been used to study the structural properties of the prepared glass system. The obtained results reveal that the formation of non-bridging oxygens occurs at higher concentration of Bi2O3.

  19. Effect of heat treatment on the infrared absorption spectra of strontium-sodium-borosilicate glass

    International Nuclear Information System (INIS)

    Infrared absorption spectra of the prepared strontium-sodium-borosilicate glass (SiO2 80%-Na2O 12.5%-B2O3 5%-SrO 2.5%) are studied in the frequency range 200-4000 cm-1, where strontium oxide was introduced on partial replacement of soda in sodium-borosilicate glass, to show the effect of divalent metal oxide introduced on the structural units SiO4, BO4, and BO3 within the network structure of strontium-sodium-borosilicate glass, in the temperature range 27-800 degC. The deformation of SiO4 tetrahedra is investigated by using the baseline method, the temperature dependence of the relative integrated intensity, the relaxation time, and rotational energy barrier of this glass proved that the glassy phase is transformed to crystalline phase at 500 degC. A slight shift occurs in the strongest bands of SiO4 tetrahedra to higher frequencies, with temperature increase, which indicates an increase in the force constants between the components of the glass network structure. The increase of the absorbance in the temperature range 600-800 degC indicates strengthening of the SiO4 bonds. (author)

  20. Fabrication of Low Noise Borosilicate Glass Nanopores for Single Molecule Sensing

    Science.gov (United States)

    Bafna, Jayesh A.; Soni, Gautam V.

    2016-01-01

    We show low-cost fabrication and characterization of borosilicate glass nanopores for single molecule sensing. Nanopores with diameters of ~100 nm were fabricated in borosilicate glass capillaries using laser assisted glass puller. We further achieve controlled reduction and nanometer-size control in pore diameter by sculpting them under constant electron beam exposure. We successfully fabricate pore diameters down to 6 nm. We next show electrical characterization and low-noise behavior of these borosilicate nanopores and compare their taper geometries. We show, for the first time, a comprehensive characterization of glass nanopore conductance across six-orders of magnitude (1M-1μM) of salt conditions, highlighting the role of buffer conditions. Finally, we demonstrate single molecule sensing capabilities of these devices with real-time translocation experiments of individual λ-DNA molecules. We observe distinct current blockage signatures of linear as well as folded DNA molecules as they undergo voltage-driven translocation through the glass nanopores. We find increased signal to noise for single molecule detection for higher trans-nanopore driving voltages. We propose these nanopores will expand the realm of applications for nanopore platform. PMID:27285088

  1. Vanadium and Chromium Redox Behavior in borosilicate Nuclear Waste Glasses

    International Nuclear Information System (INIS)

    X-ray absorption spectroscopy (XAS) was used to characterize vanadium (V) and chromium (Cr) environments in low activity nuclear waste (LAW) glasses synthesized under a variety of redox conditions. V2O5 was added to the melt to improve sulfur incorporation from the waste; however, at sufficiently high concentrations, V increased melt foaming, which lowered melt processing rates. Foaming may be reduced by varying the redox conditions of the melt, while small amounts of Cr are added to reduce melter refractory corrosion. Three parent glasses were studied, where CO-CO2 mixtures were bubbled through the corresponding melt for increasing time intervals so that a series of redox-adjusted-glasses was synthesized from each parent glass. XAS data indicated that V and Cr behaviors are significantly different in these glasses with respect to the cumulative gas bubbling times: V4+/Vtotal ranges from 8 to 35%, while Cr3+/Crtotal can range from 15 to 100% and even to population distributions including Cr2+. As Na-content decreased, V, and especially, Cr became more reduced, when comparing equivalent glasses within a series. The Na-poor glass series show possible redox coupling between V and Cr, where V4+ populations increase after initial bubbling, but as bubbling time increases, V4+ populations drop to near the level of the parent glass, while Cr becomes more reduced to the point of having increasing Cr2+ populations.

  2. In-vitro bioactivity of zirconia doped borosilicate glasses

    International Nuclear Information System (INIS)

    Glass composition 31B2O3-20SiO2-24.5Na2O-(24.5-x) CaO-xZrO2 x=1,2,3,4,5 were prepared by melt-quenching Technique. The formation of hydroxyapatite layer on the surface of glasses after immersion in simulated body fluid (SBF) was explored through XRD, Fourier transform infrared (FTIR) and Scanning electron microscopy (SEM-EDX) analyses. In this report, we observed that hydroxyapatite formation for 5days of immersion time. Also observed that with increasing the immersion time up to 15days, higher amount of hydroxyapatite layer formation on the surface of glasses. The varying composition of zirconia in glass samples influences shown by XRD, FTIR studies. The present results indicate that, in-vitro bioactivity of glasses decreased with increasing zirconia incorporation

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

    International Nuclear Information System (INIS)

    Procedures and techniques were evaluated to mitigate thermal stress fracture in waste glass as the glass cools after casting. The two principal causes of fracture identified in small-scale testing are internal thermal stresses arising from excessive thermal gradients when cooled too fast, and shear fracturing in the surface of the glass because the stainless steel canister shrinks faster than the glass on cooling. Acoustic emission and ceramographic techniques were used to outline an annealing schedule that requires at least three weeks of controlled cooling below 5500C to avoid excessive thermal gradients and corresponding stresses. Fracture arising from canister interactions cannot be relieved by slow cooling, but can be eliminated for stainless steel canisters by using ceramic paper, ceramic or graphite paste linings, or by choosing a canister material with a thermal expansion coefficient comparable to, or less than, that of the glass

  4. In-vitro bioactivity of zirconia doped borosilicate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Samudrala, Rajkumar; Azeem, P. Abdul, E-mail: rk.satyaswaroop@gmail.com, E-mail: drazeem2002@yahoo.com [Department of Physics, National Institute of Technology, Warangal-506004 (India)

    2015-06-24

    Glass composition 31B{sub 2}O{sub 3}-20SiO{sub 2}-24.5Na{sub 2}O-(24.5-x) CaO-xZrO{sub 2} x=1,2,3,4,5 were prepared by melt-quenching Technique. The formation of hydroxyapatite layer on the surface of glasses after immersion in simulated body fluid (SBF) was explored through XRD, Fourier transform infrared (FTIR) and Scanning electron microscopy (SEM-EDX) analyses. In this report, we observed that hydroxyapatite formation for 5days of immersion time. Also observed that with increasing the immersion time up to 15days, higher amount of hydroxyapatite layer formation on the surface of glasses. The varying composition of zirconia in glass samples influences shown by XRD, FTIR studies. The present results indicate that, in-vitro bioactivity of glasses decreased with increasing zirconia incorporation.

  5. The Coordination State of B and Al of Borosilicate Glass by IR Spectra

    Institute of Scientific and Technical Information of China (English)

    WAN Junpeng; CHENG Jinshu; LU Ping

    2008-01-01

    The IR spectra of R2O-RO-B2O3-SiO2 and R2O-RO-B2O3-Al2O3-SiO2 glasses were tested for the study of coordination state of B, Al and their content. The results show that no matter Na2O/B2O3>1,=1, or<1, both [Bo3] and destroyed Si-O bond exist in glass structure; the addition of Al2O3 to borosilicate glass reduced both the number of non-bridging oxygen in the silicate network and the number of [BO4] units.

  6. Process for the fabrication of hollow core solenoidal microcoils in borosilicate glass

    International Nuclear Information System (INIS)

    We report the fabrication of solenoidal microcoils with hollow core embedded within two 100 µm thick borosilicate glass wafers. The main process steps are the reactive ion etching of borosilicate glass, anodic wafer bonding, copper metal organic chemical vapor deposition (Cu MOCVD) and electroless galvanization. Our motivation stems from the need for a reliable, precise fabrication method of microcoils for high-resolution magnetic resonance imaging (MRI). For reduced loss at high-frequency operation, glass, with a lower dielectric constant as compared to silicon, was chosen as a substrate material. Simultaneously, this offers MRI sample observation owing to its optical transparency. Further essential parameters for the coil design were the need for small coil dimensions, a high filling factor (region of interest within the coil occupied by the sample/overall coil volume), and low-loss electrical connectability to external devices. In an attempt to achieve those requirements, the reported process demonstrates the combination of front- and backside borosilicate glass RIE of small dimensional features (down to 10 µm wall thickness) with subsequent conformal metallization of the 3D solenoidal coil by means of Cu MOCV and electroless galvanization

  7. Separation of Th and U using borosilicate glasses

    International Nuclear Information System (INIS)

    Boroaluminosilicate glasses having B2O3 to Na2O 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)

  8. Laser Induced Damage Studies in Borosilicate Glass Using nanosecond and sub nanosecond pulses

    CERN Document Server

    Rastogi, Vinay; Munda, D S

    2016-01-01

    The damage mechanism induced by laser pulse of different duration in borosilicate glass widely used for making confinement geometry targets which are important for laser driven shock multiplication and elongation of pressure pulse, is studied. We measured the front and rear surface damage threshold of borosilicate glass and their dependency on laser parameters. In this paper, we also study the thermal effects on the damage diameters, generated at the time of plasma formation. These induced damage width, geometries and microstructure changes are measured and analyzed with optical microscope, scanning electron microscope and Raman spectroscopy. The results show that at low energies symmetrical damages are found and these damage width increases nonlinearly with laser intensity. The emitted optical spectrum during the process of breakdown is also investigated and is used for the characterization of emitted plasma such as plasma temperature and free electron density. Optical emission lines from Si I at 500 nm, Si ...

  9. Effect of heat pretreatment on foaming of simulated nuclear waste in a borosilicate glass melt

    International Nuclear Information System (INIS)

    Foaming of Savannah River nuclear waste glass was studied in situ. Simulated nuclear waste was heat-treated at 8000 to 12000C and either mixed with a granular borosilicate frit or pressed into compacts and then brought into contact with molten borosilicate glass. The batches were heated at constant rate up to 11500C in quartz crucibles; the process was recorded photographically. Compacts foamed at 40 K and loose batches at 200 to 400 K below the heat-treatment temperature. The volume of melt for loose batches expanded up to 2.75 times and that of compacts up to 2.1 times if the heat-treatment temperature was below 10500C; heat-treatment temperatures above 11500C resulted in a significantly lower foam height. A minimum foam stability was recorded for heat-treatment temperatures of 10000 to 11000C

  10. Profile Control of a Borosilicate-Glass Groove Formed by Deep Reactive Ion Etching

    CERN Document Server

    Akashi, T

    2008-01-01

    Deep reactive ion etching (DRIE) of borosilicate glass and profile control of an etched groove are reported. DRIE was carried out using an anodically bonded silicon wafer as an etching mask. We controlled the groove profile, namely improving its sidewall angle, by removing excessively thick polymer film produced by carbonfluoride etching gases during DRIE. Two fabrication processes were experimentally compared for effective removal of the film : DRIE with the addition of argon to the etching gases and a novel combined process in which DRIE and subsequent ultrasonic cleaning in DI water were alternately carried out. Both processes improved the sidewall angle, and it reached 85o independent of the mask-opening width. The results showed the processes can remove excessive polymer film on sidewalls. Accordingly, the processes are an effective way to control the groove profile of borosilicate glass.

  11. Er3+–Al2O3 nanoparticles doping of borosilicate glass

    Indian Academy of Sciences (India)

    Jonathan Massera; Laeticia Petit; Joona Koponen; Benoit Glorieux; Leena Hupa; Mikko Hupa

    2015-09-01

    Novel borosilicate glasses were developed by adding in the glass batch Er3+–Al2O3 nanoparticles synthetized by using a soft chemical method. A similar nanoparticle doping with modified chemical vapour deposition (MCVD) process was developed to increase the efficiency of the amplifying silica fibre in comparison to using MCVD and solution doping. It was shown that with the melt quench technique, a Er3+–Al22O3 nanoparticle doping neither leads to an increase in the Er3+ luminescence properties nor allows one to control the rare-earth chemical environment in a borosilicate glass. The site of Er3+ in the Er3+–Al2O3 nanoparticle containing glass seems to be similar as in glasses with the same composition prepared using standard raw materials. We suspect the Er3+ ions to diffuse from the nanoparticles into the glass matrix. There was no clear evidence of the presence of Al2O3 nanoparticles in the glasses after melting.

  12. Operating Range for High Temperature Borosilicate Waste Glasses: (Simulated Hanford Enveloped)

    Energy Technology Data Exchange (ETDEWEB)

    Mohammad, J.; Ramsey, W. G.; Toghiani, R. K.

    2003-02-24

    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. Thermal and structural studies on barium borosilicate glasses containing sulphate ions

    International Nuclear Information System (INIS)

    Borosilicate glasses having composition SiO2)0.416(B2O3)0.208 (Na2O)0.218(BaO)0.157 containing up to 4 mol % sulphate ions were prepared by conventional melt-quench method. Incorporation of sulphate ions in the glass has been found to weaken the glass network as revealed by the decrease in the glass transition temperatures. Based on 29Si and 11B magic angle spinning nuclear magnetic resonance (MAS NMR) studies, it has been established that the silicate network undergoes slight depolymerisation while the boron structural units remained unaffected with sulphate addition in the glass. Above 4 mol % incorporation of sulphate ions resulted in the devitrification of the glass. (author)

  14. Characteristics of potential borosilicate glass compositions for high-level waste solidification in several countries

    International Nuclear Information System (INIS)

    Characteristics of various borosilicate glass compositions for high-level waste solidification were evaluated. There is possibility of returning to Japan the solidified high-level wastes in overseas fuel reprocessing by entrustment. In order to study the technical problems in receiving the solidified products, various potential compositions in several countries were examined. The following properties were evaluated for the basic data in preparation of the total criteria: melting characteristic, density, thermal conductivity, thermal expansion coefficient, softening temperature and leach rate. (author)

  15. Intrinsic dosimetry: Elemental composition effects on the thermoluminescence of commercial borosilicate glass

    International Nuclear Information System (INIS)

    Intrinsic dosimetry is the method of measuring total absorbed dose received by the walls of a container holding radioactive material. By considering this dose in tandem with the physical characteristics of the radioactive material housed within the container, this method can provide enhanced pathway information for interdicted radioactive samples. Thermoluminescence (TL) dosimetry was used to measure ionizing radiation dose effects on stock borosilicate glass. Differences in TL glow curve shape and intensity were observed for glasses from different geographical origins. The different TL signatures strongly correlated with the concentration of alkaline earth metals and the ratio of sodium to the total amount of alkali metal present in the borosilicate glass. -- Highlights: • Thermoluminescence (TL) properties of borosilicate were compared with composition. • TL glow curves were modeled using peaks centered at 120, 160, 225, 300, and 340 °C. • Overall TL intensity correlated with the sodium : total alkali metal content. • The 120 °C peak negatively correlated with the alkaline earth concentration. • The 160 °C peak negatively correlated with the concentration of K, Ce, and Ti

  16. Development of borosilicate glass compositions for the immobilisation of the UK's separated plutonium stocks

    International Nuclear Information System (INIS)

    The UK inventory of separated civil plutonium is expected to exceed 100 tonnes by 2010. Whilst the majority of this could be used in the manufacture of MOx (Mixed Oxide) fuel in future power generation scenarios, options for the disposal of surplus plutonium are currently being investigated by Nexia Solutions Ltd on behalf of the UK's Nuclear Decommissioning Authority (NDA). One of the options being considered is immobilisation in a durable glass matrix followed by long term storage and subsequent final repository disposal. A preliminary experimental survey assessed a selection of potential glass systems on the basis of Pu-surrogate (cerium) loading, durability, and ease of processing. Following this, a number of borosilicate compositions have been taken forward into a more detailed investigation in order to fully qualify their potential for Pu-immobilisation. The selected compositions are lanthanide borosilicate (LaBS), alkali tin silicate (ATS) and high-lanthanide alkali borosilicate (modified-MW). For this second series of experiments, hafnium was selected as the Pu surrogate, and a study of the potential waste loading as a function of temperature for the three selected compositions is described in this paper. Furthermore, several variations of the LaBS composition were fabricated in order to investigate the effect of total lanthanide content on melting temperature. The benchmark of 10 wt% HfO2 incorporation is achievable for all three glasses with temperatures of 1200, 1300 and 1400 deg. C required for ATS, modified-MW and LaBS respectively. (authors)

  17. Modeling surface area to volume effects on borosilicate glass dissolution

    International Nuclear Information System (INIS)

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

  18. Borosilicate glasses for the high activity waste vetrification

    International Nuclear Information System (INIS)

    Some results concerning the researches carried out on the high-level wastes vitrification at ENEA, Comb-Mepis-Rifiu laboratory are reported. A fission product solution referred to power plant nuclear fuel reprocessing has been selected and simulated with no radioactive chemicals. Some glass composition have been tested for the vitrification of this solution, the best of them being taken into consideration for real active tests at the hot bench scale plant ESTER in Ispra. The final glasses have been characterized from the chemical and physical point of view; moreover some microstructural investigations have been performed in order to identify few microsegregations and to test the degree of amorphousness of the products

  19. Irradiations effects on the structure of boro-silicated glasses: long term behaviour of nuclear waste glassy matrices

    International Nuclear Information System (INIS)

    This work deals with the long term behaviour of R7T7-type nuclear waste glasses and more particularly of non-active boro-silicated glasses made up of 3 or 5 oxides. Radioactivity of active glasses is simulated by multi energies ions implantations which reproduce the same defects. The damages due to the alpha particles are simulated by helium ions implantations and those corresponding to the recoil nucleus are obtained with gold ions ones. Minor actinides, stemming from the used fuel, is simulated by trivalent rare-earths (Eu3+ and Nd3+). In a first part, we have shown by macroscopic experiments (Vickers hardness - swelling) and optical spectroscopies (Raman - ATR-IR) that the structure of the glassy matrices is modified under implantations until a dose of 2,3.1013 at.cm-2, which corresponds to a R7T7 storage time estimated at 300 years. Beyond this dose, no additional modifications have been observed. The second part concerns the local environment of the rare-earth ions in glasses. Two different environments were found and identified as follows: one is a silicate rich one and the other is attributed to a borate rich one. (author)

  20. Electrical conductivity and viscosity of borosilicate glasses and melts

    DEFF Research Database (Denmark)

    Ehrt, Doris; Keding, Ralf

    2009-01-01

    by impedance measurements in a wide temperature range (250 to 1450°C). The activation energies were calculated by Arrhenius plots in various temperature regions: below the glass transition temperature, Tg, above the melting point, Tl, and between Tg and Tl. Viscosity measurements were carried out...

  1. Durability of borosilicate glass compositions for the immobilisation of the UK's separated plutonium stocks

    International Nuclear Information System (INIS)

    Several glass compositions are currently under investigation for immobilisation of the separated PuO2 that has been produced as a result of civil nuclear fuel reprocessing in the UK. Whilst a final decision on the fate of what ultimately will be over 100 tonnes of plutonium has yet to be made, all options for the disposition of this material are currently being investigated by Nexia Solutions Ltd on behalf of the Nuclear Decommissioning Authority (NDA). As one of the immobilisation options, vitrification in borosilicate glass could potentially provide a criticality-safe and stable waste form with durability suitable for long term storage and subsequent repository disposal. From an initial experimental survey of potential candidates, three borosilicate compositions were selected for a more detailed study of the waste loading and chemical durability: lanthanide borosilicate (LaBS), alkali tin silicate (ATS) and high-lanthanide alkali borosilicate (modified-MW). In these inactive tests, hafnium was used as the surrogate for plutonium. This paper describes a range of static leach tests that were undertaken in order to understand the overall durability of the waste forms, as well as the release rates of the Pu surrogate when compared to any neutrons poisons present in the glass. For the LaBS compositions it was found that the release rate of gadolinium was potentially slightly higher than that of hafnium, although both were as low as 10-5 to 10-6 g m2 day -1. The potential implications for long-term repository behaviour are discussed. (authors)

  2. Characteristics of borosilicate glass media fabricated by melting HEPA filter media with inorganic additives

    International Nuclear Information System (INIS)

    HEPA filters are widely used in the nuclear fields as a final off-gas cleaning unit. To assess the applicability of vitrification technology either to treat used filter media or to produce borosilicate glass medium for the solidification of alpha-contaminated wastes, various waste glasses of different compositions were fabricated by melting mixture of HEPA filter media and inorganic additives. Physicochemical properties such as microhardness, density, thermal expansion, and short-term leaching behavior were characterized. XRD analysis showed that amorphous glasses were formed for a wide range of mixing ratio. Leach resistances, measured by PCT-B leach tests, were superior to that of EA (Environmental Assessment) glass. Other properties were similar to those of glass media used for the vitrification of high-level radioactive wastes in foreign countries

  3. Characteristics of borosilicate glass media fabricated by melting HEPA filter media with inorganic additives

    Energy Technology Data Exchange (ETDEWEB)

    Kim, I. T.; Kim, H. Y.; Park, K. I.; Park, H. S.; Kim, J. H. [KAERI, Taejon (Korea, Republic of)

    1999-05-01

    HEPA filters are widely used in the nuclear fields as a final off-gas cleaning unit. To assess the applicability of vitrification technology either to treat used filter media or to produce borosilicate glass medium for the solidification of alpha-contaminated wastes, various waste glasses of different compositions were fabricated by melting mixture of HEPA filter media and inorganic additives. Physicochemical properties such as microhardness, density, thermal expansion, and short-term leaching behavior were characterized. XRD analysis showed that amorphous glasses were formed for a wide range of mixing ratio. Leach resistances, measured by PCT-B leach tests, were superior to that of EA (Environmental Assessment) glass. Other properties were similar to those of glass media used for the vitrification of high-level radioactive wastes in foreign countries.

  4. Molecular dynamics study of structural changes versus deposited energy dose in a sodium borosilicate glass

    International Nuclear Information System (INIS)

    The accumulation of cascades modeled by molecular dynamics in a sodium borosilicate glass allowed us to simulate the evolution of various macroscopic and structural properties up to the level of a stabilization plateau for the highest deposited nuclear energy doses. Marples' model was used to fit the glass volume expansion to the deposited energy dose, giving the damaged volume per projectile. The volume parameter from this model approximates the cascade core volume, suggesting that the underlying mechanisms of volume expansion are contained in the cascade core and are thus related to the highest-energy events: atom ejection and thermal quenching

  5. Water leaching of borosilicate glasses: experiments, modeling and Monte Carlo simulations

    International Nuclear Information System (INIS)

    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

  6. Aqueous corrosion of borosilicate glasses: experiments, modeling and Monte-Carlo simulations

    International Nuclear Information System (INIS)

    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

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

    International Nuclear Information System (INIS)

    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. Chemical compatibility of HLW borosilicate glasses with actinides

    International Nuclear Information System (INIS)

    During liquid storage of HLLW the formation of actinide enriched sludges is being expected. Also during melting of HLW glasses an increase of top-to-bottom actinide concentrations can take place. Both effects have been studied. Besides, the vitrification of plutonium enriched wastes from Pu fuel element fabrication plants has been investigated with respect to an isolated vitrification process or a combined one with the HLLW. It is shown that the solidification of actinides from HLLW and actinide waste concentrates will set no principal problems. The leaching of actinides has been measured in salt brine at 230C and 1150C. (orig.)

  9. A critical review of radiation effects on borosilicate glasses

    International Nuclear Information System (INIS)

    Most of the experimental values have been obtained by loading the glass with alpha emitters like Cm 244 and Pu 238. The data existing in literature on stored energy, and density variation are presented and discussed. Attention is given to the variation of the leaching rate due to the radiation effect. Samples loaded with alpha emitters have given data up to 0.17 dpa and such bombarded with heavy ions show large effects due to dose rate effects. A study on defect formation has shown that under electrons irradiation, formation of bubbles is possible. (DG)

  10. Elastic properties investigation of gamma-radiated barium lead borosilicate glass using ultrasonic technique

    International Nuclear Information System (INIS)

    Highlights: → Change in acoustical parameter due to composition effect and irradiation effect. → Changes in the structure of the glass (BO3 → BO4) due to the effect of radiation. → Structural changes in the BO3 to BO4 have a more compactness structure. - Abstract: The ultrasonic velocities were measured in barium lead borosilicate glass samples of different compositions before and after irradiation with γ-rays. Measurements were carried out at room temperature and 4 MHz frequency using ultrasonic technique. The ultrasonic velocities data of glass samples have been used to find the elastic modulus and micro-hardness. Densities of glass samples were measured by Archimedes's principle using n-hexane as immersion liquid. It was found that ultrasonic velocity, elastic modulus and micro-hardness increase with increasing barium oxide content and increasing γ-radiation dose.

  11. Underground migration of long-lived radionuclides leached from a borosilicate glass matrix

    International Nuclear Information System (INIS)

    A programme on the safety analysis linked to the geological disposal of radioactive wastes is under study at the Joint Research Centre of the Commission of the European Communities at Ispra. In relation to the migration of radionuclides in the terrestrial environment following a possible release from the repository, specific experimental studies are being developed in order to provide the necessary input data for the risk assessment models. The present paper reports the results of studies performed with neptunium, plutonium, americium and technetium isotopes leached from a borosilicate glass simulating the vitrified high-level wastes. In order to simulate the expected conditions of glass leaching and underground transport in the laboratory, a water pathway is established which flows over the radioactive glass and then through columns containing typical soil samples. The columns are examined during the experiment by gamma scanning or cut into thin sections at the end of the run and the distribution profile of radioisotopes measured. Experimental results obtained on soil columns are compared with data obtained using filtering membranes and ion exchange resins. These experiments using borosilicate glass demonstrate the relative importance of colloidal filtration by the geological porous medium. Following fixation it has been shown that slow rate processes probably account for the continuous small release of the radioactivity observed in the laboratory system. This long-term behaviour of colloids during the continuous percolation of groundwater is interpreted, taking into account complex ion formation with inorganic ligands present in natural waters. (author)

  12. Leach behavior of high-level borosilicate glasses under deep geological environment

    International Nuclear Information System (INIS)

    This report presents an overview of the activities in high-level radioactive waste glass which is considered as the most practicable form of waste, and also is intended to be used in the disposal of national high-level radioactive waste in future. Leach theory of waste glass and the leach effects of ground water, metal barrier, buffer materials and rocks on the waste glass were reviewed. The leach of waste glass was affected by various factors such as composition, pH and Eh of ground water, temperature, pressure, radiation and humic acid. The crystallization, crack, weathering and the formation of altered phases of waste glass which is expected to occur in real disposal site were reviewed. The results of leaching in laboratory and in-situ were compared. The behaviors of radioactive elements leached from waste glass and the use of basalt glass for the long-term natural analogue of waste glass were also written in this report. The appraisal of durability of borosilicate waste glass as a waste media was performed from the known results of leach test and international in-situ tests were introduced. (author). 134 refs., 15 tabs., 24 figs

  13. Leach behavior of high-level borosilicate glasses under deep geological environment

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seung Soo; Chun, Kwan Sik; Park, Hyun Soo

    1998-02-01

    This report presents an overview of the activities in high-level radioactive waste glass which is considered as the most practicable form of waste, and also is intended to be used in the disposal of national high-level radioactive waste in future. Leach theory of waste glass and the leach effects of ground water, metal barrier, buffer materials and rocks on the waste glass were reviewed. The leach of waste glass was affected by various factors such as composition, pH and Eh of ground water, temperature, pressure, radiation and humic acid. The crystallization, crack, weathering and the formation of altered phases of waste glass which is expected to occur in real disposal site were reviewed. The results of leaching in laboratory and in-situ were compared. The behaviors of radioactive elements leached from waste glass and the use of basalt glass for the long-term natural analogue of waste glass were also written in this report. The appraisal of durability of borosilicate waste glass as a waste media was performed from the known results of leach test and international in-situ tests were introduced. (author). 134 refs., 15 tabs., 24 figs

  14. Positive and Negative Mixed Glass Former Effects in Sodium Borosilicate and Borophosphate Glasses Studied by (23)Na NMR.

    Science.gov (United States)

    Storek, Michael; Adjei-Acheamfour, Mischa; Christensen, Randilynn; Martin, Steve W; Böhmer, Roland

    2016-05-19

    Glasses with varying compositions of constituent network formers but constant mobile ion content can display minima or maxima in their ion transport which are known as the negative or the positive mixed glass former effect, MGFE, respectively. Various nuclear magnetic resonance (NMR) techniques are used to probe the ion hopping dynamics via the (23)Na nucleus on the microscopic level, and the results are compared with those from conductivity spectroscopy, which are more sensitive to the macroscopic charge carrier mobility. In this way, the current work examines two series of sodium borosilicate and sodium borophosphate glasses that display positive and negative MGFEs, respectively, in the composition dependence of their Na(+) ion conductivities at intermediate compositions of boron oxide substitution for silicon oxide and phosphorus oxide, respectively. A coherent theoretical analysis is performed for these glasses which jointly captures the results from measurements of spin relaxation and central-transition line shapes. On this basis and including new information from (11)B magic-angle spinning NMR regarding the speciation in the sodium borosilicate glasses, a comparison is carried out with predictions from theoretical approaches, notably from the network unit trap model. This comparison yields detailed insights into how a variation of the boron oxide content and thus of either the population of silicon or phosphorus containing network-forming units with different charge-trapping capabilities leads to nonlinear changes of the microscopic transport properties. PMID:27092392

  15. Preparation and Optical Properties of Er3+ -Doped Gadolinium Borosilicate Glasses

    Institute of Scientific and Technical Information of China (English)

    Sun Jiangting; Zhang Jiahua; Chen Baojiu; Lu Shaozhe; Ren Xinguang; Wang Xiaojun

    2005-01-01

    Er3+-doped Gd2 O3 -SiO2 -B2 O3 -Na2O glasses were prepared, and formation range of glass of Gd2 O3 -SiO2 -B2O3 system was experimentally obtained. It is found that the glass phase can be formed only when the content of SiO2 is 0~50%(molar fraction), Gd2O3 is 0~30%(molar fraction) and B2 O3 is above 20%(molar fraction) in this glass system. The glass can also be obtained but becomes translucent at the contents of 60%(molar fraction) SiO2 and 30% Gd2O3 , or at the contents of 60%(molar fraction) SiO2 and 30%(molar fraction) B2O3. There is no glass phase formed in other glass components. Glass forming ability for Gd2O3 content of 10%, was characterized by the value of β, the parameter of crystallization tendency, which is 0.32~1.76, obtained from the differential thermal analysis. The absorption and emission cross section, the J-O parameters Ωt(2,4,6) and radiative transition probabilities were calculated by using the theory of McCumber and Judd-Ofelt. The emission properties at 1.5 μm of the samples are discussed with the product of full width at half maximum and stimulated emission cross section. It can be seen that the value of the FWHM×σepeak product in the prepared glass is more than those of germanate, silicate and phosphate glasses. Furthermore, the maximum value of the product among these glasses reported in this work is close to that of oxyfluoride silicate glass. Therefore, the Er3+-doped gadolinium borosilicate glass in this paper is a candidate for broadband erbium doped fiber amplifiers.

  16. Quantification of the boron speciation in alkali borosilicate glasses by electron energy loss spectroscopy

    DEFF Research Database (Denmark)

    Cheng, D.S.; Yang, G.; Zhao, Y.Q.;

    2015-01-01

    developed a method based on electron energy loss spectroscopy (EELS) data acquisition and analyses, which enables determination of the boron speciation in a series of ternary alkali borosilicate glasses with constant molar ratios. A script for the fast acquisition of EELS has been designed, from which the...... fraction of BO4 tetrahedra can be obtained by fitting the experimental data with linear combinations of the reference spectra. The BO4 fractions (N4) obtained by EELS are consistent with those from 11B MAS NMR spectra, suggesting that EELS can be an alternative and convenient way to determine the N4...

  17. Aqueous corrosion of borosilicate glasses: experiments, modeling and Monte-Carlo simulations; Alteration par l'eau des verres borosilicates: experiences, modelisation et simulations Monte-Carlo

    Energy Technology Data Exchange (ETDEWEB)

    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. Water leaching of borosilicate glasses: experiments, modeling and Monte Carlo simulations; Alteration par l'eau des verres borosilicates: experiences, modelisation et simulations Monte Carlo

    Energy Technology Data Exchange (ETDEWEB)

    Ledieu, A

    2004-10-15

    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

  19. High-level waste borosilicate glass: A compendium of corrosion characteristics. Volume 2

    Energy Technology Data Exchange (ETDEWEB)

    Cunnane, J.C. [comp.; Bates, J.K.; Bradley, C.R. [Argonne National Lab., IL (United States)] [and others

    1994-03-01

    The objective of this document is to summarize scientific information pertinent to evaluating the extent to which high-level waste borosilicate glass corrosion and the associated radionuclide release processes are understood for the range of environmental conditions to which waste glass may be exposed in service. Alteration processes occurring within the bulk of the glass (e.g., devitrification and radiation-induced changes) are discussed insofar as they affect glass corrosion.This document is organized into three volumes. Volumes I and II represent a tiered set of information intended for somewhat different audiences. Volume I is intended to provide an overview of waste glass corrosion, and Volume 11 is intended to provide additional experimental details on experimental factors that influence waste glass corrosion. Volume III contains a bibliography of glass corrosion studies, including studies that are not cited in Volumes I and II. Volume I is intended for managers, decision makers, and modelers, the combined set of Volumes I, II, and III is intended for scientists and engineers working in the field of high-level waste.

  20. High-level waste borosilicate glass: A compendium of corrosion characteristics. Volume 2

    International Nuclear Information System (INIS)

    The objective of this document is to summarize scientific information pertinent to evaluating the extent to which high-level waste borosilicate glass corrosion and the associated radionuclide release processes are understood for the range of environmental conditions to which waste glass may be exposed in service. Alteration processes occurring within the bulk of the glass (e.g., devitrification and radiation-induced changes) are discussed insofar as they affect glass corrosion.This document is organized into three volumes. Volumes I and II represent a tiered set of information intended for somewhat different audiences. Volume I is intended to provide an overview of waste glass corrosion, and Volume 11 is intended to provide additional experimental details on experimental factors that influence waste glass corrosion. Volume III contains a bibliography of glass corrosion studies, including studies that are not cited in Volumes I and II. Volume I is intended for managers, decision makers, and modelers, the combined set of Volumes I, II, and III is intended for scientists and engineers working in the field of high-level waste

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

    International Nuclear Information System (INIS)

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

  2. Development of Composite Materials Under Ecological Aspects as Recycling Concept For Borosilicate Glass Containing Iron Slags

    International Nuclear Information System (INIS)

    Composite concept in materials science can be conveniently applied in the waste treatment technology to construct specific tailor madecomposite materials, in which at least one of the phases is built by the waste material. In this work the applicability of this concept for the fixation and recycling of slags wastes is done, whereby different mixtures of blast furnace slags are mixed with two different borosilicate glasses, which serve as matrix material. Thermal behaviour of the produced compacts were studied. Both melting and powder technology are applied for the fabrication of dense products. The microstructure of sintered samples is investigated by electron microscopy. The mechanical properties such as hardness and fracture toughness are determined by a Vickers technique. An improvement of the fracture toughness of more than 50% over the value for the original glass VG 98 is achieved by slag addition

  3. Corrosion testing of a plutonium-loaded lanthanide borosilicate glass made with Frit B

    International Nuclear Information System (INIS)

    Laboratory tests were conducted with a lanthanide borosilicate (LaBS) glass made with Frit B and added PuO2 (the glass is referred to herein as Pu LaBS-B glass) to measure the dependence of the glass dissolution rate on pH and temperature. These results are compared with the dependencies used in the Defense HLW Glass Degradation Model that was developed to account for HLW glasses in total system performance assessment (TSPA) calculations for the Yucca Mountain repository to determine if that model can also be used to represent the release of radionuclides from disposed Pu LaBS glass by using either the same parameter values that are used for HLW glasses or parameter values specific for Pu LaBS glass. Tests were conducted by immersing monolithic specimens of Pu LaBS-B glass in six solutions that imposed pH values between about pH 3.5 and pH 11, and then measuring the amounts of glass components released into solution. Tests were conducted at 40, 70, and 90 C for 1, 2, 3, 4, and 5 days at low glass-surface-area-to-solution volume ratios. As intended, these test conditions maintained sufficiently dilute solutions that the impacts of solution feedback effects on the dissolution rates were negligible in most tests. The glass dissolution rates were determined from the concentrations of Si and B measured in the test solutions. The dissolution rates determined from the releases of Si and B were consistent with the 'V' shaped pH dependence that is commonly seen for borosilicate glasses and is included in the Defense HLW Glass Degradation Model. The rate equation in that model (using the coefficients determined for HLW glasses) provides values that are higher than the Pu LaBS-B glass dissolution rates that were measured over the range of pH and temperature values that were studied (i.e., an upper bound). Separate coefficients for the rate expression in acidic and alkaline solutions were also determined from the test results to model Pu LaBS-B glass dissolution directly. The

  4. Barium borosilicate glass - a potential matrix for immobilization of sulfate bearing high-level radioactive liquid waste

    International Nuclear Information System (INIS)

    Borosilicate glass formulations adopted worldwide for immobilization of high-level radioactive liquid waste (HLW) is not suitable for sulphate bearing HLW, because of its low solubility in such glass. A suitable glass matrix based on barium borosilicate has been developed for immobilization of sulphate bearing HLW. Various compositions based on different glass formulations were made to examine compatibility with waste oxide with around 10 wt% sulfate content. The vitrified waste product obtained from barium borosilicate glass matrix was extensively evaluated for its characteristic properties like homogeneity, chemical durability, glass transition temperature, thermal conductivity, impact strength, etc. using appropriate techniques. Process parameters like melt viscosity and pour temperature were also determined. It is found that SB-44 glass composition (SiO2: 30.5 wt%, B2O3: 20.0 wt%, Na2O: 9.5 wt% and BaO: 19.0 wt%) can be safely loaded with 21 wt% waste oxide without any phase separation. The other product qualities of SB-44 waste glass are also found to be on a par with internationally adopted waste glass matrices. This formulation has been successfully implemented in plant scale

  5. X-ray absorption studies of bismuth valence and local environments in borosilicate waste glasses

    International Nuclear Information System (INIS)

    Highlights: ► Bi in high level nuclear waste glasses was of interest due to melt foaming issues. ► Bi was also found associated with phosphate in some samples. ► X-ray absorption spectroscopy found similar Bi bonding within all glasses studied. ► The glasses contain Bi3+O3 environments with average Bi–O distances near 2.13 Å. ► No Bi-phosphate glass domains nor any link between Bi and melt foaming were observed. - Abstract: X-ray absorption spectra (XAS) were collected and analyzed to characterize bismuth (Bi) environments in borosilicate glass formulations developed for the immobilization of high level nuclear wastes (HLW), from the bismuth phosphate process. Therefore, the structural role of Bi in these glasses is of interest; in addition in the present study, more particular interest in Bi originated from unusual foaming that was observed during melt cooling, where it was initially suspected that Bi3+ reduction to Bi0 may generate oxygen that caused the foaming. Observations from scanning electron microscopy of some HLW glass samples indicated a Bi-phosphate association. Bi LIII XAS of 13 Bi-containing waste glass formulations of various compositions were measured that exhibited varying degrees of melt foaming. The Bi XAS are similar for all glasses investigated, and indicate Bi3+O3 nearest-neighbor environments with Bi–O distances near 2.13 Å. This environment is similar to the most localized Bi coordination characteristics in the crystalline Bi-silicates, eulytite (Bi4Si3O12) and bismutoferrite (BiFe2Si2O8OH). However, the Bi-environments in the glasses are distinctly different from the Bi-site in crystalline BiPO4; therefore, XAS indicates no evidence of Bi-phosphate domains in the glasses measured. No XAS evidence was observed in any of the glasses investigated for Bi clustering, such as metallic Bi, or Bi–O–Bi bonding. Since the local Bi environments look similar for all glasses investigated, Bi XAS data and analyses show no association

  6. Luminescence properties of Gd{sup 3+}-doped borosilicate scintillating glass

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Chunmei [Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Patent Examination Cooperation HuBei Center of The Patent Office, SIPO, Wuhan, HuBei 430070 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Liu, Shuang [Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Liu, Liwan [Shanghai University, Shanghai 201800 (China); Chen, Dan Ping, E-mail: dpchen2008@aliyun.com [Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China)

    2015-04-15

    Gd{sup 3+}-doped borosilicate glasses are prepared in different melting atmosphere. Absorption spectra, decay time, luminescence spectra under UV and X-ray excitation are investigated. With melting atmosphere changing from air to CO, the luminescence intensities of Gd{sup 3+} at 313 nm under the excitation of UV and X-ray are both enhanced. This mainly results from the reduction of Gd{sup 3+}, which is validated by electron paramagnetic resonance (EPR). The optimal Gd{sub 2}O{sub 3} content for the glasses prepared under CO atmosphere is 7.5 mol%, whose integral scintillation efficiency is 20% compared with Bi{sub 4}Ge{sub 3}O{sub 12}. - Highlights: • Glasses with various Gd{sub 2}O{sub 3} contents are prepared in the air or CO atmosphere. • The glasses show stronger photoluminescence and radioluminescence intensity. • High integral scintillation efficiency obtained for the prepared glass is 20% of BGO.

  7. Silver diffusion and coloration of soda lime and borosilicate glasses, Part 1: Effect on the transmission and coloration of stained glasses

    OpenAIRE

    ABDELLAH CHORFA; NABIL BELKHIR; FAUSTO RUBIO; JUAN RUBIO

    2012-01-01

    Using the conventional method of coloration, soda lime and borosilicate glasses have been painted. Once stained, these glasses were heat treated at temperatures close to their transition temperatures (Tg). A parametric study was carried out in order to determine at first the effect of the silver concentration in the stain spread on glass. In addition, it was studied the effect of the heat treatment duration and the chemical composition of the painted glasses on the formation and size of the s...

  8. Intrinsic dosimetry. Properties and mechanisms of thermoluminescence in commercial borosilicate glass

    Energy Technology Data Exchange (ETDEWEB)

    Clark, Richard A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2012-10-01

    Intrinsic dosimetry is the method of measuring total absorbed dose received by the walls of a container holding radioactive material. By considering the total absorbed dose received by a container in tandem with the physical characteristics of the radioactive material housed within that container, this method has the potential to provide enhanced pathway information regarding the history of the container and its radioactive contents. The latest in a series of experiments designed to validate and demonstrate this newly developed tool are reported. Thermoluminescence (TL) dosimetry was used to measure dose effects on raw stock borosilicate container glass up to 70 days after gamma ray, x-ray, beta particle or ultraviolet irradiations at doses from 0.15 to 20 Gy. The TL glow curve when irradiated with 60Co was separated into five peaks: two relatively unstable peaks centered near 120 and 165°C, and three relatively stable peaks centered near 225, 285, and 360°C. Depending on the borosilicate glass source, the minimum measurable dose using this technique is 0.15-0.5 Gy, which is roughly equivalent to a 24 hr irradiation at 1 cm from a 50-165 ng source of 60Co. Differences in TL glow curve shape and intensity were observed for the glasses from different geographical origins. These differences can be explained by changes in the intensities of the five peaks. Electron paramagnetic resonance (EPR) and multivariate statistical methods were used to relate the TL intensity and peaks to electron/hole traps and compositional variations.

  9. X-Ray excited and photoluminescence of CdS1-xSex nanocrystals embedded in borosilicate glass matrix

    Directory of Open Access Journals (Sweden)

    Gomonnai A.V.

    2001-03-01

    Full Text Available The performed experimental studies of X-ray excited and photoluminescence, optical absorption and Raman scattering of CdS1-xSex nanocrystals, embedded in borosilicate glass matrix, have enabled the nanocrystal parameters (chemical composition, average radius, acceptor levels energy depth, electron-hole Coulomb interaction energy is to be determined.

  10. Dependence of water resistance multicomponent sodium-borosilicate glasses on their composition

    International Nuclear Information System (INIS)

    Regularities affecting chemical stability of multicomponent sodium-borosilicate glasses have been revealed. Glass of the composition (mass %): 16.6 Na2O; 18.7 B2O3; 36.1 SIO2; 1.3 Al2O3; 5.7 Fe2O3; 5.1 CaO; 2.9 FeO; 6.5 MnO; 2.5 Li2O; 0.8 K2O; 3.5 CaF2 above 100-1.5 CoO have been chosen as initial one. Chemical glass stability with respect to water was determined on powder fractions of 0.50-0.85 mm and 3 g mass, which was affected with 150 ml boiling water during 2.0 h. Powder after tests was washed and dried to a constant weight at 110 deg C. Loss of powder mass in percents was an index of water resistance. It is shown that Na2O replacement with BaO and K2O causes considerable increase of water resistance as compared with a source glass

  11. Third-order Nonlinear Optical Properties of Silver Quantum Dots Doped in Sodium Borosilicate Glass

    Directory of Open Access Journals (Sweden)

    ZHAO Xiu-Li, LIANG Xiao-Juan, LUO Hong-Yan, CHEN Zhao-Ping, XIANG Wei-Dong

    2013-09-01

    Full Text Available Silver quantum dots doped in sodium borosilicate glass were synthesized through Sol-Gel method using tetraethyl orthosilicate (TEOS, boracic acid, metallic sodium as precursors. X-ray powder diffraction (XRD analyses revealed that silver quantum dots were cubic crystalline phase; size and distribution of the quantum dots were measured by transmission electron microscope (TEM as well as high-resolution transmission electron microscope (HRTEM. The results showed that spherical shape formed uniformly in the glass, and the size of these quantum dots ranged from 5 nm to 13 nm. Ultraviolet-visible (UV-Vis absorption spectrometer obtained surface plasma resonance (SPR absorption peaks as that of the Ag quantum dots at about 406 nm. Nonlinear optical properties of silver quantum dots doped glass were investigated by using Z-scan technique at the wavelength of 800 nm with femtosecond Ti: sapphire laser radiation. The values of nonlinear refraction index γ, nonlinear absorption coefficient β and the third-order nonlinear optical susceptibility χ(3 of the glass were estimated to be –1.72×10-17 m2/W, 9.96×10-11 m/W, 1.01×10-11 esu, respectively.

  12. Evolutions of Molecular Oxygen Formation and Sodium Migration in Xe Ion Irradiated Borosilicate Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Liang; Zhang, Duofei F.; Lv, Peng; Zhang, Jiandong; Du, Xing; Yuan, Wei; Nan, Shuai; Zhu, Zihua; Wang, Tieshan

    2016-07-23

    The modifications of a commercial borosilicate glass induced by Xe ion irradiation have been studied by Raman spectroscopy and ToF-SIMS depth profiling. A decrease in the average Si–O–Si angle, an increase in the population of three-membered rings and an increase of the glass polymerization are evidenced. The molecular oxygen appears in the irradiated glasses after the irradiation fluence reaches approximately 1015 ions/cm2. The O2 concentration decreaseswith the depth of irradiated glass at the ion fluence of 2 × 1016 ions/cm2. A sodiumdepleted layer at the surface and a depleted zone at around the penetration depth of 5 MeV Xe ions are observed. The thickness of the sodium depleted layer increases with the irradiation fluence. Moreover, comparing with previous results after electron and Ar ion irradiation, it can be concluded that the nuclear energy deposition can partially inhibit the formation of molecular oxygen and increase the threshold value of electron energy deposition for the molecular oxygen formation.

  13. Sol–gel synthesis and optical properties of CuGaS2 quantum dots embedded in sodium borosilicate glass

    International Nuclear Information System (INIS)

    Highlights: • The CuGaS2 quantum dots doped sodium borosilicate glass was prepared by sol–gel methods. • The obtained glass was investigated by XRD, (S)TEM and XPS. • Tetragonal crystalline phase of CuGaS2 quantum dots with spherical shape were formed uniformly in the glass matrix. • The third-order optical nonlinearity was investigated by Z-scan technique. - Abstract: I–III–VI2 ternary semiconductor CuGaS2 quantum dots embedded in sodium borosilicate glass matrix were synthesized by combining the sol–gel process and heat treatment in H2S gas. The structure and morphology of the obtained glass were studied by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The results showed that tetragonal crystalline phase of CuGaS2 quantum dots with spherical shape were formed uniformly in the sodium borosilicate glass matrix, and the sizes ranged from 5 to 25 nm with an average particle size of 12.75 nm. The optical nonlinearity was studied using Z-scan technique employing 200 fs at the wavelength of 800 nm. The glass doped with CuGaS2 quantum dots exhibited large third-order optical nonlinear susceptibility χ(3) of 1.60 × 10−9 esu

  14. Preparation and optical properties of sodium borosilicate glasses containing Sb nanoparticles

    International Nuclear Information System (INIS)

    Highlights: • The Sb nanoparticles doped in Na2O–B2O3–SiO2 glass were prepared by sol–gel methods. • Obtained glass was investigated by structural and optical measurements. • The glass was crystalline with a rhombohedral structure of Sb. • An absorption peak centered on 566 nm has been observed in doping glass. • The third-order optical nonlinearity was investigated by femtosecond Z-scan technique. - Abstract: Sb nanoparticles have been successfully prepared from SbCl3 in sodium borosilicate (Na2O–B2O3–SiO2) glass matrix by sol–gel method, involving metallic sodium as sodium source, boric acid as boron source and SiO2 come from hydrolysis of tetraethoxysilane. The feasibility of process conditions were analyzed by using Fourier Transform Infrared (FT-IR), thermal gravimetric (TG), and nuclear magnetic resonance (NMR). X-ray diffraction (XRD) study revealed that the rhombohedral structure of metal Sb have formed in the glass. The particle was found to be spherical shaped and highly monodispersed with an average size of about 32.63 nm as analyzed from transmission electron microscopy (TEM). The surface plasmon resonance (SPR) of Sb nanoparticle was studied from the UV–Vis absorption. The nonlinear optical properties were studied by using the Z-scan technique with a Ti:sapphire laser at 800 nm. Results showed that the third-order optical nonlinear susceptibility χ(3) of the glass was determined to be 4.85 × 10−11 esu

  15. GLASS FABRICATION AND PRODUCT CONSISTENCY TESTING OF LANTHANIDE BOROSILICATE FRIT B COMPOSITION FOR PLUTONIUM DISPOSITION

    Energy Technology Data Exchange (ETDEWEB)

    Marra, J

    2006-01-19

    The Department of Energy Office of Environmental Management (DOE/EM) plans to conduct the Plutonium Disposition Project at the Savannah River Site (SRS) to disposition excess weapons-usable plutonium. A plutonium glass waste form is a leading candidate for immobilization of the plutonium for subsequent disposition in a geologic repository. A reference glass composition (Lanthanide Borosilicate (LaBS) Frit B) was developed during the Plutonium Immobilization Program (PIP) to immobilize plutonium. A limited amount of performance testing was performed on this baseline composition before efforts to further pursue Pu disposition via a glass waste form ceased. Therefore, the objectives of this present task were to fabricate plutonium loaded LaBS Frit B glass and perform additional testing to provide near-term data that will increase confidence that LaBS glass product is suitable for disposal in the Yucca Mountain Repository. Specifically, testing was conducted in an effort to provide data to Yucca Mountain Project (YMP) personnel for use in performance assessment calculations. Plutonium containing LaBS glass with the Frit B composition with a 9.5 wt% PuO{sub 2} loading was prepared for testing. Glass was prepared to support Product Consistency Testing (PCT) at Savannah River National Laboratory (SRNL) and for additional performance testing at Argonne National Laboratory (ANL) and Pacific Northwest National Laboratory (PNNL). The glass was characterized using x-ray diffraction (XRD) and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS) prior to performance testing. A series of PCTs were conducted at SRNL with varying exposed surface area and test durations. The leachates from these tests were analyzed to determine the dissolved concentrations of key elements. Acid stripping of leach vessels was performed to determine the concentration of the glass constituents that may have sorbed on the vessels during leach testing. Additionally, the

  16. Optical properties of 3d transition metal ion-doped sodium borosilicate glass

    International Nuclear Information System (INIS)

    Graphical abstract: Photographs of undoped (SiO2)50 (Na2O)25 (B2O3)25 (SiNaB) glass and transition metal ion-doped (TM)0.5 (SiO2)49.5 (Na2O)25 (B2O3)25 glass samples. - Highlights: • 3d transition metal ion (from Ti to Zn) doped SiO2-Na2O-B2O3 glasses. • Optical properties of doped glasses investigated. • V(IV,V); Cr(III, VI); Mn(II,III); Fe(II,III); Co(II); Ni(II); Cu(II) by XANES, DRS. • Strong visible absorption but only vanadium ion gives strong emission in glass. - Abstract: SiO2-Na2O-B2O3 glasses doped with 3d-transition metal species from Ti to Zn were prepared by the melting-quenching technique and their optical properties were investigated. The X-ray absorption near edge spectra of V, Cr, and Mn-doped glasses indicate that the oxidation states of V(IV, V), Cr(III, VI) and Mn(II, III) exist in the studied glasses. The oxidation states revealed from the diffuse reflectance spectra of the glasses are V(IV, V), Cr(III, VI), Mn(III), Fe(II, III), Co(II), Ni(II), and Cu(II). Most of the 3d transition element ions exhibit strong absorption in the visible spectral region in the glass. Under ultraviolet excitation, the undoped sodium borosilicate glass produces weak and broad emission, while doping of vanadium introduces strong and broad emission due to the V(V) charge transfer transition. Only weak emission is observed from Ti(IV), Mn(II), Fe(III) and Cu(II), partly resulting from the strong electron–phonon coupling of the 3d-electrons and the relatively high phonon energy of the studied glass host, with the former leading to dominant nonradiative relaxation based on multiphonon processes for most of the 3d excited states

  17. Optical properties of 3d transition metal ion-doped sodium borosilicate glass

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Hongli [School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong (China); Tanner, Peter A., E-mail: peter.a.tanner@gmail.com [Department of Science and Environmental Studies, The Hong Kong Institute of Education, 10 Lo Ping Road, Tai Po, N.T., Hong Kong Special Administrative Region (Hong Kong)

    2015-03-15

    Graphical abstract: Photographs of undoped (SiO{sub 2}){sub 50} (Na{sub 2}O){sub 25} (B{sub 2}O{sub 3}){sub 25} (SiNaB) glass and transition metal ion-doped (TM){sub 0.5} (SiO{sub 2}){sub 49.5} (Na{sub 2}O){sub 25} (B{sub 2}O{sub 3}){sub 25} glass samples. - Highlights: • 3d transition metal ion (from Ti to Zn) doped SiO{sub 2}-Na{sub 2}O-B{sub 2}O{sub 3} glasses. • Optical properties of doped glasses investigated. • V(IV,V); Cr(III, VI); Mn(II,III); Fe(II,III); Co(II); Ni(II); Cu(II) by XANES, DRS. • Strong visible absorption but only vanadium ion gives strong emission in glass. - Abstract: SiO{sub 2}-Na{sub 2}O-B{sub 2}O{sub 3} glasses doped with 3d-transition metal species from Ti to Zn were prepared by the melting-quenching technique and their optical properties were investigated. The X-ray absorption near edge spectra of V, Cr, and Mn-doped glasses indicate that the oxidation states of V(IV, V), Cr(III, VI) and Mn(II, III) exist in the studied glasses. The oxidation states revealed from the diffuse reflectance spectra of the glasses are V(IV, V), Cr(III, VI), Mn(III), Fe(II, III), Co(II), Ni(II), and Cu(II). Most of the 3d transition element ions exhibit strong absorption in the visible spectral region in the glass. Under ultraviolet excitation, the undoped sodium borosilicate glass produces weak and broad emission, while doping of vanadium introduces strong and broad emission due to the V(V) charge transfer transition. Only weak emission is observed from Ti(IV), Mn(II), Fe(III) and Cu(II), partly resulting from the strong electron–phonon coupling of the 3d-electrons and the relatively high phonon energy of the studied glass host, with the former leading to dominant nonradiative relaxation based on multiphonon processes for most of the 3d excited states.

  18. Advanced HLW management strategies employing both synroc and borosilicate glass waste-forms

    International Nuclear Information System (INIS)

    Recent resurgence of interest in waste partitioning permits the consideration of advanced strategies for Righ-level waste (HLW) management based on exploitation of Synroc in conjunction with borosilicate glass. The synergies resulting from the complementary of these waste-forms and their respective process technologies opens up the opportunity to reduce the overall volume of conditioned HLW for geological disposal. The paper provides a summary of the salient features of Synroc and discusses strategies for the conditioning of partitioned wastes from the reprocessing of UOX and MOX fuels from nuclear power generation. The discussion will also explore potential in U.S. defence waste remediation and disposition of excess fissile materials such as Pu. (authors)

  19. Influence of bicarbonate ions and redox conditions on the surface composition of a leached borosilicate glass

    International Nuclear Information System (INIS)

    A serie of short leaching tests have been performed on a borosilicate glass (I117) up to a maximum of 40 days. The tests were performed in a closed system in oxic and anoxic conditions and in presence of bicarbonate ions. The bicarbonate ions do not influence the mass losses while the oxic condition gives rise to an higher mass losses. Surface analysis was performed on the surface layer for the elements uranium and iron. Uranium is always depleted at the surface of the samples. It appears that adsorption and diffusion in the layer play an important part in the uranium released. Iron on the contrary is enriched so that solubility of the formed species are responsible of its concentration

  20. Borosilicate glass (α,n) sources used with ORIGEN-type calculations

    International Nuclear Information System (INIS)

    The major part of the neutron source in vitrified high-level waste is produced from the actinide α-particle emission interacting with the light elements in borosilicate glass. Models applying thick target (α,n) yield data have been developed for the ALPHN code and ORIGEN-S at the Oak Ridge National Laboratory. The method requires the relation between the (α,n) yields and the stopping powers of elements, which are constituents in a mixture, and the total (α,n) yield of the mixture. An example is given of results computed by ALPHN, listing the calculated (α,n) sources for each α-particle emitter in addition to the total. An example computed by ORIGEN-S is given, showing both the total (α,n) spectrum and the total neutron spectrum, including spontaneous fission. A discussion of the limited validation work is also provided

  1. Borosilicate glass (α,n) sources used with ORIGEN-type calculations

    International Nuclear Information System (INIS)

    The major part of the neutron sources in vitrified high level waste is produced from the actinide α-particle emission interacting with the light elements in borosilicate glass. Models applying thick target (α,n) yield data have been developed for the ALPHN code and ORIGEN-S at the Oak Ridge national Laboratory. The method requires the relation between the (α,n) yields and the stopping powers of elements, which are constituents in a mixture, and the total (α,n) yield of the mixture. An example is shown of results computed by ALPHN, listing the calculated (α,n) sources for each α-particle emitter in addition to the total. In this paper an example computed by ORIGEN-S is given, showing both the total (α,n) spectrum and the total neutron spectrum, including spontaneous fission. A discussion of the limited validation work is also provided

  2. Structural and crystallisation study of a rare earth alumino borosilicate glass designed for nuclear waste confinement

    International Nuclear Information System (INIS)

    This work is devoted to the study of a rare earth alumino borosilicate glass, which molar composition is 61,81 SiO2 - 3,05 Al2O3 - 8,94 B2O3 - 14,41 Na2O - 6,33 CaO - 1,90 ZrO2 - 3,56 Nd2O3, and envisaged for the immobilization of nuclear wastes originating from the reprocessing of high discharge burn up spent fuel. From a structural viewpoint, we investigated the role of the modifier cations on the arrangement of the glass network through different modifications of the glass composition: variation of the Na/Ca ratio and modification of the nature of the alkali and alkaline earth cations. The NMR and Raman spectroscopic techniques were useful to determine the distribution of modifier cations among the glass network and also to cast light on the competition phenomena occurring between alkali and alkaline earth cations for charge compensation of [AlO4]- and [BO4]- species. The neodymium local environment could be probed by optical absorption and EXAFS spectroscopies which enabled to better understand the insertion mode of Nd3+ ions among the silicate domains of the glass network. Concerning the crystallization behavior we were interested in how the glass composition may influence the crystallization processes and especially the formation of the apatite phase of composition Ca2Nd8(SiO4)6O2. In particular, this work underlined the important role of both alkaline earth and rare earth cations on the crystallization of the apatite phase. (author)

  3. Radiation-induced paramagnetic defects as structural probes of pure silica and borosilicate glasses

    International Nuclear Information System (INIS)

    The short-range structure of high-purity SiO2 and B2O3-3SiO2 glasses has been studied by electron spin resonance (ESR) using γ-ray-induced defects as probes. Specific defects studied in silica include the familiar silicon E' centre (an oxygen-vacancy defect) and several oxygen-associated hole centres (OHCs). In the borosilicate glass the defects comprise the SiE' centre, the boron oxygen hole centre (BOHC), and a newly-discovered structural analogue of the SiE' centre, the boron E' centre. The derived structural information includes (1) the nature and quantity of quenched-in structural defects, (2) the degree of clustering of boron or alkali at defect sites, and (3) the average magnitude of structural distortions brought about by vitreous disorder. These estimates are based on careful computer simulations of the observed ESR spectra, taking into account the occurrence of distributions in energy level splittings which give rise to statistical distributions in spin Hamiltonian parameters. One of the most striking findings is the fact that the average variation in (defect)-A-O bond angle (A = Si or B) over the ensemble of E' sites in a given glass sample is always 0. It is inferred that tetrahedral SiO4 units without oxygen vacancies are at least this perfect. (author)

  4. Structure and chemical durability of barium borosilicate glass-ceramics containing zirconolite and titanite crystalline phases

    Science.gov (United States)

    Li, Huidong; Wu, Lang; Xu, Dong; Wang, Xin; Teng, Yuancheng; Li, Yuxiang

    2015-11-01

    In order to increase the solubility of actinides in the glass matrix, the effects of CaO, TiO2, and ZrSiO4 addition (abbreviated as CTZ, in the mole ratio of 2:2:1) on crystalline phases, microstructure, and chemical durability of barium borosilicate glass-ceramics were investigated. The results show that the samples possess both zirconolite-2M and titanite phase when the CTZ content is greater than or equal to 45 wt.%. For the glass-ceramics with 45 wt.% CTZ (CTZ-45), only zirconolite-2M phase is observed after annealing at 680-740 °C for 2 h. The CTZ-45 possess zirconolite-2M and titanite phases after annealing at 700 °C first, and then annealing at 900-1050 °C for 2 h. Furthermore, the zirconolite-2M and titanite grains show a strip and brick shape, respectively. The CTZ-45 annealing at 950 °C shows the lower normalized leaching rates of B, Na and Nd when compared to that of CTZ-0 and CTZ-55.

  5. Results of Vertical Scanning Interferometry (VSI) of Dissolved Borosilicate Glass: Evidence for Variable Surface Features and Global Surface Retreat

    International Nuclear Information System (INIS)

    Two disparate reaction mechanisms have been invoked to explain the reactivity of glass in contact with aqueous solution. One model is based on arguments from Transition State Theory (TST), which postulates that glass dissolution rates are surface reaction controlled. Alternatively, the second model argues that release of elements from glass to solution is governed by diffusion through an altered layer that forms on the surface of glass. Vertical Scanning Interferometry (VSI) is a new technique that allows one to observe surface features of specimens exposed to solution and may, potentially, be used to distinguish between competing models. We performed a series of dissolution experiments with a suite of glass compositions from chemically simple (sodium borosilicate) to complex (sixteen component borosilicate). Dissolution rates were determined using single-pass flow-through (SPFT) apparatus at 90 C and pH = 9 and over a solution saturation interval. Upon termination of the experiments, glass coupons were examined by VSI techniques. Effluent chemistry and VSI measurements indicate a nearly constant rate of 2.2 to 3.4 g m-2 d-1 over the solution interval; rates calculated from both methods are identical within experimental uncertainty. We argue that this glass is phase separated, and propose a model for dissolution based on the relative rates of dissolution of the two glass compositions. The data are consistent with a modified version of TST and indicate the potency of VSI methods to elucidate glass reaction mechanisms

  6. Microwave Absorption of Barium Borosilicate, Zinc Borate, Fe-Doped Alumino-Phosphate Glasses and Its Raw Materials

    Directory of Open Access Journals (Sweden)

    Ashis Kumar Mandal

    2015-05-01

    Full Text Available This study presents microwave absorption of raw materials used in barium borosilicate, Fe-doped alumina phosphate and zinc borate glass. Microwave absorption was investigated for the raw materials SiO2, Na2CO3, BaCO3, BPO4, Al(PO33, Mg(PO32, Al(OH3, TiO2. The study shows that SiO2 could be heated directly above 1000 °C within 30 min at 1.5 kW microwave output (MW power and 0.8 kW MW power is necessary to initiate heating (from 260 °C. Microwave heating of material with low dielectric loss has been investigated by increasing MW power. Microwave absorption of above glass systems has also been investigated. Dielectric properties such as loss tangent of glass as a function of temperature are presented. Glass melting under direct microwave heating was demonstrated for the studied glass systems. Temperature-Microwave power-Time (T-P-t profiles for the three glasses indicate maximum MW output power ~1 kW, 0.65 kW and ~1 kW for barium borosilicate, zinc borate glass and alumino-phosphate glass for 60 g glass melting.

  7. Upconversion studies of Er3+/Yb3+ doped SrO.TiO2 borosilicate glass ceramic system

    International Nuclear Information System (INIS)

    Upconversion behaviour has been studied in various matrices and fine powders of SrTiO3 by previous workers. In present work, Er3+/Yb3+ were doped in appropriate ratio in SrO.TiO2 borosilicate glass ceramic system to study the upconversion phenomenon. Dielectric properties of this class of glass ceramic system have been extensively investigated by Thakur et al. It has been observed that both upconversion efficiency and dielectric constant increases with transformation of glass into glass ceramic. Therefore, present investigation is based upon the study of optical as well as the electrical properties of same glass ceramic system. In order to prepare different crystalline matrices, two different Er3+/Yb3+:SrO.TiO2 borosilicate glasses with same amount of Er2O3 and Yb2O3 were prepared by melt quench method. Glasses were transparent with light-wine colour. Glass ceramics were prepared from the glasses by heat treatment based on DTA (Differential thermal analysis) results. Glass ceramics were fully opaque with brownish-cream colour. Powder X-ray diffraction (XRD) patterns confirmed that two different crystalline matrices, Sr3Ti2O7, Ti10O19 and SrTiO3, TiO2 were present in two glass ceramic samples respectively. Luminescence properties of glass and glass ceramic samples with 976nm laser irradiation showed that the intensities of the green and red emission increased multiple times in glass ceramic than that of the glass. Possible mechanisms responsible for upconversion eg. Energy Transfer (ET) and Excited State Absorption (ESA), were studied through laser pumping power log dependence

  8. Low temperature sintering and performance of aluminum nitride/borosilicate glass

    Institute of Scientific and Technical Information of China (English)

    Hong-sheng ZHAO; Lei CHEN; Nian-zi GAO; Kai-hong ZHANG; Zi-qiang LI

    2009-01-01

    Aluminum nitride (AlN)/borosilicate glass composites were prepared by the tape casting process and hot-press sin-tered at 950 ℃ with AlN and SiO2-B2O3-ZnO-Al2O3-Li2O glass as starting materials. We characterized and analyzed the variation of the microstructure, bulk density, porosity, dielectric constant, thermal conductivity and thermal expansion coefficient (TEC) of the ceramic samples as a function of AlN content. Results show that AlN and SiO2-B2O3-ZnO-Al2O3-Li2O glass can be sintered at 950 ℃, and ZnAl2O4 and Zn2SiO4 phase precipitated to form glass-ceramic. The performance of the ceramic samples was de-termined by the composition and bulk density of the composites. Lower AlN content was found redounding to liquid phase sin-tering, and higher bulk density of composites can be accordingly obtained. With the increase of porosity, corresponding decreases were located in the dielectric constant, thermal conductivity and TEC of the ceramic samples. When the mass fraction of AlN was 40%, the ceramic samples possessed a low dielectric constant (4.5~5.0), high thermal conductivity (11.6 W/(m·K)) and a proper TEC (3.0×10K-1, which matched that of silicon). The excellent performance makes this kind of low temperature co-fired ce-ramic a promising candidate for application in the micro-electronics packaging industry.

  9. Dissolution of borosilicate glasses under repository conditions of pressure and temperature

    International Nuclear Information System (INIS)

    This paper described laboratory experimental work in progress in the UK to examine the mechanisms of fluid buffered interactions of materials at possible repository temperatures and pressures and aims at proposing limiting temperature values for a disposal facility from the geochemist's viewpoint. At present work is concentrated on reconnaissance experiments on dissolution rates of the vitrified waste form and the changes in near-field granite surface chemistry and fissure properties which will have a bearing on nuclide adsorption immediately after release. The major conclusions: in all of the experiments the fluid state remained as liquid since temperatures never exceeded 3740C, under these subcritical conditions pressure decreases dissolution rate; the ability to extrapolate dissolution rate from values of 1000C to about 2000C, together with the maintenance of physical integrity indicate that the glasses studied are likely to be stable and predictable in leach behavior to temperatures well in excess of those currently being considered for disposal; Glass 209 dissolves more slowly over a wide pressure and temperature spectrum than does glass 189, although the latter is easier to fabricate; dissolution rate decreases with increasing time. The principal conclusions of this study so far is that experimental application of realistic repository hydrothermal PT conditions indicate for the first time that current formulations of borosilicate glass would appear to provide for an adequate waste disposal medium which would maintain stability and predictable behavior over a wider pressure and temperature spectrum than previously realized, allowing sme latitude in both pre-disposal storage period and eventual loading at the time of disposal

  10. Borosilicate nuclear waste glass alteration kinetics theoretical basis for the kinetic law of nuclear glass alteration

    International Nuclear Information System (INIS)

    Work carried out since the early 1980's to predict the long-term behavior of nuclear containment glasses has revealed the inadequacy of existing models, notably in accounting for the fundamental mechanisms involved in some complex systems (e.g. glass-water-clay), inciting us to examine and discuss the theoretical basis for the hypotheses generally assumed in our models. This paper discusses the theoretical basis for the Aagaard-Helgeson law and its application to nuclear glasses. The contribution of other types of kinetic laws is also considered to describe the alteration kinetics of nuclear glasses. (authors)

  11. TRPLS (Time Resolved Photoluminescence) studies of U and Am in sol-gel derived alkali barium borosilicate glass

    International Nuclear Information System (INIS)

    Speciation studies of U and Am in alkali barium borosilicate glasses, prepared via sol-gel route were carried out using time resolved photoluminescence (TRPLS) spectroscopic technique. The PL spectrum of the uranium containing glass showed green emission band at 540 nm without any vibronic structure along with excitation peaks at 275, 323, 348 and 412 nm. These data indicated the presence of uranium as uranate (UO6)6- in the glass matrix. Am was stabilized in the matrix in its trivalent form which was confirmed from its excitation, emission and decay time data. (author)

  12. Preparation, characterization and standard molar enthalpy of formation of BaO containing sodium borosilicate glasses and its comparison with international standard glass

    International Nuclear Information System (INIS)

    High level radioactive liquid waste (HLW) generated during reprocessing of spent nuclear fuel is immobilized in sodium borosilicate (NBS) glasses. Addition of BaO in NBS glass helps to improve the solubility of ThO2 in glass matrix. The knowledge of thermodynamic stability of glasses used for immobilization of HLW is important in predicting their long term stability. Several BaO substituted NBS glass samples were prepared by melt-quench technique and characterized by XRD, DTA, MAS-NMR. The standard molar enthalpy of formation of BaO substituted NBS glasses and the International Standard Glass (ISG) were determined. This work is done with an understanding that even though the above glass matrices are metastable in nature and meaningful measurement of equilibrium thermodynamic data is difficult; the information on relative thermodynamic stability data of NBS glasses with varying compositions prepared exactly in similar fashion will be helpful in deciding the most stable matrix for nuclear waste disposal

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

    International Nuclear Information System (INIS)

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

  14. Acquisition of rheological and calorimetric properties of borosilicate glass to determine the free energy of formation

    International Nuclear Information System (INIS)

    No fundamental thermodynamic data, such as the entropy ΔfS T) and enthalpy ΔfH T) of formation are currently available for nuclear borosilicate glasses. They are necessary to assess the glass thermodynamic stability in water, one of the most important potential long-term glass alteration vectors. Three glass composition ranges were investigated: - 8 compositions ranging from a ternary B2O3-SiO2--Na2O (BSN) glass to the simulated SON 68 industrial glass for containment of high active nuclear wastes after reprocessing spent uranium oxide fuel from light water reactors. The basic BSN glass was gradually modified with the additives: Al2O3, CaO, ZrO2, Ce2O3, Li2O and Fe2O3, and non-radioactive surrogate fission product oxides. - A second using another BSN ternary glass to which Al2O3, MgO and a group of non-radioactive surrogate fission product oxides, representative of natural uranium GCR fuel, were added. - A third range consisting of various BSN ternary glass compositions. All the glass specimens were fabricated by melting the oxides, carbonates anal nitrates at 1273 to 1473 K in a platinum crucible. Experimental methods based on calorimetry and viscosimetry techniques were used to determine the heat capacity Cp of each glass composition, a necessary parameter in addition to the known heat capacities of the basic glass component oxides, for calculating ΔfS T) and ΔfS T). The heat capacity Cp was measured between 273 K and 1480 K through a combination of three experimental devices: a low-temperature adiabatic calorimeter, a differential scanning calorimeter, and an ice calorimeter. The glass configuration entropy Sconf(Tg) necessary to obtain the glass entropy of formation (Eqn.(3)) was determined from tile glass rheological properties. A low-temperature viscosimeter was used to measure the strain ε of a glass specimen subjected to a given uniaxial stress σ to determine the viscosity η. A Couette viscosimeter was used to measure low viscosities at up to 1700 K

  15. Effect of the Callovian-Oxfordian clayey fraction on borosilicate glass alteration

    International Nuclear Information System (INIS)

    exchangeable Mg and to check whether remaining Mg, especially structural Mg could still feed the solution. The cation exchange capacity (CEC) and the exchangeable cation population after treatment were measured by the cobaltihexamine test, indicating an enrichment of Na (from 14% to 79% in equivalents) of the exchangeable population at the expense of Ca (from 50% to 4%), Mg (from 15% to 6%) and K (from 18% to 7%) compared to the pristine clay-stone. Synthetic borosilicate Mg-free glasses were used as simplified references of the French nuclear glass R7T7. Batch experiments were performed in closed system at 90 deg. C during 150 days. The clay/glass (C/G) weight ratio ranged from 0.01 to 100 for a liquid/solid (L/S) weight ratio of 20. The specific surface was estimated to be around 0.06 m2/g and 100 m2/g for the glass powder and the clayey fraction, respectively. Chemical analysis of the batch solutions were carried out with time, as well as XRD, SEM and TOF-SIMS analysis of the solids after completion of the batch experiments. Modeling was performed with the GRAAL kinetic model of glass dissolution that considers elements and water diffusion in the alteration layer (Frugier et al., 2008), implemented within the reactive transport code HYTEC (van der Lee et al., 2003). The experiments showed that the higher the clay/glass ratio, the lower the pH90deg.C and the higher the glass alteration. As shown in Fig. 1, the pH90deg.C varied from 8.9 for the lowest clay/glass proportion (C/G 1) to 5.4 for the highest one (C/G = 100). The corresponding mean glass dissolution rates are 15 nm/d and 300 nm/d, respectively. A batch test performed with the sole clayey fraction in pure water yielded a pH90deg.C of 5.2, whereas the test made with the glass alone led to a pH90deg.C around 9. The main effect of the clayey fraction in the batch tests seems to drop the pH down to more acidic values that concentrations of B (a tracer of the glass alteration) on the one hand, and of the concentrations

  16. Glass transition and crystallization kinetics of a barium borosilicate glass by a non-isothermal method

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, Andreia A. S.; Soares, Roque S.; Lima, Maria M. A.; Monteiro, Regina C. C., E-mail: rcm@fct.unl.pt [Department of Materials Science, CENIMAT/I3N, Faculty of Sciences and Technology, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal)

    2014-01-28

    The glass transition and crystallization kinetics of a glass with a molar composition 60BaO-30B{sub 2}O{sub 3}-10SiO{sub 2} were investigated by differential scanning calorimetry (DSC) under non-isothermal conditions. DSC curves exhibited an endothermic peak associated with the glass transition and two partially overlapped exothermic peaks associated with the crystallization of the glass. The dependence of the glass transition temperature (T{sub g}) and of the maximum crystallization temperature (T{sub p}) on the heating rate was used to determine the activation energy associated with the glass transition (E{sub g}), the activation energy for crystallization (E{sub c}), and the Avrami exponent (n). X-ray diffraction (XRD) revealed that barium borate (β-BaB{sub 2}O{sub 4}) was the first crystalline phase to be formed followed by the formation of barium silicate (Ba{sub 5}Si{sub 8}O{sub 21}). The variations of activation energy for crystallization and of Avrami exponent with the fraction of crystallization (χ) were also examined. When the crystallization fraction (χ) increased from 0.1 to 0.9, the value of local activation energy (E{sub c}(χ)) decreased from 554 to 458 kJ/mol for the first exothermic peak and from 1104 to 831 kJ/mol for the second exothermic peak. The value determined for the Avrami exponent was near 2 indicating a similar one-dimensional crystallization mechanism for both crystalline phases. This was confirmed by the morphological studies performed by scanning electron microscopy (SEM) on glass samples heat-treated at the first and at the second crystallization temperatures.

  17. Ultrafast opacity in borosilicate glass induced by picosecond bursts of laser-driven ions

    CERN Document Server

    Dromey, B; Adams, D; Prasad, R; Kakolee, K F; Stefanuik, R; Nersisyan, G; Sarri, G; Yeung, M; Ahmed, H; Doria, D; Dzelzainis, T; Jung, D; Kar, S; Marlow, D; Romagnani, L; Correa, A A; Dunne, P; Kohanoff, J; Schleife, A; Borghesi, M; Currell, F; Riley, D; Zepf, M; Lewis, C L S

    2014-01-01

    Direct investigation of ion-induced dynamics in matter on picosecond (ps, 10-12 s) timescales has been precluded to date by the relatively long nanosecond (ns, 10-9 s) scale ion pulses typically provided by radiofrequency accelerators1. By contrast, laser-driven ion accelerators provide bursts of ps duration2, but have yet to be applied to the study of ultrafast ion-induced transients in matter. We report on the evolution of an electron-hole plasma excited in borosilicate glass by such bursts. This is observed as an onset of opacity to synchronised optical probe radiation and is characterised by the 3.0 +/- 0.8 ps ion pump rise-time . The observed decay-time of 35 +/- 3 ps i.e. is in excellent agreement with modelling and reveals the rapidly evolving electron temperature (>10 3 K) and carrier number density (>10 17cm-3). This result demonstrates that ps laser accelerated ion bursts are directly applicable to investigating the ultrafast response of matter to ion interactions and, in particular, to ultrafast pu...

  18. Supported TiO2 on Borosilicate Glass Plates for Efficient Photocatalytic Degradation of Fenamiphos

    Directory of Open Access Journals (Sweden)

    A. El Yadini

    2014-01-01

    Full Text Available Supported titanium dioxide (TiO2 was investigated for the photodegradation of the insecticide fenamiphos in water. The photocatalyst was immobilised on borosilicate glass plates and the kinetics of degradation were studied in a stirred tank reactor under UV irradiation. Two types of TiO2, for example, Millennium PC500 (100% anatase and Degussa P25 (80% anatase, 20% rutile, were used. Their activities have been based on the rates of insecticide disappearance. Experiments were investigated to evaluate the effect of pH and initial concentrations of fenamiphos as well as catalyst doses on the photocatalytic degradation of fenamiphos. Kinetic parameters were experimentally determined and an apparent first-order kinetic was observed. For photolysis process of fenamiphos, two photoproducts were identified and characterized using high performance liquid chromatography/mass spectrometry (HPLC/MS. The plausible mechanism of photolysis involved is the oxidation of sulfonamide group. In presence of photocatalyst TiO2, photodegradation was observed. Under identical conditions, Degussa P25 shows higher photocatalytic activity in regard to PC500 Millennium and complete degradation was observed after 180 min.

  19. Synthesis, characterization, and third-order nonlinear optical properties of copper quantum dots embedded in sodium borosilicate glass

    International Nuclear Information System (INIS)

    Highlights: ► The sodium borosilicate glass doped Cu quantum dots have been prepared by sol–gel route. ► The crystal structure and composition of as-prepared glass were investigated by XRD and XPS. ► Size and distribution of indium nanocrystals was determined by TEM and STEM. ► The third-order optical nonlinearity was investigated by using Z-scan technique. - Abstract: Copper quantum dots embedded in sodium borosilicate glass matrix were fabricated and analyzed in terms of their structural, chemical, and optical properties. X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses revealed that copper quantum dots were in face-centered-cubic crystalline phase and in the metallic state. Size and distribution of the quantum dots were measured by transmission electron microscopy (TEM) as well as high-resolution transmission electron microscopy (HRTEM). The results showed spherical shape have formed uniformly in the glass, and the size of these quantum dots were range from 1.5 to 5 nm with the average particle size about 2.7 nm. The third-order nonlinear optical properties of copper quantum dots doped glass were investigated by using Z-scan technique at the wavelength of 800 nm with femtosecond Ti: sapphire laser radiation. The value of third-order optical nonlinear susceptibility χ(3) of the glass was estimated to be 2.41 × 10−11 esu.

  20. Color-converted remote phosphor prototype of a multiwavelength excitable borosilicate glass for white light-emitting diodes

    Institute of Scientific and Technical Information of China (English)

    Tian Hua; Liu Ji-Wen; Qiu Kun; Song Jun; Wang Da-Jian

    2012-01-01

    We report a unique red light-emitting Eu-doped borosilicate glass to convert color for warm white light-emitting diodes.This glass can be excited from 394 nm-peaked near ultraviolet light,466 nm-peaked blue light,to 534 nm-peaked green light to emit the desired red light with an excellent transmission in the wavelength range of 400-700 nm which makes this glass suitable for color conversion without a great cost of luminous power loss.In particular,when assembling this glass for commercial white light-emitting diodes,the tested results show that the color rendering index is improved to 84 with a loss of luminous power by 12 percent at average,making this variety of glass promising for inorganic "remote-phosphor" color conversion.

  1. Color-converted remote phosphor prototype of a multiwavelength excitable borosilicate glass for white light-emitting diodes

    International Nuclear Information System (INIS)

    We report a unique red light-emitting Eu-doped borosilicate glass to convert color for warm white light-emitting diodes. This glass can be excited from 394 nm-peaked near ultraviolet light, 466 nm-peaked blue light, to 534 nm-peaked green light to emit the desired red light with an excellent transmission in the wavelength range of 400–700 nm which makes this glass suitable for color conversion without a great cost of luminous power loss. In particular, when assembling this glass for commercial white light-emitting diodes, the tested results show that the color rendering index is improved to 84 with a loss of luminous power by 12 percent at average, making this variety of glass promising for inorganic “remote-phosphor” color conversion

  2. Volatility mechanisms of borosilicate glasses and molten glasses of nuclear interest structural effects

    International Nuclear Information System (INIS)

    This work is devoted to the study of the mechanisms which control the volatility of the reference glass used for the confinement of radioactive waste. It was conducted on simplified compositions, in the SiO2-B2O3-Al2O3-αNa2O-(1-alpha)Li2O-CaO system.The structural approach carried out by NMR, from room temperature up to 1500 deg.C, shows a strong increase in the mobility of alkalis above Tg. A rapid exchange between BIII and BIV sites near 700 deg.C, and the change of coordination number BIV- BIII near 1100 deg.C, also seem to take place. The analysis of the vapor phase, carried out by High Temperature Mass Spectrometry coupled to Knudsen cells, reveals the presence between 780 deg.C and 830 deg.C of NaBO2(g), LiBO2(g) and Na2(BO2)2(g). The calculation of the partial pressure of each species shows that the total pressure of simplified glasses is dominated by the contribution of sodium. To study the volatility of glasses at higher temperature, equipment using the Transpiration method was used. The analysis of the deposits indicate the presence at 1060 deg.C of the species quoted previously. The vaporization rate and the vapor density were determined for each composition studied in a saturated state. Thus, we show that the volatility of the reference glass can be simulated by that of a simplified glass. For α=1, the kinetic of vaporization between 1060 deg.C and 1200 deg.C reveals an evaporation from the surface associated with a mechanism of diffusion in the molten glass. This is similar to the volatility of the reference glass at 1060 deg.C. To finally explain these mechanisms on a microscopic basis, we develop a model of molecular interactions. Between 780 deg.C and 830 deg.C, these mechanisms are controlled by a strong attraction between Na2O and Li2O, which maintains the total vapor pressure on a quasi-constant lever up to α=0.27. (author)

  3. Improvement in laser micromachinability of borosilicate glass by electric-field-assisted solid-state ion exchange

    International Nuclear Information System (INIS)

    In order to improve the laser machinability of borosilicate glass, copper ions were doped to the glass surface by electric-field-assisted solid-state ion-exchange method. The nanosecond ultraviolet laser irradiation of copper-containing regions produced flat, smooth and defect-free holes because of their high optical absorptions. However, the shapes of the holes were drastically degraded when the processed hole bottoms reached ion penetration depths. Therefore, well-designed and controlled ion distribution was necessary for the high-accuracy fabrication of microcomponents.

  4. Effects of magnesium minerals representative of the Callovian-Oxfordian clay-stone on borosilicate glass alteration

    International Nuclear Information System (INIS)

    Borosilicate glasses dissolution has been studied in presence of magnesium minerals. Those minerals (dolomite, illite, smectite...) belong to the Callovo-Oxfordian (COx) clay-stone layer, studied in France as a potential site for nuclear waste disposal. Such minerals contain magnesium, an element able to sustain glass alteration when it is available in solution. In the confined media of the wastes disposal, the solids reactivity controls the solution composition and can be the driving force of nuclear glass alteration. Experiments show that magnesium carbonates (hydro-magnesite and dolomite) increase in the glass alteration: the precipitation of magnesium silicates consumes silicon which slows down the formation of the glass passivating layer. The lower the magnesium mineral solubility, the lower the glass alteration. The purified clay phases (illite, smectite...) from the COx layer increase the glass alteration. Half the magnesium was replaced by sodium during the purification process. In such conditions, the effect of clay phases on glass alteration is in part due to the acidic pH-buffering effect of the clay fraction. The GRAAL model implemented in the geochemical transport code HYTEC has confirmed and quantified the mechanisms put in evidence in the experiments. Cells diffusion experiments where the two solids were separated by an inert diffusion barrier allow to valid reactive transport modelling. Such experiments are more representative of the glass package which will be separated from the COx by corrosion products. They show that glass alteration rate is reduced when solids are not close. (author)

  5. Integrated Optic Surface Plasmon Resonance Measurements in a Borosilicate Glass Substrate

    Directory of Open Access Journals (Sweden)

    Antonino Parisi

    2008-11-01

    Full Text Available The surface plasmon resonance (SPR technique is a well-known optical method that can be used to measure the refractive index of organic nano-layers adsorbed on a thin metal film. Although there are many configurations for measuring biomolecular interactions, SPR-based techniques play a central role in many current biosensing experiments, since they are the most suited for sensitive and quantitative kinetic measurements. Here we give some results from the analysis and numerical elaboration of SPR data from integrated optics experiments in a particular borosilicate glass, chosen for its composition offering the rather low refractive index of 1.4701 at 633 nm wavelength. These data regard the flow over the sensing region (metal window of different solutions with refractive indexes in the range of interest (1.3÷1.5 for the detection of contaminants in aqueous solutions. After a discussion of the principles of SPR, of the metal window design optimization by means of optical interaction numerical modeling, and of waveguide fabrication techniques, we give a description of system setup and experimental results. Optimum gold film window thickness and width in this guided-wave configuration has been for the first time derived and implemented on an integrated optic prototype device. Its characterization is given by means of the real time waveguide output intensity measurements, which correspond to the interaction between the sensing gold thin film window and the flowing analyte. The SPR curve was subsequently inferred. Finally, a modified version of the device is reported, with channel waveguides arranged in a Y-junction optical circuit, so that laser source stability requirements are lowered by a factor of 85 dB, making possible the use of low cost sources in practical applications.

  6. Visible to deep ultraviolet range optical absorption of electron irradiated borosilicate glass

    Science.gov (United States)

    Wang, Tie-Shan; Duan, Bing-Huang; Tian, Feng; Peng, Hai-Bo; Chen, Liang; Zhang, Li-Min; Yuan, Wei

    2015-07-01

    To study the room-temperature stable defects induced by electron irradiation, commercial borosilicate glasses were irradiated by 1.2 MeV electrons and then ultraviolet (UV) optical absorption (OA) spectra were measured. Two characteristic bands were revealed before irradiation, and they were attributed to silicon dangling bond (E’-center) and Fe3+ species, respectively. The existence of Fe3+ was confirmed by electron paramagnetic resonance (EPR) measurements. After irradiation, the absorption spectra revealed irradiation-induced changes, while the content of E’-center did not change in the deep ultraviolet (DUV) region. The slightly reduced OA spectra at 4.9 eV was supposed to transform Fe3+ species to Fe2+ species and this transformation leads to the appearance of 4.3 eV OA band. By calculating intensity variation, the transformation of Fe was estimated to be about 5% and the optical absorption cross section of Fe2+ species is calculated to be 2.2 times larger than that of Fe3+ species. Peroxy linkage (POL, ≡Si-O-O-Si≡), which results in a 3.7 eV OA band, is speculated not to be from Si-O bond break but from Si-O-B bond, Si-O-Al bond, or Si-O-Na bond break. The co-presence defect with POL is probably responsible for 2.9-eV OA band. Project supported by the Fundamental Research Funds for the Central Universities of China (Grant No. lzujbky-2014-16).

  7. Impact of soda-lime borosilicate glass composition on water penetration and water structure at the first time of alteration

    International Nuclear Information System (INIS)

    In this study, the impact of soda-lime borosilicate glass composition and particularly the effect of charge compensators such Ca and Na and, of network formers such Si and Zr, on water penetration and water structure at the first time of alteration were investigated. Two non-destructive techniques were combined: the Fourier transform infrared spectroscopy in attenuated total reflection geometry to precise the predominant alteration mechanisms and assess the water structure in altered zone and the grazing incidence X-ray reflectometry to determine the thickness of the altered glass zone allowing to calculate the water diffusion coefficients through the glasses. The results of glass alteration at pH = 3 and 30 degrees C have shown that hydrolysis was the predominant mechanism after few seconds for glass having a high amount of non-binding oxygen. For the other glasses, which for the diffusion was the limiting reaction, the calculated water diffusion coefficients were comprised between 10-21 and 10-19 m2.s-1 and vary as a function of glass composition. An activation energy of 76.9 kJ.mol-1 was calculated and appears to be higher than inert gas diffusion through the glass highlighting that water molecules strongly interact with the glass matrix. (authors)

  8. 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)

    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)

  9. High thermal neutron flux effects on structural and macroscopic properties of alkali-borosilicate glasses used as neutron guide substrate

    Science.gov (United States)

    Boffy, R.; Peuget, S.; Schweins, R.; Beaucour, J.; Bermejo, F. J.

    2016-05-01

    The behaviour of four alkali-borosilicate glasses under homogeneous thermal neutron irradiation has been studied. These materials are used for the manufacturing of neutron guides which are installed in most facilities as devices to transport neutrons from intense sources such as nuclear reactors or spallation sources up to scientific instruments. Several experimental techniques such as Raman, NMR, SANS and STEM have been employed in order to understand the rather different macroscopic behaviour under irradiation of materials that belong to a same glass family. The results have shown that the remarkable glass shrinking observed for neutron doses below 0.5 ·1018 n/cm2 critically depends upon the presence of domains where silicate and borate network do not mix.

  10. Mechanical and structural studies on sodium borosilicate glasses doped with Er2O3 using ultrasonic velocity and FTIR spectroscopy

    International Nuclear Information System (INIS)

    Sodium borosilicate glasses doped with different mol% content of Er2O3 have been prepared by rapid-quenching method. Ultrasonic velocities (both longitudinal and shear) measurements have been carried out at room temperature and at ultrasonic frequency of 4 MHz. Elastic moduli, Debye temperature, softening temperature, and Poisson's ratio have been obtained as a function of Er2O3 modifier content. Results show that the above-mentioned parameters have very slight change with the change of Er2O3 mol% content. Based on FTIR spectroscopy and theoretical (bond compression) model, quantitative analysis has been carried out in order to obtain more information about the structure of these glasses. The study indicated that the structure of these glasses is mainly composed of SiO4 units with four bridging oxygens (Q4), and with three bridging and one nonbridging oxygens (Q3)

  11. Formation of molecular clusters of selenium as an alternative to precipitation of CdSe nanoparticles in a borosilicate glass

    International Nuclear Information System (INIS)

    Solid-state precipitation in a borosilicate glass is a well-elaborated technique for obtaining II-VI semiconductor nanocrystals. The obtained nanocrystal size depends on the growth conditions (heat treatment temperature and duration). Here we present Raman evidence for an alternative process, precipitation of molecular clusters of selenium, which is also possible at certain growth conditions. Decoloured CdSe-doped borosilicate glass samples were subjected to thermal treatment at 625 to 700 C during 2 to 12 h. Resonant micro-Raman measurements were performed using a Dilor XY 800 spectrometer and different Ar+ laser lines for excitation. Besides the CdSe LO and 2LO phonon bands, the Raman spectra of the samples obtained at thermal treatment duration and temperature beyond the range, most suitable for the formation of CdSe nanocrystals, contained pronounced features at 323 and 646 cm-1. Based on their frequency positions, widths, intensities, and resonant behaviour, these features are attributed to Se2 clusters being formed in the glass during the thermal treatment.

  12. β-irradiation effect in alumino-borosilicate glasses: the role of RE co-doping (RE = Sm, Gd)

    International Nuclear Information System (INIS)

    The effect of Sm and Gd co-doping on the structural modifications of β-irradiated alumino-borosilicate glasses has been studied by electron paramagnetic resonance (ESR) and Raman spectroscopy. The ESR spectra showed that the relative amount of Gd3+ ions occupying network former positions (Gd[n.f.]3+) follows a nonlinear behavior as a function of the Sm/Gd ratio. This suggests that co-doping favors the occupation by Gd3+ ions of the network former positions rather than the modifier positions in alumino-borosilicate glasses. The appearance of a super-hyperfine structure of ESR lines attributed to boron-oxygen hole centers (BOHC) with increasing Sm/Gd ratio was observed. This suggests that Gd3+ ions are diluted in the vicinity of the BOHC defects. The concentration of defects created by irradiation reveals a nonlinear dependence on Sm and Gd co-doping for the lowest irradiation dose (105 Gy). Therefore, co-doping also affects the defect creation processes at least at the lowest irradiation dose. Raman spectroscopy measurements suggest that the irradiation-induced structural changes vary nonlinearly with the Sm/Gd ratio. In fact, the shift of the Si-O-Si bending vibration modes reveals a clear minimum for samples containing equal amounts of Sm and Gd (1: 1) in the investigated glasses. (authors)

  13. Comparative transportation risk assessment for borosilicate-glass and ceramic forms for immobilization of SRP Defense waste

    International Nuclear Information System (INIS)

    It is currently planned to immobilize the SRP high-level nuclear waste in solid form and then ship it from SRP to a federal repository. This report compared transportation operations and risks for SRP high-level waste in a borosilicate glass form and in a ceramic form. Radiological and nonradiological impacts from normal transport and from potential accidents during transit were determined using the Defense Waste Process Facility Environmental Impact Statement (DWPF EIS) as the source of basic data. Applicable regulations and some current regulatory uncertainties are also discussed

  14. 信息动态%Spectral Analysis of Ho3+ -doped and Ho3+, Yb3+, Er3+ Co-doped Up-conversion Luminescence Borosilicate Glass

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    A series of holmium ions doped borosilicate glass, including Ho3+ -doped, Ho3+/ Er3+ -doped, Ho3+/ Y Yb3+-doped and Ho3 Yb3 YEr3+ -doped galss, have been prepared by high-temperature melting. The up-conversion excitation spectra and emission spectra of the samples decrease. The analysis result reveals that both the intensities of excitation spectra and emission spectra were weaken with the Ho3+ concentration. The spectral intensities of Ho3+/Yb3+ -doped borosilicate glass increase with the increase of Ho3+ concentration because of the sensitization of Yb3+. The excitation and emission spectra intensities of Ho3+/Yb3 +/Er3+-doped borosilicate glass are weak, and the reason is the energy transfers from Ho3+ ions to Er3+ ions through energy resonant transfer process. Meanwhile the luminescence mechanism of broadband emission peaked at 550 nm is analyzed.

  15. Determination of boron concentration in borosilicate glass, boron carbide and graphite samples by conventional wet-chemical and nuclear analytical methods

    International Nuclear Information System (INIS)

    Boron is an important element in nuclear technology. A comparative study was carried out for the determination of boron in borosilicate glass, boron carbide and graphite samples by wet-chemical and nuclear analytical methods. Wet chemical methods namely titrimetry, Inductively Coupled Plasma Mass Spectrometry and ICP Optical Emission Spectrometry and nuclear analytical methods namely Particle Induced Gamma-Ray Emission and Nuclear Reaction Analysis were used. Boron concentrations were in trace (mg kg-1) level in graphite and percentage level in borosilicate glass and boron carbide. (author)

  16. Effect of 10B(n, α)7Li irradiation on the structure of a sodium borosilicate glass

    International Nuclear Information System (INIS)

    The effects of the nuclear reaction 10B(n, α)7Li on the properties and structure of a sodium borosilicate glass were analysed by density, hardness and fracture toughness measurements, Raman and Nuclear Magnetic Resonance spectroscopy and Transmission Electronic Microscopy (TEM) characterization. The TEM observations showed a homogeneous irradiated glass structure up to the nanometer scale. Modifications of the local order around the main cations were noticed, mainly a slight decrease of the mean boron coordination number and an increase of non-bridging oxygen concentrations. At the glass medium range order, the appearance of the D2 Raman band and a modification of the Si–O–Si angle distribution were also observed after irradiation. A comparison with other irradiation conditions with Swift Heavy Ions (Kr with 74 MeV) and Gold irradiation (with energies ranging from 1 to 7 MeV) is presented. Raman spectroscopy showed a similar final structure for irradiation conditions under which the glass evolutions are controlled by electronic energy loss in the ion tracks formation regime or nuclear energy loss. Despite important differences in energy deposition regimes, the similarities observed between the final glass structures suggest that structural evolutions are controlled by the glass relaxation mechanisms during the high quenching rate step that follows the energy deposition step

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

    International Nuclear Information System (INIS)

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

  18. Effects of cobalt-60 gamma radiation on the strength-related internal structure of the borosilicate glass

    International Nuclear Information System (INIS)

    Borosilicate glass in the form of glass slides (1.Omm in thickness and cut into 12.5mm x 55.Omm surface area) was examined to determine the reusability or recyclability and strength of glass apparatuses or compartments after exposing to gamma irradiation from Co-60 source. After knowing the initial parameters using EDXRF under six secondary targets, glass specimens prepared was subjected to gamma radiation for doses 3kGy, 6kGy, 15kGy, 25kGy, and 100kGy. Results of characterization under FTIR provides information about the occurred extension of B-O-Si and B-O-B linkages for lower doses (3-25kGy), while destruction of Si-O bonds for higher dose (100kGy). It shows direct relationship on the observed color change from clear ransparent to deep brown corresponding to the change in optical densities as irradiation dose increases. Ability to fade the induced deep brown color was also observed for a certain time interval which satisfies that this type of glass exhibits self healing property. Although, average energy of about 1.25MeV causes rearrangement of atoms within the glass, according to the XRD result, it remained to be an amorphous solid even in higher dose applied which satisfies that remanufacturing and recycling is possible. (author)

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

    International Nuclear Information System (INIS)

    Highlights: • Er3+ doped borosilicate glasses were processed with different compositions and characterizations. • An increase in the SiO2 content leads to a silicate-rich environment around the Er3+ site. • An increase in the SiO2 content decreases the Er3+ absorption cross-section at 980 nm. • Glasses with 60 mol% of SiO2 exhibit a stronger emission intensity at 1530 nm than glasses with x = 50. • Highest 1.5 μm emission intensity was achieved for the Al and P containing glass with 60 mol% of SiO2. - Abstract: The influence of the silica content on several properties of Er-doped borosilicate glasses in the presence of various amounts of P2O5 and Al2O3 has been investigated. The introduction of P2O5 and/or Al2O3 are responsible for structural modifications in the glass network through a charge-compensation mechanism related to the formation of negatively-charged PO4 and AlO4 groups or through the formation of AlPO4-like structural units. In this paper, we show that an increase in the SiO2 content leads to a silicate-rich environment around the Er3+ site, resulting in an increased dependence of the Er3+ ions optical and luminescence properties on the P2O5 and/or Al2O3 concentration. The highest emission intensity at 1.5 μm was achieved for the glass with an equal proportion of P and Al in the glass system with 60 mol% of SiO2

  20. A comparative study by Molecular Dynamics of the ballistic effects and the thermal quenching effects in a sodium borosilicate glass

    International Nuclear Information System (INIS)

    The understanding of the aging under irradiation of nuclear glasses requires to study the induced changes at the atomic scale. A sodium borosilicate glass has been modeled by molecular dynamics and then submitted to low energies (4 keV) cascades series. Between each cascade, the structural evolutions have been analyzed and have shown a linear correlation between the glass swelling and its polymerization degree. The deep analysis of the different units constituting the glass shows that the lattice depolymerization instigated by the damage is mainly induced by the BO4 units conversion to BO3 and by the increase of the non bridging oxygen number. On account of the established structural changes, a comparison of the structural effects induced by irradiation to those generated by thermal quenching has been carried out. For that, the same glass has been prepared with various quench velocities (5*1012 and 1014 k.s-1) and the different structures obtained have been analyzed. It has been shown an increase of the BO3 units to the detriment of the BO4 units when the quench velocity increases, as well the non-bridging oxygen number. Thus qualitatively, the irradiation effects lead to structural consequences equivalent to those induced by thermal quenching effects. (O.M.)

  1. Calcium-borosilicate glass-ceramics wasteforms to immobilize rare-earth oxide wastes from pyro-processing

    Science.gov (United States)

    Kim, Miae; Heo, Jong

    2015-12-01

    Glass-ceramics containing calcium neodymium(cerium) oxide silicate [Ca2Nd8-xCex(SiO4)6O2] crystals were fabricated for the immobilization of radioactive wastes that contain large portions of rare-earth ions. Controlled crystallization of alkali borosilicate glasses by heating at T ≥ 750 °C for 3 h formed hexagonal Ca-silicate crystals. Maximum lanthanide oxide waste loading was >26.8 wt.%. Ce and Nd ions were highly partitioned inside Ca-silicate crystals compared to the glass matrix; the rare-earth wastes are efficiently immobilized inside the crystalline phases. The concentrations of Ce and Nd ions released in a material characterization center-type 1 test were below the detection limit (0.1 ppb) of inductively coupled plasma mass spectroscopy. Normalized release values performed by a product consistency test were 2.64·10-6 g m-2 for Ce ion and 2.19·10-6 g m-2 for Nd ion. Results suggest that glass-ceramics containing calcium neodymium(cerium) silicate crystals are good candidate wasteforms for immobilization of lanthanide wastes generated by pyro-processing.

  2. Investigation on radiation shielding parameters of bismuth borosilicate glass from 1 keV to 100 GeV

    International Nuclear Information System (INIS)

    Highlights: ► Radiation shielding parameters of bismuth borosilicate glasses have been investigated. ► The energy variation of effective atomic number was observed. ► Shielding properties of glasses are better than some standard shielding materials. - Abstract: The radiation shielding parameters of (50 − x)SiO2: 15B2O3: 2Al2O3: 10CaO: 23Na2O: xBi2O3 glass systems (where x = 0, 5, 10, 15 and 20 mol%) were theoretically calculated using WinXCom program. The characteristics of radiation shielding parameters for the glass systems of different bismuth compositions were found to be dependent on energy regions. At low-energy region, the radiation shielding parameters show several discontinuous jumps correspond to photoelectric absorption edges. At medium-energy region, the radiation shielding parameters are almost constant and the effective atomic number is close to the mean atomic number, dominated by Compton scattering process. In high-energy regions, pair production becomes the main interaction process and tends to be constant over energy. The mean free paths of the glasses were compared with several standard shielding concretes and it had been shown with lower values of MFP (from 10 MeV to 100 GeV) than serpentite, odinary, chromite, ferrite and barite except for the glass systems with 0 and 5 mol% of Bi2O3. The investigation was carried out to explore the advantages of the glass systems in radiation shielding applications

  3. Incorporation of Fines and Noble Metals into HLW Borosilicate Glass: Industrial Responses to a Challenging Issue - 13056

    Energy Technology Data Exchange (ETDEWEB)

    Chauvin, E.; Chouard, N.; Prod' homme, A. [AREVA, AREVA NC, Paris (France); Boudot, E. [AREVA, AREVA NC, La Hague (France); Gruber, Ph.; Pinet, O. [CEA Marcoule LCV, France (France); Grosman, R. [AREVA, SGN, Paris (France)

    2013-07-01

    During the early stages of spent fuel reprocessing, the fuel rods are cut and dissolved to separate the solid metallic parts of the rods (cladding and end pieces) from the radioactive nitric acid solution containing uranium, plutonium, minor actinides and fission products (FP). This solution contains small, solid particles produced during the shearing process. These small particles, known as 'fines', are then separated from the liquid by centrifugation. At the La Hague plant in France, the fines solution is transferred to the vitrification facilities to be incorporated into borosilicate glass along with the highly radioactive FP solution. These fines are also composed of Zr, Mo and other noble metals (i.e. Ru, Pd, Rh, etc.) that are added before vitrification to the the FP solution that already contained noble metals. As noble metals has the potential to modify the glass properties (including viscosity, electrical conductivity, etc.) and to be affected by sedimentation inside the melter, their behavior in borosilicate glass has been studied in depth over the years by the AREVA and CEA teams which are now working together in the Joint Vitrification Laboratory (LCV). At La Hague, the R7 vitrification facility started operation in 1989 using induction-heated metallic melter technology and was quickly followed by the T7 vitrification facility in 1992. Incorporating the fines into glass has been a challenge since operation began, and has given rise to several R and D studies resulting in a number of technological enhancements to improve the mixing capability of the melters (multiple bubbling technology and mechanical stirring in the mid-90's). Nowadays, the incorporation of fines into R7T7 glass is well understood and process adaptations are deployed in the La Hague facilities to increase the operating flexibility of the melters. The paper will briefly describe the fines production mechanisms, give details of the resulting fines characteristics, explain

  4. Silver diffusion and coloration of soda lime and borosilicate glasses, Part 1: Effect on the transmission and coloration of stained glasses

    Directory of Open Access Journals (Sweden)

    ABDELLAH CHORFA

    2012-03-01

    Full Text Available Using the conventional method of coloration, soda lime and borosilicate glasses have been painted. Once stained, these glasses were heat treated at temperatures close to their transition temperatures (Tg. A parametric study was carried out in order to determine at first the effect of the silver concentration in the stain spread on glass. In addition, it was studied the effect of the heat treatment duration and the chemical composition of the painted glasses on the formation and size of the silver nanoparticles, the silver diffusion depth and also the glasses coloration. The characterization was made using UV-Vis spectroscopy, Raman confocal spectroscopy, SEM, EDX Technique and Abbe Refractometer. The obtained results shows that the coloration intensity of both glass types painted by the conventional method differs and depends essentially on the proportion of alkali ions in the glass. Moreover, it was found that the effect of the silver concentration in the stain is primordial and the heat treatment duration has a limited effect.

  5. 3 and 4 oxidation state element solubilities in borosilicate glasses. Implement to actinides in nuclear glasses; Solubilite des elements aux degres d'oxydation (3) et (4) dans les verres de borosilicate. Application aux actinides dans les verres nucleaires

    Energy Technology Data Exchange (ETDEWEB)

    Cachia, J.N

    2005-12-15

    In order to ensure optimal radionuclides containment, the knowledge of the actinide loading limits in nuclear waste glasses and also the comprehension of the solubilization mechanisms of these elements are essential. A first part of this manuscript deals with the study of the differences in solubility of the tri and tetravalent elements (actinides and surrogates) particularly in function of the melting temperature. The results obtained indicate that trivalent elements (La, Gd, Nd, Am, Cm) exhibit a higher solubility than tetravalent elements (Hf, Th, Pu). Consequently, it was planned to reduce plutonium at the oxidation state (III), the later being essentially tetravalent in borosilicate glasses. An innovating reduction process of multi-valent elements (cerium, plutonium) using silicon nitride has been developed in a second part of this work. Reduced plutonium-bearing glasses synthesized by Si{sub 3}N{sub 4} addition made it possible to double the plutonium solubility from 2 to 4 wt% at 1200 deg C. A structural approach to investigate the differences between tri and tetravalent elements was finally undertaken. These investigations were carried out by X-rays Absorption Spectroscopy (EXAFS) and NMR. Trivalent rare earth and actinide elements seem to behave as network modifiers while tetravalent elements rather present true intermediaries' behaviour. (author)

  6. Interaction of borosilicate glass and granodiorite at 1000C, 50 MPa: implications for models of radionuclide release

    International Nuclear Information System (INIS)

    The interaction of a simulated borosilicate waste glass, granodiorite and deionized water at 1000C, 50 MPa under closed system experimental conditions has revealed the rapid achievement of steady-state fluid concentrations for many chemical components of interest, (e.g., SiO2, La) and their rates of release from the near-field would be most appropriately modelled by a function of solubility and groundwater flow-rate. The conversion of these solubilities into conventional leach-rates has shown over five orders of magnitude range in relative release rates and emphasizes the need for source-term models to consider each radionuclide separately in terms of mechanisms of release

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

    International Nuclear Information System (INIS)

    Viscosity and electrical conductivity of 79 simulated borosilicate glasses in the expected range of compositions to be produced in the Hanford Waste Vitrification Plant were measured within the temperature span from 950 to 1250 degree C. The nine major oxide components were SiO2, B2O3, Li2O, Na2O, CaO, MgO, Fe2O3, Al2O3, and ZrO2. The test compositions were generated statistically. The data were fitted by Fulcher and Arrhenius equations with temperature coefficients being multilinear functions of the mass fractions of the oxide components. Mixture models were also developed for the natural logarithm of viscosity and that of electrical conductivity at 1150 degree C. Least squares regression was used to obtain component coefficients for all the models

  8. Mild solvothermal synthesis and characterization of ZnO crystals with various morphologies on borosilicate glass substrate

    Science.gov (United States)

    Long, Tengfa; Takabatake, Kouta; Yin, Shu; Sato, Tsugio

    2009-01-01

    ZnO crystals with various morphologies were successfully prepared on borosilicate glass substrate in mild solution. Water and 50 vol% ethylene glycol aqueous solution were used as reaction solvents to investigate the crystal growth behavior. The effects of solvents and reaction time on the properties of crystals were investigated by Brunauer-Emmett-Teller (BET), scanning electron microscope (SEM), X-ray diffraction (XRD) analysis, photoluminescence spectroscopy, and photocatalytic characterization. The results indicated that the addition of ethylene glycol led to uniform crystal growth; however, the ZnO crystals synthesized in water possessed more excellent photoluminescence and photocatalytic activities. About 4.25%, 6.38% and 29.78% of 1 ppm NO x gas could be continuously removed under irradiation of light wavelength >510, >410 and >290 nm, respectively.

  9. The geochemical interactions of simulated borosilicate waste glass, granite and water at 100-3500C and 50MPa

    International Nuclear Information System (INIS)

    Four interactions experiments involving a simulated borosilicate waste glass, granite and deionised water have been carried out at 1000, 1500, 2000 and 3500C at a total pressure of 50 MPa to simulate the near-field geochemistry of a high level waste repository in granite. Experiments were conducted in gold-titanium cell, direct sampling autoclaves for run durations of 200 days (1000, 1500 and 2000C) and 30 days (3500C), during which time solution samples were extracted for the analysis of 25 chemical species. Solid phases retrieved at the end of the experiments were examined using X-ray diffraction and scanning electron microscopy. The high temperature speciation characteristics and degrees of mineral saturation of the fluids were investigated using the geochemical software packages, EQ3 and SOLMNEQ. (author)

  10. Rhenium Solubility In Borosilicate Nuclear Waste Glass Implications For The Processing And Immobilization Of Technetium-99 (And Supporting Information With Graphical Abstract)

    International Nuclear Information System (INIS)

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-08-13

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

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

    Science.gov (United States)

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

    2006-07-01

    Bioactive glasses with controllable conversion rates to hydroxyapatite (HA) may provide a novel class of scaffold materials for bone tissue engineering. The objective of the present work was to comprehensively characterize the conversion of a silicate bioactive glass (45S5), a borate glass, and two intermediate borosilicate glass compositions to HA in a dilute phosphate solution at 37 degrees Celsius. The borate glass and the borosilicate glasses were derived from the 45S5 glass by fully or partially replacing the SiO(2) with B(2)O(3). Higher B(2)O(3) content produced a more rapid conversion of the glass to HA and a lower pH value of the phosphate solution. Whereas the borate glass was fully converted to HA in less than 4 days, the silicate (45S5) and borosilicate compositions were only partially converted even after 70 days, and contained residual SiO(2) in a Na-depleted core. The concentration of Na(+) in the phosphate solution increased with reaction time whereas the PO(4) (3-) concentration decreased, both reaching final limiting values at a rate that increased with the B(2)O(3) content of the glass. However, the Ca(2+) concentration in the solution remained low, below the detection limit of atomic absorption, throughout the reaction. Immersion of the glasses in a mixed solution of K(2)HPO(4) and K(2)CO(3) produced a carbonate-substituted HA but the presence of the K(2)CO(3) had little effect on the kinetics of conversion to HA. The kinetics and mechanisms of the conversion process of the four glasses to HA are compared and used to develop a model for the process. PMID:16770542

  13. Analysis of barium borosilicate glass matrix for uranium determination by using ns-IR-LIBS in air and Ar atmosphere

    International Nuclear Information System (INIS)

    In this paper, an attempt to explore the use of laser induced breakdown spectroscopy (LIBS) technique for determination of uranium in the vitrified simulated high level barium borosilicate waste glass matrix was made with a commercial portable LIBS system. The emission spectrum of the waste glass being very complex, detailed study was done for proper choice of the emission lines. Investigations were carried out to optimize the experimental parameters like laser energy and acquisition delay time for the analysis. Calibration curves were obtained for two emission lines of U in these glasses. Effect of Ar atmosphere was also studied and the signal intensity was found to be ∝5 times higher than in air atmosphere. The emission lines used for normalization with vast difference in the upper energy level compared to the line of interest were found to give poor precision in air. In the Ar atmosphere, this effect was found to be much less significant and such emission lines can be used as an internal standard to achieve precise calibration curves. LIBS approach will be useful for real time determination of U in such samples, eliminating quantitative dissolution step required in many other analytical techniques like solution based ICP-MS/OES.

  14. Study of phase separation and crystallization phenomena in soda-lime borosilicate glass enriched in MoO3

    International Nuclear Information System (INIS)

    Molybdenum oxide immobilization (MoO3, as fission product) is one of the major challenges in the nuclear glass formulation issues for high level waste solutions conditioning since many years, these solutions arising from spent nuclear fuel reprocessing. Phase separation and crystallisation processes may arise in molten glass when the MoO3 content is higher than its solubility limit that may depend on glass composition. Molybdenum combined with other elements such as alkali and alkaline-earth may form crystalline molybdates, known as 'yellow phases' in nuclear glasses which may decrease the glass durability. In order to confine high level wastes (HLW) such as the fission product solutions arising from the reprocessing of high burn-up UOX-type nuclear spent fuels, a new glass composition (HLW glass) is being optimized. This work is devoted to the study of the origin and the mechanism of phase separation and crystallization phenomena induced by molybdenum oxide incorporation in the HLW glass. From microstructural and structural point of view, the molybdenum oxide behavior was studied in glass compositions belonging to the SiO2-B2O3- Na2O-CaO simplified system which constituted basis for the HLW glass formulation. The structural role of molybdenum oxide in borosilicate network explaining the phase separation and crystallization tendency was studied through the coupling of structural (95Mo, 29Si, 11B, 23Na MAS NMR, XRD) and microstructural (SEM, HRTEM) analysis techniques. The determination of phase separation (critical temperature) and crystallization (liquidus temperature) appearance temperatures by in situ viscosimetry and Raman spectroscopy experiments allowed us to propose a transformation scenario during melt cooling. These processes and the nature of the crystalline phases formed (CaMoO4, Na2MoO4) that depend on the evolution of MoO3, CaO and B2O3 contents were correlated with changes of sodium and calcium cations proportions in the environment of molybdate

  15. Effect of the nature of alkali and alkaline-earth oxides on the structure and crystallization of an alumino-borosilicate glass developed to immobilize highly concentrated nuclear waste solutions

    International Nuclear Information System (INIS)

    A complex rare-earth rich alumino-borosilicate glass has been proved to be a good candidate for the immobilization of new high level radioactive wastes. A simplified seven-oxides composition of this glass was selected for this study. In this system, sodium and calcium cations were supposed in other works to simulate respectively all the other alkali (R+ = Li+, Rb+, Cs+) and alkaline-earth (R2+ = Sr2+, Ba2+) cations present in the complex glass composition. Moreover, neodymium or lanthanum are used here to simulate all the rare-earths and actinides occurring in waste solutions. In order to study the impact of the nature of R+ and R2+ cations on both glass structure and melt crystallization tendency during cooling, two glass series were prepared by replacing either Na+ or Ca2+ cations in the simplified glass by respectively (Li+, K+, Rb+, Cs+) or (Mg2+, Sr2+, Ba2+) cations. From these substitutions, it was established that alkali ions are preferentially involved in the charge compensation of (AlO4)- entities in the glass network comparatively to alkaline-earth ions. The glass compositions containing calcium give way to the crystallization of an apatite silicate phase bearing calcium and rare-earth ions. The melt crystallization tendency during cooling strongly varies with the nature of the alkaline-earth. (authors)

  16. Leach mechanisms of borosilicate glass Defense Waste Forms - effects of composition

    International Nuclear Information System (INIS)

    The study described below concerns the mechanisms which control the leaching of two Defense Wasteforms, viz. SRL TDS-131 glass and MCC Defense Waste Reference Glass. It is shown that both the leach mechanisms and the structure of the leached surface are strongly dependent not only on the composition of the leachant and the contact time between the leachant and the glass but also on the exact composition of the glass. The relatively minor differences in composition between the two glasses investigated here were observed to give rise to large differences in leach behavior, in particular upon prolonged contact with water, rather than to limited changes in leach rate alone

  17. First investigations of the influence of IVB elements (Ti, Zr, and Hf) on the chemical durability of soda-lime borosilicate glasses

    International Nuclear Information System (INIS)

    The influence of IVB elements (Zr, Ti, and Hf) on the glass structure and on the alteration kinetics of soda-lime borosilicate glasses has been studied at various stages of glass leaching corresponding to the initial dissolution rate, rate drop, and residual rate regimes. The effect of these elements on the limiting mechanisms of the glass durability as well as the chemistry of both solution and alteration layer are inter-related, depending on the reaction progress. The effect of IVB elements on the glass structure was investigated using 11B MAS NMR. The IVB elements are compensated primarily by Na rather than Ca, at the expense of tetra-coordinated boron. The addition of HfO2 or ZrO2 decreases the initial dissolution rate in a similar way. Moreover, adding ZrO2 limits the rate drop in saturated media. The initial dissolution rate decrease is less significant when Ti is added, and a quick drop of the dissolution rate is observed up to 4 mol% TiO2. At low IVB element concentration, glasses containing Ti and Zr show different residual rates arising from the precipitation of magadiite (Na2Si14O29 center dot 11H2O), at the surface of Ti-bearing glasses. The influence of IVB elements on glass alteration indicates that, unlike Ti, Zr and Hf plays a similar role in the structure of borosilicate glasses. (authors)

  18. A container closure system that allows for greater recovery of radiolabeled peptide compared to the standard borosilicate glass system

    International Nuclear Information System (INIS)

    Objectives: Often peptides used in synthesis of radiopharmaceutical PET tracers are lipophilic and adhere to the walls of container closure systems (CCS) such that costly peptide and product are not fully recoverable after synthesis occurs. This investigation compares a standard United States Pharmacopeia (USP) Type I borosilicate glass CCS to a cyclic polyolefin copolymer Crystal Zenith® (CZ) CCS, for 68Ga-chloride and 68Ga-DOTATOC ([68Ga] Ga-DOTA-D-Phe1-Tyr3-octreotide) retention in the reaction vial after labeling. Methods: 68Gallium labeling of DOTATOC was conducted by adding 68Ga-chloride, 2 M HEPES (4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid) or 0.75 M sodium acetate, and 1–30 µg of DOTATOC into the CZ or glass CCS. The reaction mixture was heated for 15 min and cooled to room temperature. The crude reaction mixture was then withdrawn via syringe, for final processing. The CCS was then assayed using a dose calibrator to determine the amount of retained 68Ga-DOTATOC. Statistical significance was assessed using an unpaired Student's t-test. Results: In all experiments (n=72) with various amounts of peptide and different buffering systems, the CZ CCS retained less activity than the glass CCS. Using 2 M HEPES and 15 µg or 30 µg of DOTATOC, the CZ CCS retained approximately 10% less of the labeled DOTATOC compared to the glass CCS (p68Ga-chloride. Conclusion: For applications involving the labeling of peptides such as 68Ga-DOTATOC, the CZ CCS compared to the glass CCS, results in an improved recovery of product. - Highlights: • We examined the adhesion of 68Ga-DOTATOC to glass and CZ CCS. • The adhesion of the 68Ga-DOTATOC was 10% less in CZ CCS compared to glass CCS. • Overall recovery of 68Ga-DOTATOC reaction solution is higher in CZ CCS than glass CCS. • Adhesion to the CCS is due to 68Ga-DOTATOC, not 68Ga-chloride

  19. Determination of the free enthalpies of formation of borosilicate glasses; Determination des enthalpies libres de formation des verres borosilicates. Application a l'etude de l'alteration des verres de confinement de dechets radioactifs

    Energy Technology Data Exchange (ETDEWEB)

    Linard, Y

    2000-07-01

    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)

  20. Irradiations effects on the structure of boro-silicated glasses: long term behaviour of nuclear waste glassy matrices; Effets d'irradiations sur la structure de verres borosilicates - comportement a long terme des matrices vitreuses de stockage des dechets nucleaires

    Energy Technology Data Exchange (ETDEWEB)

    Bonfils, J. de

    2007-09-15

    This work deals with the long term behaviour of R7T7-type nuclear waste glasses and more particularly of non-active boro-silicated glasses made up of 3 or 5 oxides. Radioactivity of active glasses is simulated by multi energies ions implantations which reproduce the same defects. The damages due to the alpha particles are simulated by helium ions implantations and those corresponding to the recoil nucleus are obtained with gold ions ones. Minor actinides, stemming from the used fuel, is simulated by trivalent rare-earths (Eu{sup 3+} and Nd{sup 3+}). In a first part, we have shown by macroscopic experiments (Vickers hardness - swelling) and optical spectroscopies (Raman - ATR-IR) that the structure of the glassy matrices is modified under implantations until a dose of 2,3.10{sup 13} at.cm{sup -2}, which corresponds to a R7T7 storage time estimated at 300 years. Beyond this dose, no additional modifications have been observed. The second part concerns the local environment of the rare-earth ions in glasses. Two different environments were found and identified as follows: one is a silicate rich one and the other is attributed to a borate rich one. (author)

  1. A dynamic fatigue study of soda-lime silicate and borosilicate glasses using small scale indentation flaws

    International Nuclear Information System (INIS)

    The dynamic fatigue characteristics of two glasses, soda-lime silicate and borosilicate, in water have been studied using a controlled indentation flaw technique. It is argued that the indentation approach offers several advantages over more conventional fatigue testing procedures: (i) the reproducibility of data is relatively high, eliminating statistics as a basis of analysis: (ii) the flaw ultimately responsible for failure is well defined and may be conveniently characterised before and after (and during, if necessary) the strength test; (iii) via adjustment of the indentation load, the size of the flaw can be suitably predetermined. Particular attention is devoted to the third point because of the facility it provides for systematic investigation of the range of flaw sizes over which macroscopic crack behaviour remains applicable. The first part of the paper summarises the essential fracture mechanics theory of the extension of an indentation flaw to failure. In the next part of the paper the results of dynamic fatigue tests on glass rods in distilled water are described. Data are obtained for Vickers indentation loads in the range 0.05 to 100 N, corresponding to contact dimensions of 2 to 100 μm. Finally, the implications of the results in relation to the response of 'natural' flaws are discussed. (author)

  2. Sol–gel synthesis of silver nanocrystals embedded in sodium borosilicate monolithic transparent glass with giant third-order optical nonlinearities

    International Nuclear Information System (INIS)

    Highlights: • We prepared Ag-doped sodium borosilicate monolithic glass. • The influence of temperature on the SPR absorption peak intensity was studied. • Nonlinear optical properties of the glass were investigated. • A mechanism for the formation of Ag quantum dots glass was proposed. - Abstract: We report the preparation of uniform spherical shape silver nanocrystals doped sodium borosilicate monolithic transparent glass by sol–gel method. The characterization of the resulting Ag nanocrystals was accomplished by using X-ray powder diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectrum. Surface plasma resonance absorption peaks of the silver nanocrystals glass at about 406 nm have been obtained from ultraviolet–visible absorption spectrometer and their intensity is changed with different heat treatment temperatures. We have investigated the nonlinear optical properties of silver quantum dots doped glass using Z-scan technique. Third-order nonlinear optical susceptibility χ(3) of the glass was estimated to be 1.01 × 10−11 esu. In particular, a mechanism for the formation of Ag quantum dots glass is proposed. This work will significantly promote the obtained material applications in optical devices

  3. FTIR and optical assessment of zinc doped calcium phospho-borosilicate sol-gel glasses/glass-ceramics

    Science.gov (United States)

    Kumar, V.; Arora, N.; Pandey, O. P.; Kaur, G.

    2015-08-01

    CaO-P2O5-ZnO-SiO2-B2O3 glasses with varying compositions of calcium oxide and phosphorous oxide are synthesized using sol-gel technique. The glasses are heat-treated for a duration of 10 h at 500°C to obtain the glass-ceramics. The glass-ceramics and glasses are characterized using Fourier transform infrared spectroscopy (FTIR) and UV-Visible spectroscopy. Extinction coefficients, attenuation coefficients and dielectric constant have been obtained for all the glasses as well as glass ceramics. The results are discussed in light of non-bridging oxygens (NBO) and heat-treatment of glasses. In addition to this, the effect of calcium and phosphorous on the infra-red spectra has been analysed thoroughly.

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

    International Nuclear Information System (INIS)

    This study is related to the question of the long-term behaviour of the nuclear waste confinement glass. A glass alteration layer (known as the 'gel'), formed at the glass surface in contact with water, can limit the exchanges between the glass and the solution. We studied five oxide based glasses SiO2-B2O3-Na2O-CaO-ZrO2. Two series of glasses were synthesized by substituting CaO for Na2O and ZrO2 for SiO2. The leaching showed that the presence of Ca improves the reticulation of the vitreous network, inducing a decrease in the final degree of corrosion and the presence of Zr prevents the hydrolysis of silicon, which leads to a decrease of the initial dissolution rate. However, the introduction of Zr delays the drop of the alteration rate and leads to an increase in the alteration degree. In order to explain this unexpected behaviour, the gel morphology was investigated by small angle X-ray scattering. These experiments showed that the restructuring of porous network during the glass alteration process is limited by the increase of the Zr-content. Then, the restructuring of gel is at the origin of the major drop in the alteration rate observed for the low Zr-content glasses. Besides, both time-of-flight secondary-ion mass spectroscopy (ToF-SIMS) that provides an evaluation of extraneous element penetration into the gel pores and neutron scattering with index matching showed that the porosity closed during the corrosion in the glass without zirconia, but remained open in the high Zr-content glasses. These experiments, associated to simulations by a Monte Carlo method, establish a relationship between the morphologic transformations of gel and the alteration kinetics. (author)

  5. Long-term aqueous alteration kinetics of an alpha-doped SON68 borosilicate glass

    OpenAIRE

    TRIBET M.; ROLLAND Séverine; S. Peuget; Magnin, Magali; BROUDIC Véronique; JANSSEN ARNE; Wiss, Thierry; JEGOU C.; Toulhoat, Pierre

    2013-01-01

    The long-term behavior of nuclear glass subjected to alpha radiation by minor actinides must be investigated with a view to geological disposal. This study focuses on the effect of alpha radiation on the chemical reactivity of R7T7 glass with pure water, mainly on the residual alteration rate regime. A glass specimen doped with 0.85 wt% 239PuO2 (α emitter) is leached under static conditions in argon atmosphere at 90°C and at a high surface-area-to-volume ratio (S/V = 20 cm-1). The alteration ...

  6. Electrical conductivity and 11B NMR studies of sodium borosilicate glasses

    International Nuclear Information System (INIS)

    A large number of compositions within the SiO2-NaO2-B2O3 (SNB) ternary glass system were investigated by various complementary techniques. Impedance spectroscopy was used to determine the parameters related to sodium ion diffusion in the glass structure; high-field boron NMR measurements on a series of samples identified and quantified the boron coordination as a function of the composition; exhaustive DTA measurements gave the glass transition temperature for all the compositions studied. Based on these results we demonstrate that the activation energy of sodium ion diffusion is closely related to the boron coordination number and involves two types of structural motifs: one corresponding to the sodium associated to non-bridging oxygen atoms, and the other to sodium compensating B(IV) motif. We also show that simple DTA measurements of the glass transition temperature can be used to define structural domains within this ternary composition range. (authors)

  7. Effect of cerium oxide addition on electrical and physical properties of alkali borosilicate glasses

    International Nuclear Information System (INIS)

    The study of electrical conductivity, density and coefficient of thermal expansion (CTE) of Na2O:K2O:B2O3:SiO2:BaO glass samples with addition of cerium oxide has been carried out. It has been observed that the addition of cerium oxide affects the electrical conductivity, density and CTE. The results have been explained on the basis of the variation in number of bridging oxygens (BOs) and non-bridging oxygens (NBOs) present in the glass. In general, the glass with more NBOs has a weak network which exhibits higher electrical conductivity. The weakening of the network has been supported by the observed decrease in density and increase in CTE for the glasses.

  8. Experimental Study and Monte Carlo Modeling of Calcium Borosilicate Glasses Leaching

    International Nuclear Information System (INIS)

    During aqueous alteration of glass an alteration layer appears on the glass surface. The properties of this alteration layer are of great importance for understanding and predicting the long-term behavior of high-level radioactive waste glasses. Numerical modeling can be very useful for understanding the impact of the glass composition on its aqueous reactivity and long-term properties but it is quite difficult to model these complex glasses. In order to identify the effect of the calcium content on glass alteration, seven oxide glass compositions (57SiO2 17B2O3 (22-x)Na2OxCaO 4ZrO2; 0 < x < 11) were investigated and a Monte Carlo model was developed to describe their leaching behavior. The specimens were altered at constant temperature (T = 90 deg. C) at a glass-surface-area-to-solution-volume (SA/V) ratio of 15 cm-1 in a buffered solution (pH 9.2). Under these conditions all the variations observed in the leaching behavior are attributable to composition effects. Increasing the calcium content in the glass appears to be responsible for a sharp drop in the final leached boron fraction. In parallel with this experimental work, a Monte Carlo model was developed to investigate the effect of calcium content on the leaching behavior especially on the initial stage of alteration. Monte Carlo simulations performed with this model are in good agreement with the experimental results. The dependence of the alteration rate on the calcium content can be described by a quadratic function: fitting the simulated points gives a minimum alteration rate at about 7.7 mol% calcium. This value is consistent with the figure of 8.2 mol% obtained from the experimental work. The model was also used to investigate the role of calcium in the glass structure and it pointed out that calcium act preferentially as a network modifier rather than a charge compensator in this kind of glasses. (authors)

  9. Deep wet etching of borosilicate glass and fused silica with dehydrated AZ4330 and a Cr/Au mask

    International Nuclear Information System (INIS)

    This research highlights a superior glass-wet-etch technique which enables a glass wafer to be etched for more than 20 h in 49 wt% hydrofluoric acid (HF) only with Cr/Au film and a common positive photoresist, AZ4330. We demonstrated that pits on the wet-etched glass wafer were generated not only due to HF diffusion through the Cr/Au film but also due to pinholes on the Cr/Au films created by the diffusion of the Cr/Au etchant through a photoresist etching-mask during the Cr/Au wet etching process. These two types of diffusion, HF diffusion and Cr/Au etchant diffusion, were eliminated by the thermal curing of a photoresist (PR), AZ4330, before the Cr/Au wet etching process. The curing process allowed the PR to dehydrate, increased the hydrophobicity, and prevented the diffusion of the hydrophilic HF and Cr/Au etchant. Optimization of the curing process was performed, showing that curing at 130 °C for 20 min was the proper condition. With the optimized process, a 525 µm thick borosilicate glass wafer was penetrated with 49%wt HF. A fused silica wafer 525 µm thick was also wet-etched and penetrated with 49 wt% HF at 10 h. Moreover, no pits were found in wet etching of the fused silica for 20 h in 49 wt% HF. These findings demonstrate that the proposed technique allows the wet etching of a glass wafer for more than 20 h in 49%wt HF, the best result thus far. We fabricated a glass substrate with a 217.0 µm deep cavity and a penetrating through-via using the proposed technique, proving the feasibility of the product as an optical component with a surface roughness of 45.5 Å in the cavity. (paper)

  10. Molecular dynamics study of structural changes versus deposited energy dose in a sodium borosilicate glass

    Energy Technology Data Exchange (ETDEWEB)

    Bureau, G.; Delaye, J.M.; Peuget, S. [DEN/DTCD/SECM, CEA Marcoule, BP 17171, Bagnols-sur-Ceze cedex, 30207 (France); Calas, G. [IMPMC, 140 rue de Lourmel, Paris, 75015 (France)

    2008-07-01

    Assessing the long-term behavior of nuclear glass implies evaluating the impact of cumulative alpha decay induced by the minor actinides it contains. When subjected to alpha decay ({sup 244}Cm-doped glass specimens) or to external ion irradiation, some macroscopic properties vary appreciably with the dose. Above a given dose level, the properties do not evolve any more. To improve our understanding of these modifications, studies are carried out on simplified glass compositions (three oxides SiO{sub 2}, B{sub 2}O{sub 3}, Na{sub 2}O), modeled by molecular dynamics in which irradiation effects are simulated by accelerating uranium projectiles. Accumulation of displacements cascades have been performed up to 4.5*10{sup 20} keV/cm{sup 3} nuclear energy deposited in the glass. The density variations observed in actinide-doped materials is qualitatively reproduced. At high doses, the swelling tends to stabilize. Marples model is used to fit the glass swelling versus the deposited energy dose, giving the volume damaged per projectile. This volume approximates the cascade core volume, suggesting that the underlying mechanisms of volume expansion are contained in the cascade core and are thus related to the highest energy events: atom ejection and thermal quenching. On the contrary, the volumetric parameter of the Marples model applied to the other structural properties is related to a volume corresponding to the core + periphery of the cascades. (authors)

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

    International Nuclear Information System (INIS)

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

  12. The structure of phosphate and borosilicate glasses and their structural evolution at high temperatures as studied with solid state NMR spectroscopy: Phase separation, crystallisation and dynamic species exchange

    International Nuclear Information System (INIS)

    In this contribution we present an in-depth study of the network structure of different phosphate based and borosilicate glasses and its evolution at high temperatures. Employing a range of advanced solid state NMR methodologies, complemented by the results of XPS, the structural motifs on short and intermediate length scales are identified. For the phosphate based glasses, at temperatures above the glass transition temperature Tg, structural relaxation processes and the devitrification of the glasses were monitored in situ employing MAS NMR spectroscopy and X-ray diffraction. Dynamic species exchange involving rapid P-O-P and P-O-Al bond breaking and reforming was observed employing in situ 27Al and 31P MAS NMR spectroscopy and could be linked to viscous flow. For the borosilicate glasses, an atomic scale investigation of the phase separation processes was possible in a combined effort of ex situ NMR studies on glass samples with different thermal histories and in situ NMR studies using high temperature MAS NMR spectroscopy including 11B MAS, 29Si MAS and in situ 29Si{11B} REAPDOR NMR spectroscopy. (authors)

  13. Study of powellite-rich glass-ceramics for nuclear waste immobilization

    International Nuclear Information System (INIS)

    MoO3 is poorly soluble in borosilicate glasses which can lead to the crystallization of undesired phases when its concentration or the charge load (minor actinides and fission products concentration) is too high. Crystallization control is needed to guarantee good immobilization properties. We studied powellite-rich glass-ceramics obtained from a simplified nuclear glass in the system SiO2 - B2O3 - Na2O - CaO - Al2O3 - MoO3 - RE2O3 (RE = Gd, Eu, Nd) by various heat treatments. Rare earth elements (REE) were added as minor actinides surrogates and as spectroscopic probes. The influence of MoO3 and RE2O3 content on powellite (CaMoO4) crystallization was investigated. Various glass-ceramics (similar residual glass + powellite) were obtained with large crystal size distributions. Phase separation due to molybdenum occurs during quenching when [MoO3] ≥ 2.5 mol%. We showed that increasing the rare earth content can suppress the phase separation due to molybdenum but it leads to spinodal decomposition of the residual glass. Furthermore, we studied the effects of parent glass complexifying and the insertion of Gd3+ ions into the powellite structure. In order to understand the influence of microstructure on evolutions under β-irradiation, we studied point defects creation and structural changes. We showed that the damage induced by electronic excitations in the glass-ceramics is driven by the damage in the residual glass. (author)

  14. Methodology of leach testing of boro-silicate glasses in water

    International Nuclear Information System (INIS)

    The leaching rate is the principal parameter to be taken into account in the optimization of the conditioning glasses. It is also important for the analysis of the possible release rate of radioactive elements. In this context leaching tests must provide an answer to the release rate of radioactive nuclides under three different conditions: radioactive leaks in cooling pools (when asked by the management scheme) during engineering storage; release of radioactive elements when, due to a possible (even if highly improbable) accident, a large amount of water leaches the glass up to its complete dissolution; long term degradation of the conditioning barrier in the repository. To find a single test which complies to these different requirements does not seem probable. The task is aggravated by the complexity of the leaching mechanism

  15. Corrosion behaviour of the high level waste forms borosilicate glass and spent fuel in salt brines

    International Nuclear Information System (INIS)

    The objective of the first part of this work is to describe the extent to which Np, Pu, Am and Tc are mobilized from vitrified high-level radioactive waste into the near field of an HLW repository in a salt formation, when a hot and concentrated salt solution comes into contact with the glass. Waste form corrosion studies are conducted with a salt solution representing the composition of a fluid phase encountered in drill holes in the Gorleben salt dome. Test temperatures are determined by the designed maximum surface temperature of 200 deg. C for the vitrified waste in the Gorleben salt. The following results were obtained: 1. pH changes of the radioactive leachate are the same as in inactive leachates. 2. The time and temperature dependence of the reaction for the radioactive glass are in excellent agreement with that of the inactive glass. 3. Np, Pu, Am, and Tc have not been reimmobilized in secondary minerals. Hence, mobilization of these radionuclides is governed by the kinetics of glass dissolution. Pu oxidation states were analyzed and related to Pu concentrations. The second part is focused on the corrosion behaviour of spent fuel in contact with salt solution. For characterizing the potential chemical reactions of spent UO2 fuel during direct disposal in salt formations, corrosion tests were performed at various particle sizes with both high burnup spent fuel and unirradiated UO2. Studied effects include temperature, pH, radiolysis, oxidant concentration, surface to volume ratio (S/V) and the presence of container material. Results are applicable not only to salt media but also to others: (1) 90Sr data are indicative of matrix dissolution. (2) Except at high S/V ratios, spent fuel dissolution rates are proportional to surface area and are similar in both saline media and deionized water. (3) Dissolution rates of unirradiated UO2 are much lower and are proportional to oxidant concentration but almost independent of the nature of the oxidant. (4) It is

  16. Lanthanide-activated Na5Gd9F32 nanocrystals precipitated from a borosilicate glass: Phase-separation-controlled crystallization and optical property

    International Nuclear Information System (INIS)

    Highlights: • Na5Gd9F32 nanocrystals embedded glass ceramics were fabricated for the first time. • Such glass ceramics were achieved by phase-separation-controlled crystallization. • Elemental mapping evidenced the segregation of activators into the Na5Gd9F32 lattice. • Luminescent color could be tuned by controlling glass crystallization temperature. - Abstract: Lanthanide-activated cubic Na5Gd9F32 nanocrystals were precipitated from a borosilicate glass with a specifically designed composition. The precursor glass is already phase-separated after melt-quenching, which is beneficial to the realization of the controllable glass crystallization for affording desirable size, morphology and activator partition. Elemental mapping in the scanning transmission electron microscopy evidenced that the segregation of lanthanide ions into the Na5Gd9F32 lattice was in situ formed without the requirement of long-range ionic diffusion. Impressively, such fabricated glass ceramic co-doped with Yb3+/Er3+ ions exhibited intense upconversion luminescence, which was about 500 times higher than that of the precursor glass, and its luminescent color could be easily tuned from red to green by controlling glass crystallization temperature. It is anticipated that such phase-separation synthesis strategy with precise control over nanostructure of glass ceramics offer a great opportunity to design other highly transparent nanocomposites with a wide range of tunable optical properties

  17. Effects of alpha, gamma, and alpha-recoil radiation on borosilicate glass containing Savannah River Plant defense high-level nuclear waste

    International Nuclear Information System (INIS)

    At the Savannah River Plant, the reference process for the immobilization of defense high-level waste (DHLW) for geologic storage is vitrification into borosilicate glass. During geologic storage for 106 y, the glass would be exposed to approx. 3 x 1010 rad of β radiation, approx. 1010 rad of γ radiation, and 1018 particles/g glass for both α and α-recoil radiation. This paper discusses tests of the effect of these radiations on the leachability and density of the glass. Even though the doses were large, no effect of the radiations was detected that reduced the effectiveness of the glass for long-term storage of DHLW even at doses corresponding to 106 years storage for the actual glass. For the tests, glass containing simulated DHLW was prepared from frit of the reference composition. Three methods were used to irradiate the glass: external irradiations with beams of approx. 200 keV Xe or Pb ions, internal irradiations with Cm-244 doped glass, and external irradiations with Co-60 γ rays. Results with both Xe and Pb ions indicate that a dose of 3 x 1013 ions/cm2 (simulating > 106 years storage) does not significantly increase the leachability of the glass in deionized water. Tests with Cm-244 doped glass show no increase in leach rate in water or brine up to a dose of 1018 α and α-recoils/g glass. Results of larger doses are being examined. The density of the Cm-244 doped glass has decreased by 1% at a dose of 1018 particles/g glass. With γ-radiation, the density has changed by 10 rad. Results of leach tests in deionized water and brine indicated that this very large dose of γ-radiation increased the leach rate by only 20%. Also, the leach rates are lower in brine

  18. Effect of Eu{sub 2}O{sub 3} concentration on luminescent properties of Ce/Tb/Eu co-doped calcium borosilicate glass for white LED

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Linjiao; Lei, Xiaohua, E-mail: xhlei@cqu.edu.cn; Du, Xiaoqing; Jin, Lei; Chen, Weimin; Feng, Yong’an

    2013-10-15

    Luminescent properties of Ce/Tb/Eu co-doped calcium borosilicate glass were investigated through excitation and emission spectra, fluorescence lifetimes and colorimetric analysis. The spectra results show that the concentration quenching of Eu{sup 3+} ions occurs when the concentration of Eu{sub 2}O{sub 3} ranges from 0.75 mol% to 1.00 mol% and Ce{sup 3+}, Tb{sup 3+} and Eu{sup 2+} ions are all the donors which can transfer energy to Eu{sup 3+}. It can be indicated from the analysis of lifetimes that through nonradiative transition, Tb{sup 3+} ions can accept energy from Eu{sup 2+} ions and also transfer energy to Eu{sup 3+} ions. Furthermore, the colorimetric analysis show that the correlated color temperatures (CCT) of Ce/Tb/Eu co-doped calcium borosilicate glass can be adjusted from cold white to warm white by controlling the concentration of Eu{sub 2}O{sub 3}. -- Highlights: • Effect of Eu{sub 2}O{sub 3} concentration was investigated from the excitation and emission spectra, the fluorescence lifetimes and the colorimetric analysis. • The energy transfers from Ce{sup 3+}, Tb{sup 3+} and Eu{sup 2+} ions to Eu{sup 3+} ions were discussed. • Tb{sup 3+} can accept energy from Eu{sup 2+} and transfer energy to Eu{sup 3+} with different Eu{sub 2}O{sub 3} concentrations. • The CCTs of Ce/Tb/Eu co-doped calcium borosilicate glass can be adjusted from cold white to warm white by controlling the concentration of Eu{sub 2}O{sub 3}.

  19. A Comparison of Modifications Induced by Li3+ and Ag14+ Ion Beam in Spectroscopic Properties of Bismuth Alumino-Borosilicate Glass Thin Films

    Directory of Open Access Journals (Sweden)

    Ravneet Kaur

    2013-01-01

    Full Text Available Ion irradiation effects on the glass network and structural units have been studied by irradiating borosilicate glass thin film samples with 50 MeV Li3+ and 180 MeV Ag14+ swift heavy ions (SHI at different fluence rates ranging from 1012 ions/cm2 to 1014 ions/cm2. Glass of the composition (65-x Bi2O3-10Al2O3-(65-y B2O3-25SiO2 (x = 45, 40; y = 20, 25 has been prepared by melt quench technique. To study the effects of ionizing radiation, the glass thin films have been prepared from these glasses and characterized using XRD, FTIR, and UV-Vis spectroscopic techniques. IR spectra are used to study the structural arrangements in the glass before and after irradiation. The values of optical band gap, Urbach energy, and refractive index have been calculated from the UV-Vis measurements. The variation in optical parameters with increasing Bi2O3 content has been analyzed and discussed in terms of changes occurring in the glass network. A comparative study of the influence of Li3+ ion beam on structural and optical properties of the either glass system with Ag14+ ion is done. The results have been explained in the light of the interaction that SHI undergo on entering the material.

  20. Intense upconversion luminescence of Er3+/Yb3+ codoped oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals

    Institute of Scientific and Technical Information of China (English)

    ZHAO

    2010-01-01

    Er3+/Yb3+-codoped transparent oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals were prepared and spectroscopic properties of rare earth ions were investigated.Fluoride nanocrystals Ba2GdF7 were successfully precipitated in glass matrix,which was confirmed by X-ray diffraction(XRD)and transmission electron microscopy(TEM)results.In comparison with the as-made precursor,significant enhancement ofupconversion luminescence was observed in the Er3+/Yb3+codoped oxyfluoride glass ceramics,which may be due to the variation of coordination environment around Er3+and Yb3+ions after crystallization.The transition mechanisms of the green and red upconversion luminescence were ascribed to a two-photon process,and that of the blue upconversion luminescence was a three-photon process.

  1. Elaboration and experimental study of the Borosilicate glass GP 98/12 for the vitrification of the radioactive wastes of KfKarlsruhe Centre (R.F.A.)

    International Nuclear Information System (INIS)

    The transformation into a vitrified block of highly radioactive liquid wastes is actually the best solution for the storage in long run. In West Germany, the research institute in the field of nuclear energy (KfK) has been oriented in this way by developing industrial processes of vitrification and by following studies on the behaviour of the final products. For the fission products, the chosen glasses present good stability characteristics and are used as a first barrier during confinement. Our work, which is part of the research program on radioactive waste vitrification, consists of preparing borosilicate glass GP 98/12 and studying physical and chemical characteristics. We have also contributed to the development and the realization of glass blocks sampling system prepared at pilot scale

  2. Conceptual waste package interim product specifications and data requirements for disposal of borosilicate glass defense high-level waste forms in salt geologic repositories

    Energy Technology Data Exchange (ETDEWEB)

    1983-06-01

    The conceptual waste package interim product specifications and data requirements presented are applicable specifically to the normal borosilicate glass product of the Defense Waste Processing Facility (DWPF). They provide preliminary numerical values for the defense high-level waste form parameters and properties identified in the waste form performance specification for geologic isolation in salt repositories. Subject areas treated include containment and isolation, operational period safety, criticality control, waste form/production canister identification, and waste package performance testing requirements. This document was generated for use in the development of conceptual waste package designs in salt. It will be revised as additional data, analyses, and regulatory requirements become available.

  3. Conceptual waste package interim product specifications and data requirements for disposal of borosilicate glass defense high-level waste forms in salt geologic repositories

    International Nuclear Information System (INIS)

    The conceptual waste package interim product specifications and data requirements presented are applicable specifically to the normal borosilicate glass product of the Defense Waste Processing Facility (DWPF). They provide preliminary numerical values for the defense high-level waste form parameters and properties identified in the waste form performance specification for geologic isolation in salt repositories. Subject areas treated include containment and isolation, operational period safety, criticality control, waste form/production canister identification, and waste package performance testing requirements. This document was generated for use in the development of conceptual waste package designs in salt. It will be revised as additional data, analyses, and regulatory requirements become available

  4. Studies of local structure of Cm3+ in borosilicate glass using laser and x-ray spectroscopic methods and computational modeling

    International Nuclear Information System (INIS)

    The local environment of Cm3+ in a borosilicate glass has been probed by a combination of laser spectroscopy, structural modeling, and extended x-ray absorption fine structure (EXAFS) spectroscopy. The Stark splitting for the Cm f-f state transitions is significantly larger than the inhomogeneous line broadening that results from the disordered environment. As a result, the Cm optical spectrum can be fit using an effective operator Hamiltonian to obtain a set of crystal-field parameters. The fitting procedure, which requires the use of a descent-in-symmetry approach, provides a set of parameters for a best fit within tetragonal symmetry. These parameters are then linked to the local environment of Cm through exchange-charge modeling (ECM) of crystal field interactions. Cm in our borosilicate glass is best modeled with six oxygen ions with approximately tetragonal symmetry, and at an average distance of 2.31 (3) Aa. The results of crystal-field modeling are supported by EXAFS results. (c) 2000 American Institute of Physics

  5. Modification of molybdenum structural environment in borosilicate glasses with increasing content of boron and calcium oxide by 95Mo MAS NMR

    International Nuclear Information System (INIS)

    In nuclear borosilicate glasses, when molybdenum is in too high concentration and when it combines with other elements such as alkali and alkaline-earth elements it may form crystalline molybdates, including sodium molybdate, Na2MoO4, during melt cooling. In a nuclear vitrification context, the origin of this phenomenon must be understood to control and to avoid the appearance of this water-soluble crystalline phase. The solubility limit of MoO3 was found to be 2.5 mol% in a simplified SiO2-B2O3-Na2O-CaO nuclear glass at about 1300 degrees C. Higher MoO3 concentrations induced liquid phase separation followed by crystallization of Na2MoO4 and CaMoO4. This study assessed the impact of increasing the CaO and B2O3 content on the tendency of the melts to crystallize and the impact on the glass network structure. Structural analysis (Mo-95 MAS NMR and B-11 MAS NMR) of several glass series and standard SiO2-Na2O-MoO3 or SiO2-CaO-MoO3 glass showed that the nature of the crystallized phases that may appear during cooling of the melt can be controlled by correlation of the proportion of Na+ cations remaining free in the glass network with the soda/lime environment of tetrahedral MoO42- entities. (authors)

  6. Modification of Molybdenum Structural Environment in Borosilicate Glasses with Increasing Content of Boron and Calcium Oxide by 95Mo MAS NMR

    International Nuclear Information System (INIS)

    In nuclear borosilicate glasses, when molybdenum is in too high concentration and when it combines with other elements such as alkali and alkaline-earth elements it may form crystalline molybdates, including sodium molybdate, Na2MoO4, during melt cooling. In a nuclear vitrification context, the origin of this phenomenon must be understood to control and to avoid the appearance of this water-soluble crystalline phase. The solubility limit of MoO3 was found to be 2.5 mol% in a simplified SiO2-B2O3-Na2O-CaO nuclear glass at about 1300 degrees C. Higher MoO3 concentrations induced liquid phase separation followed by crystallization of Na2MoO4 and CaMoO4. This study assessed the impact of increasing the CaO and B2O3 content on the tendency of the melts to crystallize and the impact on the glass network structure. Structural analysis (95Mo MAS NMR and 11B MAS NMR) of several glass series and standard SiO2-Na2O-MoO3 or SiO2-CaO-MoO3 glass showed that the nature of the crystallized phases that may appear during cooling of the melt can be controlled by correlation of the proportion of Na+ cations remaining free in the glass network with the soda/lime environment of tetrahedral MoO42- entities. (authors)

  7. Influence of zirconium on the structure of pristine and leached soda-lime borosilicate glasses: towards a quantitative approach by 17O MQMAS NMR

    International Nuclear Information System (INIS)

    17O MQMAS NMR was used to characterize the influence of zirconium on the structural organization of soda-lime borosilicate glasses. A new method of quantitative analysis of the 17O MQMAS spectra is presented, by a direct fit of the two-dimensional MQMAS spectrum which provides the resolution of all the structural groups in glasses containing up to five oxides. Additional data were also obtained from the quantitative deconvolution of the 11B MAS NMR spectra, with the help of the direct fit of MQMAS data as well. Excess of non-bridging oxygen is clearly identified in these glasses. Six-folded zirconium is preferentially compensated rather than the tetrahedral boron and calcium only partially compensate the tetrahedral boron. Alteration gels arising from glass leaching were probed by oxygen-17 supplied by the alteration solution. Most of the zirconium is inserted in the silicate network forming Si-O-Zr bonds with the same configuration in the glass and in the gel. During leaching, calcium clearly remains in the alteration gel, either near non-bridging oxygen or as a zirconium charge compensator. This quantitative approach applied to 17O MQMAS spectra demonstrates its potential for investigating the structure of increasingly complex glass and gel compositions. (authors)

  8. In-situ characterization of femtosecond laser-induced crystallization in borosilicate glass using time-resolved surface third-harmonic generation

    International Nuclear Information System (INIS)

    Coherent phonon dynamics in condensed-phase medium are responsible for important material properties including thermal and electrical conductivities. We report a structural dynamics technique, time-resolved surface third-harmonic generation (TRSTHG) spectroscopy, to capture transient phonon propagation near the surface of polycrystalline CaF2 and amorphous borosilicate (BK7) glass. Our approach time-resolves the background-free, high-sensitivity third harmonic generation (THG) signal in between the two crossing near-IR pulses. Pronounced intensity quantum beats reveal the impulsively excited low-frequency Raman mode evolution on the femtosecond to picosecond timescale. After amplified laser irradiation, danburite-crystal-like structure units form at the glass surface. This versatile TRSTHG setup paves the way to mechanistically study and design advanced thermoelectrics and photovoltaics

  9. Erbium-doped borosilicate glasses containing various amounts of P{sub 2}O{sub 5} and Al{sub 2}O{sub 3}: Influence of the silica content on the structure and thermal, physical, optical and luminescence properties

    Energy Technology Data Exchange (ETDEWEB)

    Bourhis, Kevin [Politecnico di Torino, DISAT, Istituto di Ingegneria e Fisica dei Materiali, Corso Duca degli Abruzzi 24, I-10129 Torino (Italy); Massera, Jonathan [Department of Electronics and Communications Engineering, Tampere University of Technology, Korkeakoulunkatu 3, FI-33720 Tampere (Finland); BioMediTech, Tampere (Finland); Petit, Laeticia, E-mail: laeticia.petit@nlight.net [Process Chemistry Centre, Åbo Akademi University, Biskopsgatan 8, FI-20500 Turku (Finland); nLIGHT Corporation, Sorronrinne 9, FI-08500 Lohja (Finland); Koponen, Joona [nLIGHT Corporation, Sorronrinne 9, FI-08500 Lohja (Finland); Fargues, Alexandre; Cardinal, Thierry [CNRS, Université de Bordeaux, ISM, 351 Cours de la Libération, F-33405 Talence (France); Hupa, Leena; Hupa, Mikko [Process Chemistry Centre, Åbo Akademi University, Biskopsgatan 8, FI-20500 Turku (Finland); Dussauze, Marc; Rodriguez, Vincent [CNRS, Université de Bordeaux, ICMCB, 87 Avenue du Dr Schweitzer, F-33608 Pessac (France); Ferraris, Monica [Politecnico di Torino, DISAT, Istituto di Ingegneria e Fisica dei Materiali, Corso Duca degli Abruzzi 24, I-10129 Torino (Italy)

    2015-10-15

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

  10. A novel interferometric dilatometer in the 4–300 K temperature range: thermal expansion coefficient of SRM-731 borosilicate glass and stainless steel-304

    International Nuclear Information System (INIS)

    We present a newly designed heterodyne interferometric dilatometer for the measurement of the coefficient of thermal expansion of solids in the 4–300 K temperature range. The instrument can measure non-monotonic thermal expansion curves and has an accuracy better than 200 nm across the whole 4–300 K measurement range. The compensation for the misalignment of the interferometer design and the configuration of the sample holder make the instrument suitable to carry out measurements on any kind of sample that can be produced in a bar or rod shape. The measurement of a standard SRM-731 borosilicate glass and an SS-304 sample are presented and compared with literature data. (paper)

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

    Science.gov (United States)

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

    2010-10-01

    Bioactive glass scaffolds with a microstructure similar to that of dry human trabecular bone but with three different compositions were evaluated for potential applications in bone repair. The preparation of the scaffolds and the effect of the glass composition on the degradation and conversion of the scaffolds to a hydroxyapatite (HA)-type material in a simulated body fluid (SBF) are reported here (Part I). The in vitro response of osteogenic cells to the scaffolds and the in vivo evaluation of the scaffolds in a rat subcutaneous implantation model are described in Part II. Scaffolds (porosity = 78-82%; pore size = 100-500 microm) were prepared using a polymer foam replication technique. The glasses consisted of a silicate (13-93) composition, a borosilicate composition (designated 13-93B1), and a borate composition (13-93B3), in which one-third or all of the SiO2 content of 13-93 was replaced by B2O3, respectively. The conversion rate of the scaffolds to HA in the SBF increased markedly with the B2O3 content of the glass. Concurrently, the pH of the SBF also increased with the B2O3 content of the scaffolds. The compressive strengths of the as-prepared scaffolds (5-11 MPa) were in the upper range of values reported for trabecular bone, but they decreased markedly with immersion time in the SBF and with increasing B2O3 content of the glass. The results show that scaffolds with a wide range of bioactivity and degradation rate can be achieved by replacing varying amounts of SiO(2) in silicate bioactive glass with B2O3. PMID:20544804

  12. Synthesis, IR, crystallization and dielectric study of (Pb, Sr)TiO3 borosilicate glass-ceramics

    International Nuclear Information System (INIS)

    Eleven glass compositions were prepared by melt and quench method with progressive substitution of SrO for PbO (0 ≤ x ≤ 1.0) with a step-wise increment of 0.10 in the glass ((PbxSr1-x)OTiO2)-((2SiO2B2O3))-(BaO.K2O).Nb2O5 (mol percentage) system. The infrared spectra (IR) of various glass compositions in the above mentioned glass system was recorded over a continuous spectral range 400-4000 cm-1 to study their different oxides structure systematically. Differential thermal analysis (DTA) was recorded from room temperature (∼27°C) to 1400°C employing a heating rate of 10°C/min to determine glass transition temperature, Tg and crystallization temperature, Tc. The melting temperature, Tm, of these glass compositions was found to be in the range 597-1060°C depending on the composition under normal atmospheric conditions. Tg and Tm of glasses were found to increase with increasing SrO content. X-ray diffraction analysis of these glass-ceramic samples shows that major crystalline phase of the glass-ceramic sample with x ≤ 0.5 was found to have cubic structure similar to SrTiO3 ceramic. Scanning electron microscopy has been carried out to see the surface morphology of the crystallites dispersed in the glassy matrix. (author)

  13. Effect of X-ray irradiation on the optical absorption of SdSe1−xTex nanocrystals embedded in borosilicate glass

    International Nuclear Information System (INIS)

    The effect of X-ray irradiation on the optical absorption spectra of CdSe1−xTex nanocrystals embedded in a borosilicate matrix is studied. The observed blue shift of the absorption edge and bleaching of the confinement-related features in the spectra are related to X-ray induced negative ionization of the nanocrystals with charge transfer across the nanocrystal/matrix interface. The radiation-induced changes are observed to recover after longer post-irradiation storage at room temperature. - Highlights: ► Absorption edge of glass-embedded CdSe1−x Tex nanocrystals is blue shifted under X-ray irradiation. ► Radiation-induced bleaching bands appear at the position of HOMO-LUMO transitions. ► The reason is charge transfer between the nanocrystals and radiation-induced centres in the glass. ► Contrary to photoionization, this is a long-lived process (over 2000 h).

  14. Optical parameters of Nd3+:Er3+:Yb3+co-doped borosilicate glasses and their energy transfers at high temperature

    Institute of Scientific and Technical Information of China (English)

    Li Cheng-Ben; Li Shu-Feng; Dong Bin; Cheng Yu-Qi; Yin Hai-Tao; Yang Jing; Chen Yu

    2011-01-01

    This paper reports that a series of Nd3+:Er3+:yb3+ co-doped borosilicate glasses have been prepared and their absorption spectra measured. The J-O intensity parameters Ωk (k = 2, 4, 6), spontaneous radiative lifetime Τrad,spontaneous transition probability A, fluorescence branching ratio β and oscillator strength fed of the Nd3+ ions at room temperature are calculated based on Judd-Ofelt (J-O) theory. The temperature dependence of the up-conversion photoluminescence characteristics in a Nd3+:Er3+:yb3+ co-doped sample is studied under a 978 nm semiconductor laser excitation, and the energy transfer mechanisms among Yb3+, Er3+ and Nd3+ ions are analysed. The results show that the J-O intensity parameters Ω2 increase when the Nd3+ concentration of the Nd3+:Er3+:yb3+ co-doped boresilicate glasses increases. The possibility of spontaneous transition is small and lifetimes are long at levels of 4F5/2and 4F3/2. The intensity of Nd3+ emissions at 595, 691, 753, 813 and 887 nm are markedly enhanced when the sample temperature exceeds 400 K. The reasons being the cooperation of the secondary sensitization from Er3+ to Nd3+ and the contribution of a multi-phonon.

  15. Oxygen bubble development on a platinum electrode in borosilicate glass melt by the effect of alternating current

    Czech Academy of Sciences Publication Activity Database

    Matěj, J.; Jebavá, Marcela

    2014-01-01

    Roč. 58, č. 4 (2014), s. 249-259. ISSN 0862-5468 R&D Projects: GA TA ČR TA01010844 Institutional support: RVO:67985891 Keywords : glass melt * platinum electrode * alternating current * oxygen bubble Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass Impact factor: 0.435, year: 2014 http://www.ceramics-silikaty.cz/2014/pdf/2014_04_249.pdf

  16. Modelling the dissolution of borosilicate glasses for radioactive waste disposal with the PHREEQE/GLASSOL code: theory and practice

    International Nuclear Information System (INIS)

    A model describing the corrosion kinetics of silicate glasses has been developed by Grambow in recent years. In this report, the theoretical background of the model is thoroughly discussed, and its practical use demonstrated. The main objectives were: 1) to test the validity of the basic assumptions on which the model relies, and 2) to assess whether it can be applied to the safety analysis of a Swiss final repository for high-level radioactive waste. Transition State Theory, a tool based on quantum mechanical principles, has been used by Grambow to derive a general kinetic equation for the corrosion of silicate glasses. This equation predicts successfully the observed dependence of the corrosion rate on the silicic acid concentration in solution according to a first order kinetics law. However, some parameters required by this equation are determined on the base of questionable assumptions. In particular, the simplistic surface complexation model used for the calculation of the free energy of the glass-water reaction yields, for the protonation of silicon on the glass surface, results which are not consistent with the experimental findings. Further, although the model predicts a unique value, common to all silicate glasses, for the activation energy of the rate-determining elementary reaction, leaching experiments conducted on a wide variety of glasses suggest that this quantity may vary by a factor 2. In its present form, the model is judged to be unsuitable for the safety analysis of the Swiss final repository. The reasons include: 1) the model neglects the potential effects of diffusive transport and silica sorption in a bentonite backfill on the glass corrosion kinetics, 2) the release of radionuclides can be only modelled assuming congruent dissolution, and 3) the magnitude of the final rates of corrosion, the parameter defining the maximal lifetime of the glass matrix, is still not known with sufficient precision. (author) figs., tabs., 27 refs

  17. Effect of focusing condition on molten area characteristics in micro-welding of borosilicate glass by picosecond pulsed laser

    Science.gov (United States)

    Nordin, I. H. W.; Okamoto, Y.; Okada, A.; Takekuni, T.; Sakagawa, T.

    2016-05-01

    The characteristics of the molten area are attributed not only by laser energy condition but also the focusing condition. In this study, a picosecond pulsed laser of 1064 nm in wavelength and 12.5 ps in pulse duration was used as a laser source for joining glass material. Influence of focusing condition on micro-welding of glasses was experimentally investigated by using an objective lens with and without spherical aberration correction, and its molten area was characterized. The usage of objective lens with spherical aberration correction led to a larger molten area inside the bulk material of glass even under the same pulse energy, which related to the efficient micro-welding of glass materials. In addition, an optical system with the spherical aberration correction led to a stable absorption of laser energy inside the bulk glass material, stabilizing the shape of molten area, which resulted in the reliable weld joint. On the other hand, breaking strength of the specimens with spherical aberration correction was higher than that without spherical aberration correction. Therefore, it is concluded that the focusing condition with spherical aberration correction led to the larger and stable molten area, which resulted in higher joining strength in micro-welding of glass materials.

  18. Investigation of the oxidation states of Cu additive in colored borosilicate glasses by electron energy loss spectroscopy

    International Nuclear Information System (INIS)

    Three optically transparent colorful (red, green, and blue) glasses were synthesized by the sol-gel method. Nano-sized precipitates were found in scanning electron microscopy images. The precipitates were analyzed by transmission electron microscopy (TEM) and high resolution TEM. The measured lattice parameters of these precipitates were found to fit the metallic copper in red glass but deviate from single valenced Cu oxides in green and blue glasses. The chemistry of these nano-sized particles was confirmed by electron energy loss spectroscopy (EELS). By fitting the EELS spectra obtained from the precipitates with the linear combination of reference spectra from Cu reference compounds, the oxidation states of Cu in the precipitates have been derived. First principle calculations suggested that the Cu nano-particles, which are in the similar oxidation states as our measurement, would show green color in the visible light range

  19. Effects of the iron content and redox state on the structure of sodium borosilicate glasses: A Raman, Moessbauer and boron K-edge XANES spectroscopy study

    International Nuclear Information System (INIS)

    The structure of iron-bearing sodium borosilicate glasses with up to 10 mol% FeO has been investigated in the range 0.15 ≤ Fe3+/SFe ≤ 0.95. According to Moessbauer spectroscopy, Fe3+ and Fe2+ are mainly in tetrahedral and octahedral coordination, respectively, although other coordination states exist for both cations. From XANES experiments, we conclude that increasing Fe content and varying redox states have only a minor effect on the relative proportions of BO3 and BO4 units. In Raman spectra, a decrease of the proportion of BO4 species present in danburite-like units (Na2O.B2O3.2SiO2) is found upon increasing iron content and oxidizing state. Whereas the insensitivity of the overall boron speciation to iron content and redox state points to weak interactions between boron and iron, the changes affecting BO4 species do indicate a more subtle interplay between Fe3+ and the other tetrahedrally coordinated cations (Si,B) because of the competition between tetrahedral Fe3+ and B3+ for charge compensation by Na+. (authors)

  20. OXYGEN BUBBLE DEVELOPMENT ON A PLATINUM ELECTRODE IN BOROSILICATE GLASS MELT BY THE EFFECT OF ALTERNATING CURRENT

    Directory of Open Access Journals (Sweden)

    Jiri Matej

    2014-10-01

    or on alternating reduction and re-forming of oxidic layer on the electrode in the transition range, has been suggested. Start of bubble evolution at low alternating current density has also been observed in simple sodium-calcium-silicate glass melt. A relation between bubble release and platinum corrosion caused by reduced silicon has been suggested

  1. Coupling of microanalytical techniques to study the relationships between chemical durability and irradiation resistance of alumino-borosilicate glasses

    International Nuclear Information System (INIS)

    Safety assessment of a nuclear waste deposit is based on the chemical durability and irradiation resistance of the nuclear waste forms. It is well-known that the consequences of the impact of α, β and γ irradiation on glass integrity essentially affect the level of its recrystallized fraction and its initial dissolution rate. Complex alkali-borosilico-aluminate glasses were submitted to aqueous leaching tests at temperature ranging from 25 to 100 deg. C, from pH = 0 to pH = 12. Simple glasses containing one or two transition metal oxides have been synthesized. Some of them have been irradiated before being leached at 90 deg. C. Irradiation experiments have been performed with 150 keV Xe+ions mainly producing displacement cascades in the first hundreds of nanometers beneath the sample surfaces. The leached samples were then characterized by coupling performance techniques such as scanning electron microscopy (SEM), electron microprobe analysis (EMA), secondary ion mass spectrometry (SIMS) and ion beam analytical (IBA) methods: Rutherford backscattering and elastic recoil spectrometries (RBS and ERDA)

  2. In-can hot pressing of borosilicate glass for the immobilization of high- and medium-level wastes

    International Nuclear Information System (INIS)

    The paper presents a method for the immobilization of different waste streams based in the uniaxial in-can hot pressing of a glass frit together with the waste oxides. The process reported herein offers engineering simplicity in combination with many technological advantages such as significant decrease in temperature, use of small pressure, improved homogeneity of the products, production in easily arrangeable and interchangeable units. Furthermore, the proposed method has also proved to be suitable for treating intermediate-level waste streams containing Zry-4 cladding fragments. 9 references, 2 figures, 3 tables

  3. Homogeneous glass processing region defined for a lanthanide borosilicate glass composition for the mobilization of plutonium using thorium as a surrogate

    International Nuclear Information System (INIS)

    A ternary diagram showing the homogeneous glass processing region of a base frit, rare earth oxide and thorium oxide has been developed for a residence temperature of 1475 C. Thorium oxide was used as a plutonium surrogate. All ThO2 glasses that were processed included a 1:1 mole ratio of Th to Gd. Gadolinium is added to the glass as a neutron absorber. Forty individual glass compositions were melted at 1475 C for 4 to 6 hours with periodic stirring. Two glasses (B-20-25 and B-25-25) were processed with a ThO2 loading of 25 weight percent (oxide) without amorphous phase separation or crystalline species detected by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) or Transmission Electron Microscopy (TEM). These were processed with 55 weight percent frit, 20 weight percent rare earth oxides and 50 percent frit, 25 percent rare earth oxides. Crystalline species that formed outside of the homogeneous glass processing region due to solubility limits or insufficient processing temperature were identified. Amorphous phase separation was detected and examined by TEM at high ThO2 loadings (20 to 30 weight percent oxide). The base frit was able to dissolve up to 65 weight percent rare earth oxides when thorium oxide was not present. Durability testing will be performed on three glasses from three different regions of the homogeneous glass processing region. Product Consistency Test (PCT) results are pending and will be added to this document under a future revision

  4. Luminescence Properties of Eu/Tm/Tb-doped Borosilicate Glass%Eu/Tm/Tb掺杂硼硅酸盐玻璃的发光性能

    Institute of Scientific and Technical Information of China (English)

    石冬梅; 赵营刚

    2016-01-01

    Eu/Tm/Tb-doped singly, doubly and triply borosilicate glasses were prepared using a conventional melting-quenching method. The luminescent properties of Eu/Tm/Tb-doped samples under the UV excitation were investigated in detail by measuring the excitation and emission spectra and calculating CIE chromaticity coordinates. The results show that the sharp emission peak centered at 459 nm originating from 1 D2→3 F4 of Tm3+ is observed, and the characteristic emission intensity centered at 437 nm ascribing to the broad peak of Eu2+, 589 nm( 5 D0→7 F1 ) and 612 nm( 5 D0→7 F2 ) of Eu3+ is reduced due to the energy transfer from Eu3+,Eu2+ to Tm3+ ion. Red, green and blue light can be observed in Eu/Tm/Tb-doped triply samples simultaneously under the excitation of 377 nm. The luminescent intensity and color of borosilicate glasses might be changed by adjusting Eu2 O3 content, and the sample with CIE chromaticity coordinates(0. 33, 0. 386 7)are obtained.%采用熔融淬冷法制备了性能优越的Eu/Tm/Tb单掺、双掺和三掺的硼硅酸盐玻璃。测试了样品的激发和发射光谱,计算了CIE色坐标,研究了紫外激发下Eu/Tm/Tb掺杂的硼硅酸盐玻璃的发光性能。结果表明:在361 nm激发下,随着Tm3+加入到Eu2O3掺杂的硼硅酸盐样品中,观察到Tm3+的459 nm(1D2→3F4)锐线特征发射峰,同时由于Eu3+,Eu2+→Tm3+的能量传递的存在降低了Eu2+的437 nm宽带峰及Eu3+的589 nm(5 D0→7 F1)和612 nm(5 D0→7 F2)的特征发射峰强度。在377 nm激发下,Eu/Tm/Tb三掺样品能够同时出现红、绿和蓝光。调节 Eu2O3的含量能有效改变发光玻璃的发光强度和颜色,最终得到色坐标为(0.33,0.3867)的发光玻璃。

  5. Atomistic Model of Physical Ageing in Se-rich As-Se Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Golovchak,R.; Shpotyuk, O.; Kozdras, A.; Bureau, B.; Vlcek, M.; Ganjoo, A.; Jain, H.

    2007-01-01

    Thermal, optical, X-ray excited and magnetic methods were used to develop a microstructural model of physical ageing in Se-rich glasses. The glass composition As10Se90, possessing a typical cross-linked chain structure, was chosen as a model object for the investigations. The effect of physical ageing in this glass was revealed by differential scanning calorimetry, whereas the corresponding changes in its atomic arrangement were studied by extended X-ray absorption fine structure, Raman and solid-state 77Se nuclear magnetic resonance spectroscopy. Straightening-shrinkage processes are shown to be responsible for the physical ageing in this Se-rich As-Se glass.

  6. Effects of alpha, gamma, and alpha-recoil radiation on borosilicate glass containing Savannah River Plant defense high-level nuclear waste. [Lead ions-250 keV; xenon ions-160 keV

    Energy Technology Data Exchange (ETDEWEB)

    Bibler, N.E.

    1981-01-01

    At the Savannah River Plant, the reference process for the immobilization of defense high-level waste (DHLW) for geologic storage is vitrification into borosilicate glass. During geologic storage for 10/sup 6/ y, the glass would be exposed to approx. 3 x 10/sup 10/ rad of ..beta.. radiation, approx. 10/sup 10/ rad of ..gamma.. radiation, and 10/sup 18/ particles/g glass for both ..cap alpha.. and ..cap alpha..-recoil radiation. This paper discusses tests of the effect of these radiations on the leachability and density of the glass. Even though the doses were large, no effect of the radiations was detected that reduced the effectiveness of the glass for long-term storage of DHLW even at doses corresponding to 10/sup 6/ years storage for the actual glass. For the tests, glass containing simulated DHLW was prepared from frit of the reference composition. Three methods were used to irradiate the glass: external irradiations with beams of approx. 200 keV Xe or Pb ions, internal irradiations with Cm-244 doped glass, and external irradiations with Co-60 ..gamma.. rays. Results with both Xe and Pb ions indicate that a dose of 3 x 10/sup 13/ ions/cm/sup 2/ (simulating > 10/sup 6/ years storage) does not significantly increase the leachability of the glass in deionized water. Tests with Cm-244 doped glass show no increase in leach rate in water or brine up to a dose of 10/sup 18/ ..cap alpha.. and ..cap alpha..-recoils/g glass. Results of larger doses are being examined. The density of the Cm-244 doped glass has decreased by 1% at a dose of 10/sup 18/ particles/g glass. With ..gamma..-radiation, the density has changed by < 0.05% at a dose of 8.5 x 10/sup 10/ rad. Results of leach tests in deionized water and brine indicated that this very large dose of ..gamma..-radiation increased the leach rate by only 20%. Also, the leach rates are lower in brine.

  7. Liquid phase sintering of 20Bi(Zn0.5Ti0.5)O 3-80BaTiO3 dielectrics with bismuth-zinc-borate and bismuth borosilicate glasses

    Science.gov (United States)

    Shahin, David I.

    Dielectrics in the Bi(Zn0.5Ti0.5)O3-BaTiO 3 system (specifically 20BZT-80BT, in mol%) are promising candidates for high energy density capacitor applications due to broad temperature-dependent dielectric constant maxima and a relatively field-independent permittivity. Bulk samples require sintering temperatures of greater than 1180°C to reach useful densities. Due to incompatibility of Bi with low-pO2 processing, BZT-BT-based multilayer capacitors must utilize noble metal electrodes that resist oxidation during sintering. Sintering temperatures must be reduced to allow use of less expensive electrode materials (Cu, etc.). This work studies the reduced temperature sintering behavior and dielectric properties of BZT-BT sintered with 30Bi2O3-30ZnO-40B 2O3 and 50Bi2O3-25B2O 3-25SiO2 (mol%) liquid phase formers. Dielectrics sintered with 1v% borate additions and 5v% additions of either the borate or borosilicate achieved relative densities greater than 95% after sintering at 1000°C for four hours. All compositions retained the relaxor behavior exhibited by pure 20BZT-80BT. Increased borate additions led to greater dielectric constant reductions, while increased borosilicate additions yielded no clear trend in the dielectric constant reduction. Energy densities were estimated between 0.3-0.5 J/cm3; smaller glass additions typically led to larger energy densities. Dielectrics sintered with 1v% borate additions are of interest due to their high relative densities (approx. 96%) and energy densities of approximately 0.5 J/cm3 under 100kV/cm electric fields. Studies of BZT-BT/glass interfaces revealed the formation of crystalline interfacial layers less than 10 microns thick. The borate formed a bismuth titanate phase (likely Bi4Ti3O12) during heating to 700°C, whereas the borosilicate formed a barium silicate phase (likely BaSiO3) during processing to 800°C. Similar phases are expected to be present in the liquid phase sintered dielectrics and likely affect the BZT

  8. Structural and crystallisation study of a rare earth alumino borosilicate glass designed for nuclear waste confinement; Etude de la structure et du comportement en cristallisation d'un verre nucleaire d'aluminoborosilicate de terre rare

    Energy Technology Data Exchange (ETDEWEB)

    Quintas, A

    2007-09-15

    This work is devoted to the study of a rare earth alumino borosilicate glass, which molar composition is 61,81 SiO{sub 2} - 3,05 Al{sub 2}O{sub 3} - 8,94 B{sub 2}O{sub 3} - 14,41 Na{sub 2}O - 6,33 CaO - 1,90 ZrO{sub 2} - 3,56 Nd{sub 2}O{sub 3}, and envisaged for the immobilization of nuclear wastes originating from the reprocessing of high discharge burn up spent fuel. From a structural viewpoint, we investigated the role of the modifier cations on the arrangement of the glass network through different modifications of the glass composition: variation of the Na/Ca ratio and modification of the nature of the alkali and alkaline earth cations. The NMR and Raman spectroscopic techniques were useful to determine the distribution of modifier cations among the glass network and also to cast light on the competition phenomena occurring between alkali and alkaline earth cations for charge compensation of [AlO{sub 4}]{sup -} and [BO{sub 4}]{sup -} species. The neodymium local environment could be probed by optical absorption and EXAFS spectroscopies which enabled to better understand the insertion mode of Nd{sup 3+} ions among the silicate domains of the glass network. Concerning the crystallization behavior we were interested in how the glass composition may influence the crystallization processes and especially the formation of the apatite phase of composition Ca{sub 2}Nd{sub 8}(SiO{sub 4}){sub 6}O{sub 2}. In particular, this work underlined the important role of both alkaline earth and rare earth cations on the crystallization of the apatite phase. (author)

  9. Calorimetric study of tellurium rich Se-Te-Sn glasses

    Science.gov (United States)

    Heera, Pawan; Kumar, Anup; Jharwal, Manish; Sharma, Raman

    2016-05-01

    We report the calorimetric study of amorphous Se30Te70-x Snx alloys for x= 0, 1.5, 2.5, 4.5 in terms of kinetic parameters. The DSC curves recorded at four different heating rates are analyzed to determine the transition temperatures, activation energy, thermal stability, glass forming ability. The crystallization process has been investigated using Kissinger, Matusita, Augis and Bennett, and Gao and Wang models. Various kinetic parameters have been calculated for a better understanding of the growth mechanism. The glass transition temperatures Tg, onset crystallization Tc, peak crystallization Tp, and melting temperature Tm are found to increase with the increase in Sn content. The system under investigation is found to be thermally stable for at lower at% of Sn. The values of parameters HR, Hw, and S indicate that Glass forming ability (GFA) decays with an increase in Sn content.

  10. Disorderly crystal structures in transition metal rich-metalloid alloys: implications for glass formation

    International Nuclear Information System (INIS)

    Easy glass formation usually occurs near eutectics where the glass forming temperature is close to the melting point. However, as Anderson observed [1], other factors also enter. Citing covalent systems such as SiO2 and GeS2, he noted that glass formation is favored when the crystal structure(s) of the compounds are complicated. The purpose of the present communication is to see what transition metal rich-metalloid compounds have complicated structures and what implications this might have for glass formation

  11. Effect of Zn- and Ca-oxides on the structure and chemical durability of simulant alkali borosilicate glasses for immobilisation of UK high level wastes

    International Nuclear Information System (INIS)

    Highlights: • Spinel crystallization incorporates ZnO from base glass, displacing Mg and Ni. • Raman spectroscopy demonstrates significant impact on glass structure by addition of ZnO to base glass. • Addition of ZnO reduces glass dissolution rate at early time periods (up to 28 days). - Abstract: Compositional modification of United Kingdom high level nuclear waste (HLW) glasses was investigated with the aim of understanding the impact of adopting a ZnO/CaO modified base glass on the vitrified product phase assemblage, glass structure, processing characteristics and dissolution kinetics. Crystalline spinel phases were identified in the vitrified products derived from the Na2O/Li2O and the ZnO/CaO modified base glass compositions; the volume fraction of the spinel crystallites increased with increasing waste loading from 15 to 20 wt%. The spinel composition was influenced by the base glass components; in the vitrified product obtained with the ZnO/CaO modified base glass, the spinel phase contained a greater proportion of Zn, with a nominal composition of (Zn0.60Ni0.20Mg0.20)(Cr1.37Fe0.63)O4. The addition of ZnO and CaO to the base glass was also found to significantly alter the glass structure, with changes identified in both borate and silicate glass networks using Raman spectroscopy. In particular, these glasses were characterised by a significantly higher Q3 species, which we attribute to Si–O–Zn linkages; addition of ZnO and CaO to the glass composition therefore enhanced glass network polymerisation. The increase in network polymerisation, and the presence of spinel crystallites, were found to increase the glass viscosity of the ZnO/CaO modified base glass; however, the viscosities were within the accepted range for nuclear waste glass processing. The ZnO/CaO modified glass compositions were observed to be significantly more durable than the Na2O/Li2O base glass up to 28 days, due to a combination of the enhanced network polymerisation and the

  12. Effect of Zn- and Ca-oxides on the structure and chemical durability of simulant alkali borosilicate glasses for immobilisation of UK high level wastes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hua, E-mail: nzhangh@aliyun.com [Immobilisation Science Laboratory, Department of Materials Science and Engineering, The University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield S1 3JD (United Kingdom); China Institute of Atomic Energy, P.O. Box 275-93, 102413 Beijing (China); Corkhill, Claire L.; Heath, Paul G.; Hand, Russell J.; Stennett, Martin C. [Immobilisation Science Laboratory, Department of Materials Science and Engineering, The University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield S1 3JD (United Kingdom); Hyatt, Neil C., E-mail: n.c.hyatt@sheffield.ac.uk [Immobilisation Science Laboratory, Department of Materials Science and Engineering, The University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield S1 3JD (United Kingdom)

    2015-07-15

    Highlights: • Spinel crystallization incorporates ZnO from base glass, displacing Mg and Ni. • Raman spectroscopy demonstrates significant impact on glass structure by addition of ZnO to base glass. • Addition of ZnO reduces glass dissolution rate at early time periods (up to 28 days). - Abstract: Compositional modification of United Kingdom high level nuclear waste (HLW) glasses was investigated with the aim of understanding the impact of adopting a ZnO/CaO modified base glass on the vitrified product phase assemblage, glass structure, processing characteristics and dissolution kinetics. Crystalline spinel phases were identified in the vitrified products derived from the Na{sub 2}O/Li{sub 2}O and the ZnO/CaO modified base glass compositions; the volume fraction of the spinel crystallites increased with increasing waste loading from 15 to 20 wt%. The spinel composition was influenced by the base glass components; in the vitrified product obtained with the ZnO/CaO modified base glass, the spinel phase contained a greater proportion of Zn, with a nominal composition of (Zn{sub 0.60}Ni{sub 0.20}Mg{sub 0.20})(Cr{sub 1.37}Fe{sub 0.63})O{sub 4}. The addition of ZnO and CaO to the base glass was also found to significantly alter the glass structure, with changes identified in both borate and silicate glass networks using Raman spectroscopy. In particular, these glasses were characterised by a significantly higher Q{sup 3} species, which we attribute to Si–O–Zn linkages; addition of ZnO and CaO to the glass composition therefore enhanced glass network polymerisation. The increase in network polymerisation, and the presence of spinel crystallites, were found to increase the glass viscosity of the ZnO/CaO modified base glass; however, the viscosities were within the accepted range for nuclear waste glass processing. The ZnO/CaO modified glass compositions were observed to be significantly more durable than the Na{sub 2}O/Li{sub 2}O base glass up to 28 days, due to

  13. Primary crystallisation in Al-rich metallic glasses at unusually low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Bokeloh, Joachim; Wilde, Gerhard [Institut fuer Materialphysik, Westfaelische Wilhelms-Universitaet Muenster (Germany); Boucharat, Nancy [Institut fuer Nanotechnologie, Forschungszentrum Karlsruhe (Germany)

    2009-07-01

    The initial stage of the primary crystallisation reaction and the glass transition of the marginal metallic glass Al-Y-Fe has been investigated in conventional and modulated DSC, microcalorimetry, XRD and TEM. A sharp onset of the primary crystallisation was found in microcalorimetry and XRD studies at temperatures 120 K below the primary crystallisation peak observed in conventional DSC. A systematic MDSC study of annealed samples revealed a wide spectrum of glass transition onsets which show a strong dependence on the annealing temperature and duration. In addition, the glass transition onsets can be linked to the initial stage primary crystallisation. The observed spectrum of glass transition onsets may be interpreted as experimental evidence for a phase separation that precedes the nucleation and growth of aluminium nanocrystals in the respective al-rich metallic glasses.

  14. Condensation of Si-rich region inside soda-lime glass by parallel femtosecond laser irradiation.

    Science.gov (United States)

    Sakakura, Masaaki; Yoshimura, Kouhei; Kurita, Torataro; Shimizu, Masahiro; Shimotsuma, Yasuhiko; Fukuda, Naoaki; Hirao, Kazuyuki; Miura, Kiyotaka

    2014-06-30

    Local melting and modulation of elemental distributions can be induced inside a glass by focusing femtosecond (fs) laser pulses at high repetition rate (>100 kHz). Using only a single beam of fs laser pulses, the shape of the molten region is ellipsoidal, so the induced elemental distributions are often circular and elongate in the laser propagation direction. In this study, we show that the elongation of the fs laser-induced elemental distributions inside a soda-lime glass could be suppressed by parallel fsing of 250 kHz and 1 kHz fs laser pulses. The thickness of a Si-rich region became about twice thinner than that of a single 250 kHz laser irradiation. Interestingly, the position of the Si-rich region depended on the relative positions between 1 kHz and 250 kHz photoexcited regions. The observation of glass melt during laser exposure showed that the vortex flow of glass melt occurred and it induced the formation of a Si-rich region. Based on the simulation of the transient temperature and viscosity distributions during laser exposure, we temporally interpreted the origin of the vortex flow of glass melt and the mechanism of the formation of the Si-rich region. PMID:24977898

  15. Single-pulse laser ablation threshold of borosilicate, fused silica, sapphire, and soda-lime glass for pulse widths of 500  fs, 10  ps, 20  ns.

    Science.gov (United States)

    Nieto, Daniel; Arines, Justo; O'Connor, Gerard M; Flores-Arias, María Teresa

    2015-10-10

    In this work, we report a comparative study of the laser ablation threshold of borosilicate, fused silica, sapphire, and soda-lime glass as a function of the pulse width and for IR laser wavelengths. We determine the ablation threshold for three different pulse durations: τ=500  fs, 10 ps, and 20 ns. Experiments have been performed using a single laser pulse per shot in an ambient (air) environment. The results show a significant difference, of two orders of magnitude, between the group of ablation thresholds obtained for femtosecond, picosecond, and nanosecond pulses. This difference is reduced to 1 order of magnitude in the soda-lime substrate with tin impurities, pointing out the importance of the incubation effect. The morphology of the marks generated over the different glass materials by one single pulse of different pulse durations has been analyzed using a scanning electron microscope (FESEM ULTRA Plus). Our results are important for practical purposes, providing the ablation threshold data of four commonly used substrates at three different pulse durations in the infrared regime (1030-1064 nm) and complete data for increasing the understanding of the differences in the mechanism's leading ablation in the nanosecond, picosecond, and femtosecond regimes. PMID:26479792

  16. Kinetics of light-assisted physical ageing in S-rich arsenic sulphide glasses

    Indian Academy of Sciences (India)

    A KOZDRAS

    2016-08-01

    The obtained results show that kinetics of light-assisted physical ageing in S-rich glasses can be well fitted with stretch-exponential Kohlrausch-type function, in which exponent $\\beta$-values and the effective time relaxationconstant τ depend on the wavelength of incident photons. The obtained $\\beta$-values exhibit well-expressedminimum for the structural relaxation stimulated by light with energy of quanta comparable with the optical gap of the material. This effect is found to be similar to Se-rich glasses.

  17. Magneto-Optical and Magnetic Studies of Co-Rich Glass-Covered Microwires

    Directory of Open Access Journals (Sweden)

    Alexander Chizhik

    2012-01-01

    Full Text Available The magnetization reversal process in the surface and volume areas of Co-rich glass-covered microwires has been investigated. The study has been performed in the wide series of microwires with chemical composition, geometry (thickness of glass coating with the purpose of the tailoring of the giant magnetoimpedance effect. The comparative analysis of the magnetoelectric, magnetic, and magneto-optical experiments permits to optimise the giant magnetoimpedance ratio and elucidate the main properties of the magnetization reversal process in the different parts of the Co-rich microwire.

  18. Glass ceramic of high hardness and fracture toughness developed from iron-rich wastes

    Institute of Scientific and Technical Information of China (English)

    Weixin HAN

    2009-01-01

    A study has been carried out on the feasibility of using high iron content wastes, gen-erated during steel making, as a raw material for the production of glass ceramic. The iron-rich wastes were mixed and melted in different proportions with soda-lime glass cullet and sand. The devitrification of the parent glasses produced from the different mixtures was investigated using differential thermal analysis, X-ray diffraction, and scanning electron microscopy. The mechanical properties of the glass-ceramic were assessed by hardness and indentation fracture toughness measurement. A glass ce-ramic with mixture of 60 wt pct iron-rich wastes, 25 wt pct sand, and 15 wt pct glass cullet exhibited the best combination of properties, namely, hardness 7.9 GPa and fracture toughness 3.75 MPa.m1/2, for the sake of containing magnetite in marked dendritic morphology. These new hard glass ceramics are candidate materials for wear resistant tiles and paving for heavy industrial floors.

  19. Glass-Coated Beryllium Mirrors for the LHCb RICH1 Detector

    CERN Document Server

    Barber, G J; Cameron, W; D'Ambrosio, C; Frei, C; Harnew, N; Head, R; Khimitch, Y P; Khmelnikov, V A; Loveridge, P W; Metlica, F; Obraztsov, V F; Piedigrossi, D; Sizenev, V; Kompozit Joint Stock Company, Moscow, Russia; Szczypka, P M; Ullaland, O; Vygosky, E; Websdale, D M

    2007-01-01

    The design, manufacture and testing of lightweight glass-coated beryllium spherical converging mirrors for the RICH1 detector of LHCb are described. The mirrors need to be lightweight to minimize the material budget and fluorocarbon-compatible to avoid degradation in the RICH1 C4F10 gas radiator. Results of the optical measurements for the small-sized prototypes and for the first full-sized prototype mirror are reported.

  20. Phase separation and crystallization in soda-lime borosilicate glass enriched in MoO3 studied by in situ Raman spectroscopy at high temperature

    OpenAIRE

    Magnin, Magali; Schuller, Sophie; Caurant, Daniel; Majérus, Odile; De Ligny, Dominique; Advocat, Thierry

    2008-01-01

    Phase separation and crystallisation processes may arise in molten glass when the MoO3 content exceeds its solubility limit. Molybdenum combined with other elements such as alkali and alkaline-earth may form crystalline molybdates, known as "yellow phases" in nuclear glasses. In order to establish the sequence of phase separation and crystallization processes occurring during the cooling of the melt, a non-radioactive simplified glass composition was chosen in the SiO2-B2O3Na2O-CaO system, wi...

  1. Domain walls collision in Fe-rich and Co-rich glass covered microwires

    Directory of Open Access Journals (Sweden)

    Gonzalez J.

    2013-01-01

    Full Text Available We report the results of the investigation of domain walls propagation in Fe-rich and Co-rich microwires performed using Sixtus-Tonks and magneto-optical Kerr effect techniques. It was found that under certain experimental conditions we are able to create the regime of the motion of two domain walls moving to opposite directions which terminates by the collision of the domain walls. Also the domain walls collision was visualized using magneto-optical Kerr effect microscope when the surface giant Barkhausen jump induced by circular magnetic field has been observed.

  2. Structural characterizations of rare earth-rich glasses for nuclear waste immobilization

    International Nuclear Information System (INIS)

    New nuclear glass compositions, able to immobilize highly active liquid wastes arising from high burn-up UO2 fuel reprocessing, are being studied. Investigations are being performed on rare earth rich glasses, known as durable matrices. After a preliminary study, a basic glass composition was selected (Glass A, wt. %): 51.0 SiO2 - 8.5 B2O3 - 12.2 Na2O - 4.3 Al2O3 - 4.8 CaO - 3.2 ZrO2 - 16.0 Nd2O3. The aim of this study is to determine the local environment of the rare earth in this glass and its evolution according to neodymium. To achieve this objective, glasses were prepared from the baseline Glass A with variable neodymium oxide amounts (from 0 to 30 wt. % Nd2O3). By coupling characterization methods such as EXAFS (Extended X-Ray Absorption Fine Structure) spectroscopy at the neodymium LIII-edge, optical absorption spectroscopy, 11B, 27Al MAS-NMR and Raman spectroscopy, pieces of information the rare earth surroundings in the glass were obtained. (authors)

  3. Why neutron guides may end up breaking down? Some results on the macroscopic behaviour of alkali-borosilicate glass support plates under neutron irradiation

    International Nuclear Information System (INIS)

    In this paper we report on a first part of a study on the mechanisms leading to brittle fracture in neutron guides made of glass as structural element. Such devices are widely used to deliver thermal and cold neutron beams to experimental lines in most large neutron research facilities. We present results on macroscopic properties of samples of guide glass substrates which are subjected to neutron irradiation at relatively large fluences. The results show a striking dependence of some of the macroscopic properties such as density, shape or surface curvature upon the specific chemical composition of a given glass. The relevance of the present findings for the installation of either replacement guides at the existing facilities or for the deployment of instruments for ongoing projects such as the European Spallation Source is briefly discussed

  4. Why neutron guides may end up breaking down? Some results on the macroscopic behaviour of alkali-borosilicate glass support plates under neutron irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Boffy, R.; Kreuz, M. [Institut Laue-Langevin, 71 avenue des Martyrs, CS 20156, F-38042 Grenoble Cedex 9 (France); Beaucour, J., E-mail: beaucour@ill.fr [Institut Laue-Langevin, 71 avenue des Martyrs, CS 20156, F-38042 Grenoble Cedex 9 (France); Köster, U. [Institut Laue-Langevin, 71 avenue des Martyrs, CS 20156, F-38042 Grenoble Cedex 9 (France); Bermejo, F.J. [Instituto de Estructura de la Materia, Consejo Superior de Investigaciones Cientificas, Serrano 123, E-20886 Madrid (Spain)

    2015-09-01

    In this paper we report on a first part of a study on the mechanisms leading to brittle fracture in neutron guides made of glass as structural element. Such devices are widely used to deliver thermal and cold neutron beams to experimental lines in most large neutron research facilities. We present results on macroscopic properties of samples of guide glass substrates which are subjected to neutron irradiation at relatively large fluences. The results show a striking dependence of some of the macroscopic properties such as density, shape or surface curvature upon the specific chemical composition of a given glass. The relevance of the present findings for the installation of either replacement guides at the existing facilities or for the deployment of instruments for ongoing projects such as the European Spallation Source is briefly discussed.

  5. Interfacial reactions between PbO-rich glasses and aluminium composites

    CERN Document Server

    Ison, S J

    2000-01-01

    565 deg C occurs when dissolution rate exceeds oxidation rate, exposing the fresh Al anode to the glass melt. Under inert atmosphere (at 583 deg C), air oxidation is not possible and galvanic cell redox reactions generate an excessive copper interlayer as the system attempts to sustain the oxide layer at the anode. Similar behaviour is observed in those coatings formed on the alloy using glass C (containing Al sub 2 O sub 3 and Na sub 2 O). In this case, the interfacial reactions involve the PbO of the glass and Pb-rich spherical precipitates are formed in the interfacial region, along side sodium aluminosilicate phases, precipitated from the PbO-depleted glass. The behaviour in both systems indicates that oxygen diffuses through the edge of the glass drop, from the atmosphere, to the substrate/glass interface. Coatings formed on the MMCs in air exhibited a porosity of approx 10%, attributed to the production of CO sub 2 gas through the oxidation of SiC at the glass/MMC interface by oxygen diffusion from the ...

  6. Structure and properties of rare earth-rich glassed for nuclear waste immobilisation

    International Nuclear Information System (INIS)

    A new nuclear glass composition, able to immobilize highly radioactive liquid wastes from high burn-up UO2 fuel, was established and its structure studied. The composition of the selected rare earth-rich glass is (molar %): 61.79 SiO2 - 8.94 B2O3 - 3.05 Al2O3 - 14.41 Na2O - 6.32 CaO - 1.89 ZrO2 - 3.60 RE2O3 (with RE = La, Ce, Pr and Nd). The aim of this study was to determine the local environment of the rare earth in this glass and also to glean information about the effect of glass composition on the rare earth neighbouring (influence of Si, B, Al, Na and Ca contents). To this end, several series of glasses, prepared from the baseline glass, were studied by different characterisation methods such as EXAFS spectroscopy at the neodymium LIII-edge, optical absorption spectroscopy, Raman spectroscopy and 29Si, 27Al and 11B MAS-NMR. By coupling all the results obtained, several hypotheses about the nature of the rare earth neighbouring in the glass were proposed. (author)

  7. Structure study and properties of rare earth-rich glassed for the conditioning of nuclear waste

    International Nuclear Information System (INIS)

    A new nuclear glass composition, able to immobilize highly radioactive liquid wastes from high burn-up UO2 fuel, was established and its structure studied. The composition of the selected rare earth-rich glass is (molar %): 61.79 SiO2 - 8.94 B2O3 - 3.05 Al2O3 - 14.41 Na2O - 6.32 CaO - 1.89 ZrO2 - 3.60 RE2O3 (with RE = La, Ce, Pr and Nd) The aim of this study was to determine the local environment of the rare earth in this glass and also to glean information about the effect of glass composition on the rare earth neighbouring (influence of Si, B, Al, Na and Ca contents). To this end, several series of glasses, prepared from the baseline glass, were studied by different characterisation methods such as EXAFS spectroscopy at the neodymium LIII-edge, optical absorption spectroscopy, Raman spectroscopy and 29Si, 27Al and 11B MAS-NMR. By coupling all the results obtained, several hypotheses about the nature of the rare earth neighbouring in the glass were proposed. (author)

  8. Synthesis and thermophysical property measurements on various types of glasses for nuclear waste immobilization

    International Nuclear Information System (INIS)

    Borosilicate glasses (BSG) are worldwide known host matrices for immobilization of radioactive High Level Waste (HLW). Different types of borosilicate glasses were prepared by changing the modifier concentrations and compositions to know the efficacy of the resulting glass in terms of glass formation, durability towards various waste elements, stability at higher temperatures, mobility of ionic species etc. towards nuclear applications. In this study BSG, Aluminium borosilicate glass (AlBSG), Barium borosilicate glass (BaBSG) and Lead borosilicate glasses (PbBSG) were prepared and characterised to confirm the glass formations. Percentage linear thermal expansion and glass transition temperatures were measured by dilatometric techniques

  9. Sulfur Isotopes in Gas-rich Impact-Melt Glasses in Shergottites

    Science.gov (United States)

    Rao, M. N.; Hoppe, P.; Sutton, S. R.; Nyquist, Laurence E.; Huth, J.

    2010-01-01

    Large impact melt glasses in some shergottites contain huge amounts of Martian atmospheric gases and they are known as gas-rich impact-melt (GRIM) glasses. By studying the neutron-induced isotopic deficits and excesses in Sm-149 and Sm-150 isotopes resulting from Sm-149 (n,gamma) 150Sm reaction and 80Kr excesses produced by Br-79 (n,gamma) Kr-80 reaction in the GRIM glasses using mass-spectrometric techniques, it was shown that these glasses in shergottites EET79001 and Shergotty contain regolith materials irradiated by a thermal neutron fluence of approx.10(exp 15) n/sq cm near Martian surface. Also, it was shown that these glasses contain varying amounts of sulfates and sulfides based on the release patterns of SO2 (sulfate) and H2S (sulfide) using stepwise-heating mass-spectrometric techniques. Furthermore, EMPA and FE-SEM studies in basaltic-shergottite GRIM glasses EET79001, LithB (,507& ,69), Shergotty (DBS I &II), Zagami (,992 & ,994) showed positive correlation between FeO and "SO3" (sulfide + sulfate), whereas those belonging to olivine-phyric shergottites EET79001, LithA (,506, & ,77) showed positive correlation between CaO/Al2O3 and "SO3".

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

    Directory of Open Access Journals (Sweden)

    BO LI

    2011-03-01

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

  11. Effect of the addition of Na2O on the thermal stability of alumino silicated glasses rich in rare earths

    International Nuclear Information System (INIS)

    Alumino silicated glasses rich in rare earths have been prepared by concentrated solar way. Their recrystallization, the structural and microstructural properties as well as the mechanical and thermal properties of these glasses have been studied. The results show the effect of sodium addition on the thermal stability of the materials, the vitreous transition temperature and the recrystallization temperature. A heat treatment has allowed to reveal the formation of sodium apatite micro-crystallites and of lanthanum silicate in the glasses. (O.M.)

  12. Gasification slag rheology and crystalline phase formation in titanium-calcium-alumina-silica-rich glass

    Energy Technology Data Exchange (ETDEWEB)

    Brooker, D.D. [Texaco, Inc., Beacon, NY (United States); Oh, M.S. [Hongik Univ., Seoul (Korea, Republic of)

    1996-10-01

    The Texaco Gasification Process employs a high temperature and pressure slagging gasifier, in which the viscosity of the slag plays a key role in determining operating conditions. The empirical models available in the literature as well as laboratory testing have concentrated on low titanium feeds. During the gasification of waste material, titanium oxide will become an important element in controlling the ash and slag behavior. Slag viscosity was measured at temperatures in the range of 1150-1500{degrees}C under reducing atmosphere with 0-30% titanium in combination with calcium-alumina-silica rich feeds to gain a better understanding of the slag theology. The slag viscosities with most titanium-rich slags showed the behavior of a crystalline slag with T{sub cv} of 1250{degrees}C. Crystalline phase analyses of the slag samples revealed that titanium oxide crystal will nucleate, but the glass phase is dominated by calcium-titanium-silicate and calcium-alumina-silicate glasses which have low melting points.

  13. Corrosion of K-3 glass-contact refractory in sodium-rich aluminosilicate melts

    International Nuclear Information System (INIS)

    The corrosion of the glass-contact refractory Monofrax K-3 in two sodium-rich aluminosilicate melts has been studied at 1,208 and 1,283 C using a modified ASTM procedure with constant agitation of the melt by air bubbling. The results for the monolithic refractory indicate a fast initial stage involving phase dissolution and transformation and a later passivated stage in which the surface of the refractory has been substantially modified. The composition of the stable spinel phase in the altered layer on monolithic coupons of K-3 is almost identical to the equilibrium composition bracketed by the dissolution of powdered K-3 into under-saturated melts on the other. The temperature and melt shear viscosity were found to have significant effects on the rates of K-3 dissolution and transformation

  14. EFFECTS OF LIGHTWEIGHT MULLITE-SILICA RICH GLASS COMPOSITE AGGREGATES ON PROPERTIES OF CASTABLES

    Directory of Open Access Journals (Sweden)

    Li Y.

    2013-09-01

    Full Text Available Mullite-silica rich glass (MSRG composite is a material which is more efficient than chamotte for refractory utilization of clay. The effects of lightweight MSRG composite aggregate on the properties of refractory castables were studied by XRD, SEM and EDS, etc. Comparing with a common lightweight chamotte aggregate, it was found that the hot modulus of rupture, refractoriness under load and thermal shock resistance of the castable with lightweight MSRG aggregate were higher than those of the castable with a common lightweight chamotte aggregate because MSRG did not contain silica crystalline phases and contained a liquid phase with very high viscosity at high temperature. The castables with lightweight chamotte aggregate have higher thermal expansion because of existence of cristobalite and quartz, and have lower thermal conductivity because of higher porosity.

  15. Structure, thermal stability and external irradiation resistance of rare earth and molybdenum rich-aluminoborosilicate glasses

    OpenAIRE

    Chouard, Nolwenn

    2011-01-01

    In France, the highly radioactive nuclear liquid wastes arising from spent nuclear fuel reprocessing (fission products + minor actinides (FPA)) are currently immobilized in an aluminoborosilicate glass called "R7T7". In the future, the opportunity of using new aluminoborosilicate glass compositions (HTC glasses) is considered in order to increase the waste loading in glasses and thus significantly decrease the number of glass canisters. However, the increase of the concentration of FPA could ...

  16. Structure of Se-rich As-Se glasses by high-resolution x-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    To establish the validity of various proposed structural models, we have investigated the structure of the binary AsxSe100-x chalcogenide glass family (x≤40) by high-resolution x-ray photoelectron spectroscopy. From the composition dependence of the valence band, the contributions to the density of states from the 4p lone pair electrons of Se and the 4p bonding states and 4s electrons of Se and As are identified in the top part of the band. The analysis of Se 3d and As 3d core-level spectra supports the so-called chain crossing model for the atomic structure of Se-rich AsxSe100-x bulk glasses. The results also indicate small deviations (∼3-8%) from this model, especially for glass compositions with short Se chains (2540Se60 and of Se-Se-Se fragments in a glass with composition x=30 is established

  17. Effect of ZnO and CaO on Alkali Borosilicate Glass Waste-form Immobilizing Simulated Mixed HLW%ZnO 和 CaO对模拟高放废液硅酸盐玻璃固化体性能的影响研究

    Institute of Scientific and Technical Information of China (English)

    张华; N.C.Hyatt; J.R.Stevens; R.Hand

    2015-01-01

    针对有些高放废液含有较多Fe、Cr、Ni过渡金属元素,在玻璃固化工艺过程中易于形成晶体,导致熔融玻璃体的黏度增加、化学稳定性变差以及工艺过程中易出现出料口堵塞等问题,研究了废物包容量为15%和20%、添加ZnO (5.6%)和CaO (1.75%)的配方对形成的4种玻璃固化体的物理性能(密度、硬度、断裂韧性)、化学性能(产品一致性测试和蒸汽腐蚀测试)和结构(X射线衍射析晶分析、拉曼光谱分析)的影响。研究分析显示,提高废物包容量至20%以及添加ZnO和CaO均可促进硼硅酸盐玻璃固化体网络结构的稳定性和化学稳定性,并增强玻璃体的密度,提高硬度;但玻璃固化体的高温黏度升高,断裂韧性下降。%Since the transit metals ,such as Fe ,Cr and Ni ,contained in some kinds of mixed HLW ,can likely to form crystal ,increase the melt viscosity ,destroy the chemi‐cal durability and block the discharge port .T he results obtained from investigating four glass waste‐forms ,including the alkali borosilicate glass matrix and alkali borosilicate glass matrix doped with 5.6% ZnO and 1.75% CaO in base matrixes ,immobilizing the simulated mixed HLW with 15% and 20% waste loadings aiming to determinate the effect of ZnO on the alkali borosilicate glass chemical durability with waste loading increasing ,were presented in this paper .Glass samples were characterized with XRD and Raman spectroscopy .The chemical durability was investigated using the standard protocols PCT and VHT .The XRD analysis results show that spinel crystal appears and grows in glass samples at the waste loading in 20% without ZnO addition and waste loading in 15% and 20% added ZnO .T he Raman spectroscopy analysis results indicate that ZnO and CaO can enhance the glass network connective ,and the chemical durability test results display that the addition of ZnO and CaO can improve the short term

  18. Characterization of Glasses in One Type of Alumina Rich Fly Ash by Chemical Digestion Methods: Implications for Alumina Extraction

    Directory of Open Access Journals (Sweden)

    Lijun Zhao

    2016-01-01

    Full Text Available In recent years, one type of alumina rich fly ash (ARFA with about 50 wt% of alumina has been extensively investigated for alumina extraction in China. Due to the silica in ARFA, alumina extraction would have to generate a huge amount of solid waste. There is a growing interest in the glasses in ARFA, because they are composed mainly of silica and could be removed prior to alumina extraction. In this work, the glasses in ARFA have been investigated by chemical methods, that is, acid and base digestions. The chemical compositions have been measured by XRF for ARFA from the digestion processes. The K2O standard, XRD, and FTIR spectroscopies were successfully used to define the digestions processes, and size analysis and SEM-EDX provided rich information on particle transformations. As a result, acid and base digestion methods were found to produce very similar results for the glasses in ARFA. The K2O standard was attributed to the formation of glasses by illites, and TiO2 and Fe2O3 were proposed to originate from ilmenite in alumina rich coals (ARC. Some implications of the results were also discussed for the alumina extraction from ARFA.

  19. On the transition from tin-rich to antimony-rich European white soda-glass trade beads for the Senecas of Northeastern North America

    International Nuclear Information System (INIS)

    It has been shown that several modifications occurred, over the span of the 17th to 19th centuries, in the agents used to opacify European-made white soda-glass beads that were transmitted as trade goods to northeastern North America. Tin was used at the beginning of the 17th century, followed by Sb later in the century, and then by As during the 18th and 19th centuries. In an attempt to define more closely the transition from Sn-rich to Sb-rich white beads, 198 white glass beads from a number of archaeological sites in western New York State were analyzed. It was shown that the arrival of Sb-white soda-glass trade beads began in this region during the period from approximately A.D. 1625-1640, and that they had completely replaced Sn-white beads by A.D. 1675. Specific bead chemistries link a number of the archaeological sites. (author)

  20. Characterization of Glasses in One Type of Alumina Rich Fly Ash by Chemical Digestion Methods: Implications for Alumina Extraction

    OpenAIRE

    Lijun Zhao; Hanshuang Xiao; Baodong Wang; Qi Sun

    2016-01-01

    In recent years, one type of alumina rich fly ash (ARFA) with about 50 wt% of alumina has been extensively investigated for alumina extraction in China. Due to the silica in ARFA, alumina extraction would have to generate a huge amount of solid waste. There is a growing interest in the glasses in ARFA, because they are composed mainly of silica and could be removed prior to alumina extraction. In this work, the glasses in ARFA have been investigated by chemical methods, that is, acid and base...

  1. Inward Cationic Diffusion and Formation of Silica-Rich Surface Nanolayer of Glass

    DEFF Research Database (Denmark)

    Smedskjær, Morten Mattrup; Deubener, Joachim; Yue, Yuanzheng

    2009-01-01

    surface to the interior of the glass. The inward diffusion is induced by the reduction of V5+ to V4+ ions, when the glass is heat-treated in H2/N2 (1/99 v/v) at the glass transition temperature (Tg) for certain durations (ta). During the reduction of vanadium by H2, structurally bonded hydroxyl groups...

  2. Primary crystallization in Al-rich metallic glasses at unusually low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Bokeloh, J., E-mail: joachim.bokeloh@uni-muenster.de [Westfaelische Wilhelms-Universitaet Muenster, Institut fuer Materialphysik, Wilhelm-Klemm-Strasse 10, D-48149 Muenster (Germany); Boucharat, N. [Westfaelische Wilhelms-Universitaet Muenster, Institut fuer Materialphysik, Wilhelm-Klemm-Strasse 10, D-48149 Muenster (Germany)] [Forschungszentrum Karlsruhe, Institute of Nanotechnology, D-76021 Karlsruhe (Germany); Roesner, H.; Wilde, G. [Westfaelische Wilhelms-Universitaet Muenster, Institut fuer Materialphysik, Wilhelm-Klemm-Strasse 10, D-48149 Muenster (Germany)

    2010-06-15

    The initial stage of the primary crystallization reaction and the glass transition of the marginal metallic glass Al{sub 89}Y{sub 6}Fe{sub 5} were investigated by conventional differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC), microcalorimetry, X-ray diffraction (XRD) and transmission electron microscopy. A sharp onset of the primary crystallization was found by microcalorimetry and XRD studies at temperatures which were 120 deg. C below the primary crystallization peak observed in conventional DSC. A systematic MDSC study of annealed samples revealed a wide spectrum of glass transition onsets, which show a strong dependence on the annealing conditions. In addition, the glass transition onsets can be linked to the initial stage of the primary crystallization. The spectrum of glass transition onsets observed is discussed with respect to the occurrence of phase separation preceding the nucleation and growth of dendritic aluminium nanocrystals.

  3. Primary crystallization in Al-rich metallic glasses at unusually low temperatures

    International Nuclear Information System (INIS)

    The initial stage of the primary crystallization reaction and the glass transition of the marginal metallic glass Al89Y6Fe5 were investigated by conventional differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC), microcalorimetry, X-ray diffraction (XRD) and transmission electron microscopy. A sharp onset of the primary crystallization was found by microcalorimetry and XRD studies at temperatures which were 120 deg. C below the primary crystallization peak observed in conventional DSC. A systematic MDSC study of annealed samples revealed a wide spectrum of glass transition onsets, which show a strong dependence on the annealing conditions. In addition, the glass transition onsets can be linked to the initial stage of the primary crystallization. The spectrum of glass transition onsets observed is discussed with respect to the occurrence of phase separation preceding the nucleation and growth of dendritic aluminium nanocrystals.

  4. Domain wall dynamics in Fe-rich glass covered amorphous microwires

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Jesus Daniel [Departamento de Fisica, Facultad de Ciencias, Universidad de Oviedo (Spain); Institute of Physics, Faculty of Science, UPJS, Kosice (Slovakia); Ruiz, Alvaro; Cobos, Raul F.; Ribot, Ivan; Vega, Victor; Alvarez, Pablo; Sanchez, Maria Luisa; Sanchez Ll., Jose Luis; Prida, Victor M. de la; Hernando, Blanca [Departamento de Fisica, Facultad de Ciencias, Universidad de Oviedo (Spain)

    2009-04-15

    The influence of glass covering on domain wall propagation in Fe{sub 65}B{sub 15}Si{sub 15}C{sub 5} amorphous microwires is studied, before and after glass removal. High values of domain wall velocity and mobility have been obtained. The domain wall velocity depends linearly on the driving magnetic field. However, the mobility of the domain wall is very different in both situations studied. The results are explained due to the modification of internal stress distribution after glass removing, that change the domain structure of the sample. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  5. INCONEL 690 CORROSION IN WTP (WASTE TREATMENT PLANT) HLW (HIGH LEVEL WASTE) GLASS MELTS RICH IN ALUMINUM & BISMUTH & CHROMIUM OR ALUMINUM/SODIUM

    Energy Technology Data Exchange (ETDEWEB)

    KRUGER AA; FENG Z; GAN H; PEGG IL

    2009-11-05

    Metal corrosion tests were conducted with four high waste loading non-Fe-limited HLW glass compositions. The results at 1150 C (the WTP nominal melter operating temperature) show corrosion performance for all four glasses that is comparable to that of other typical borosilicate waste glasses, including HLW glass compositions that have been developed for iron-limited WTP streams. Of the four glasses tested, the Bi-limited composition shows the greatest extent of corrosion, which may be related to its higher phosphorus content. Tests at higher suggest that a moderate elevation of the melter operating temperature (up to 1200 C) should not result in any significant increase in Inconel corrosion. However, corrosion rates did increase significantly at yet higher temperatures (1230 C). Very little difference was observed with and without the presence of an electric current density of 6 A/inch{sup 2}, which is the typical upper design limit for Inconel electrodes. The data show a roughly linear relationship between the thickness of the oxide scale on the coupon and the Cr-depletion depth, which is consistent with the chromium depletion providing the material source for scale growth. Analysis of the time dependence of the Cr depletion profiles measured at 1200 C suggests that diffusion of Cr in the Ni-based Inconel alloy controls the depletion depth of Cr inside the alloy. The diffusion coefficient derived from the experimental data agrees within one order of magnitude with the published diffusion coefficient data for Cr in Ni matrices; the difference is likely due to the contribution from faster grain boundary diffusion in the tested Inconel alloy. A simple diffusion model based on these data predicts that Inconel 690 alloy will suffer Cr depletion damage to a depth of about 1 cm over a five year service life at 1200 C in these glasses.

  6. Introduction - Acid decomposition of borosilicate ores

    International Nuclear Information System (INIS)

    The complex processing of mineral raw materials is an effective way for the extraction of valuable components. One of these raw materials are borosilicate ores from which the boric acid, aluminium and iron salts and building materials can be obtained. In the Institute of Chemistry of the Academy of Sciences of the Republic of Tajikistan the flowsheets of the processing of borosilicate raw materials by acid and chloric methods were elaborated. The acid methods of decomposition of borosilicate ores of Ak-Arkhar Deposit were considered in present monograph. The carried out researches on elaboration of physicochemical aspects and technological acid methods allowed to define the optimal ways of extraction of valuable products from borosilicate raw materials of Tajikistan.

  7. Sulfur and iron speciation in gas-rich impact-melt glasses from basaltic shergottites determined by microXANES

    Energy Technology Data Exchange (ETDEWEB)

    Sutton, S.R.; Rao, M.N.; Nyquist, L.E. (UofC); (Johnson Space Center)

    2008-04-28

    Sulfur and iron K XANES measurements were made on GRIM glasses from EET 79001. Iron is in the ferrous state. Sulfur speciation is predominately sulfide coordination but is Fe coordinated in Lith B and, most likely, Ca coordinated in Lith A. Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Moessbauer studies on rocks at Meridian and Gusev, whereas MgSO{sub 4} is deduced from MgO-SO{sub 3} correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum and alunogen/S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. On Earth, volcanic rocks contain measurable quantities of sulfur present as both sulfide and sulfate. Carroll and Rutherford showed that oxidized forms of sulfur may comprise a significant fraction of total dissolved sulfur, if the oxidation state is higher than {approx}2 log fO{sub 2} units relative to the QFM buffer. Terrestrial samples containing sulfates up to {approx}25% in fresh basalts from the Galapagos Rift on one hand and high sulfide contents present in oceanic basalts on the other indicate that the relative abundance of sulfide and sulfate varies depending on the oxygen fugacity of the system. Basaltic shergottites (bulk) such as Shergotty, EET79001 and Zagami usually contain small amounts of sulfur ({approx}0.5%) as pyrrhotite. But, in isolated glass pockets containing secondary salts (known as GRIM glasses) in these meteorites, sulfur is present in high abundance ({approx}1-12%). To

  8. Sulfur and Iron Speciation in Gas-rich Impact-melt Glasses from Basaltic Shergottites Determined by Microxanes

    Science.gov (United States)

    Sutton, S. R.; Rao, M. N.; Nyquist, L. E.

    2008-01-01

    Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Mossbauer studies on rocks at Meridian and Gusev, whereas MgSO4 is deduced from MgO - SO3 correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum and alunogen/ S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/ sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. To understand the implications of these observations for the formation of the Gas-rich Impact-melt (GRIM) glasses, we determined the oxidation state of Fe in the GRIM glasses using Fe K micro-XANES techniques.

  9. Evidence for formation of Se molecular clusters during precipitation of CdSe1-xSx nanoparticles in glass

    International Nuclear Information System (INIS)

    While studying the effect of thermal treatment at 625-700 C on the formation of borosilicate glass-embedded CdSe or CdSe1-xSx nanocrystals, pronounced bands at 323 and 646 cm-1 were observed in the Raman spectra. They are assigned to Se2 clusters on the base of their frequency positions, widths, intensities, and resonance behavior. The precipitation of Se2 molecular clusters in borosilicate glass is shown to occur when the heat treatment temperature and/or duration are beyond the range, most suitable for the formation of CdSe or CdSe-rich CdSe1-xSx nanocrystals. (orig.)

  10. Under-water superoleophobic Glass: Unexplored role of the surfactant-rich solvent

    OpenAIRE

    Waghmare, Prashant R.; Das, Siddhartha; Mitra, Sushanta K.

    2013-01-01

    Preparing low energy liquid-repellant surfaces (superhydrophobic or superoleophobic) have attracted tremendous attention of late. In all these studies, the necessary liquid repellency is achieved by irreversible micro-nano texturing of the surfaces. Here we show for the first time that a glass surface, placed under water, can be made superoleophobic (with unprecedented contact angles close to 180 degrees and roll off angles only a few fractions of 1 degree) by merely changing the surfactant c...

  11. Microbial colonization of basaltic glasses in hydrothermal organic-rich sediments at Guaymas Basin

    Directory of Open Access Journals (Sweden)

    Nolwenn eCallac

    2013-08-01

    Full Text Available Oceanic basalts host diverse microbial communities with various metabolisms involved in C, N, S and Fe biogeochemical cycles which may contribute to mineral and glass alteration processes at, and below the seafloor. In order to study the microbial colonization on basaltic glasses and their potential biotic/abiotic weathering products, two colonization modules called AISICS (Autonomous In Situ Instrumented Colonization System were deployed in hydrothermal deep-sea sediments at the Guaymas Basin for 8 days and 22 days. Each AISICS module contained 18 colonizers (including sterile controls filled with basaltic glasses of contrasting composition. Chemical analyses of ambient fluids sampled through the colonizers showed a greater contribution of hydrothermal fluids (maximum temperature 57.6°C for the module deployed during the longer time period. For each colonizer, the phylogenetic diversity and metabolic function of bacterial and archaeal communities were explored using a molecular approach by cloning and sequencing. Results showed large microbial diversity in all colonizers. The bacterial distribution is primarily linked to the deployment duration, as well as the depth for the short deployment time module. Some 16s rRNA sequences form a new cluster of Epsilonproteobacteria. Within the Archaea the retrieved diversity could not be linked to either duration, depth or substrata. However, mcrA gene sequences belonging to the ANME-1 mcrA-guaymas cluster were found sometimes associated with their putative sulfate-reducers syntrophs depending on the colonizers. Although no specific glass alteration texture was identified, nano-crystals of barite and pyrite were observed in close association with organic matter, suggesting a possible biological mediation. This study gives new insights into the colonization steps of volcanic rock substrates and the capability of microbial communities to exploit new environmental conditions.

  12. Saturation magnetostriction of Co-rich glass-covered amorphous wires

    Energy Technology Data Exchange (ETDEWEB)

    Neagu, Maria E-mail: mneagu@phys-iasi.ro; Chiriac, H.; Vazquez, M.; Borza, Firuta; Ovari, T.A

    2003-01-01

    The influence of Fe addition on saturation magnetostriction at zero applied stress, {lambda}{sub s}(0), for Co{sub 72.5-x}Fe{sub x}Si{sub 12.5}B{sub 15} (x=0, 3, 4.35, 5, and 7 at%) glass-covered amorphous wires was investigated. Samples were tested in as-cast state and after AC Joule-heating under applied stress. In as-cast state the alloys with 0, 3 and 4.35 at% Fe have negative {lambda}{sub s}(0) while the alloys with 5 and 7 at% Fe have positive {lambda}{sub s}(0)

  13. Saturation magnetostriction of Co-rich glass-covered amorphous wires

    International Nuclear Information System (INIS)

    The influence of Fe addition on saturation magnetostriction at zero applied stress, λs(0), for Co72.5-xFexSi12.5B15 (x=0, 3, 4.35, 5, and 7 at%) glass-covered amorphous wires was investigated. Samples were tested in as-cast state and after AC Joule-heating under applied stress. In as-cast state the alloys with 0, 3 and 4.35 at% Fe have negative λs(0) while the alloys with 5 and 7 at% Fe have positive λs(0)

  14. Dissolution of vitrified wastes in a high-pH calcium-rich solution

    Science.gov (United States)

    Utton, C. A.; Hand, R. J.; Bingham, P. A.; Hyatt, N. C.; Swanton, S. W.; Williams, S. J.

    2013-04-01

    The current baseline for the conditioning of most UK intermediate-level radioactive waste (ILW) is immobilisation using cement. However, vitrification of some UK ILW is being considered as an alternative. One option for the disposal of the resulting vitrified ILW would be to place it in a geological disposal facility in a high-pH environment with cemented ILW and a cement-based backfill. Therefore, the potential effects of such a high pH (˜12.5), calcium-rich cement-based environment on the dissolution behaviour of simulant ILW glasses have been studied using the product consistency test (PCT). Three non-radioactive waste compositions were assessed: a laboratory simulant ILW vitrified in a borosilicate glass and two full-scale simulant vitrified products (a slag containing simulant plutonium-contaminated material and Magnox sludge; and a glass containing clinoptilolite). Powdered samples were leached in saturated Ca(OH)2 solutions for up to 42 days at temperatures between 30 and 90 °C. In general the rates of dissolution were lower than expected at such a high pH compared to studies in the literature under alkaline conditions. In contrast to the typical dissolution behaviour of high level waste (HLW) glasses, dissolution of the simulant borosilicate ILW glass was initially slow, followed by a period of faster boron and alkali metal release. The saturation/residual regime was not reached within experimental timescales. The rate of dissolution during the period of faster release increased with increasing temperature; the activation energy for this stage of dissolution was calculated to be 47 ± 2 kJ mol-1 based on boron release. The two full-scale simulant glasses, which contained negligible boric oxide, exhibited conventional static dissolution profiles, and entered the residual rate regime after 7-14 days at 50 °C. The greater durability of the full-scale simulants is thought to be due to the greater content of network-forming oxides in these glasses compared to

  15. Comparison of glass and crystalline nuclear waste forms

    International Nuclear Information System (INIS)

    Nuclear waste forms may be divided into two broad categories: single phase glasses with minor crystalline components (e.g., borosilicate glasses) and crystalline waste forms, either single phase (e.g., monazite) or polyphase (e.g., SYNROC). This paper reviews the materials properties data that are available for each of these two types of waste forms. The principal data include: physical, thermal and mechanical properties, chemical durability; and radiation damage effects. Complete data are only available for borosilicate glasses and SYNROC; therefore, this comparison focuses on the performance assessment of borosilicate glass and SYNROC

  16. Under-water superoleophobic Glass: Unexplored role of the surfactant-rich solvent

    Science.gov (United States)

    Waghmare, Prashant R.; Das, Siddhartha; Mitra, Sushanta K.

    2013-05-01

    Preparing low energy liquid-repellant surfaces (superhydrophobic or superoleophobic) have attracted tremendous attention of late. In all these studies, the necessary liquid repellency is achieved by irreversible micro-nano texturing of the surfaces. Here we show for the first time that a glass surface, placed under water, can be made superoleophobic (with unprecedented contact angles close to 180 degrees and roll off angles only a few fractions of 1 degree) by merely changing the surfactant content of the water medium in which the oil (immiscible in water) has been dispersed. Therefore, we propose a paradigm shift in efforts to achieve liquid-repellant systems, namely, altering the solvent characteristics instead of engineering the surfaces. The effect occurs for a surfactant concentration much larger than the critical micelle concentration, and is associated to strong adsorption of surfactant molecules at the solid surface, triggering an extremely stable Cassie-Baxter like conformation of the oil droplets.

  17. Glasses

    DEFF Research Database (Denmark)

    Dyre, Jeppe

    2004-01-01

    The temperature dependence of the viscosity of most glassforming liquids is known to depart significantly from the classical Arrhenius behaviour of simple fluids. The discovery of an unexpected correlation between the extent of this departure and the Poisson ratio of the resulting glass could lead...... to new understanding of glass ageing and viscous liquid dynamics....

  18. Titanium impregnated borosilicate zeolites for epoxidation catalysis

    Czech Academy of Sciences Publication Activity Database

    Přech, Jan; Vitvarová, Dana; Lupínková, Lenka; Kubů, Martin; Čejka, Jiří

    2015-01-01

    Roč. 212, AUG 2015 (2015), s. 28-34. ISSN 1387-1811 R&D Projects: GA ČR GAP106/11/0819 Institutional support: RVO:61388955 Keywords : borosilicate * titanium impregnation * epoxidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.453, year: 2014

  19. Low-field non-resonant microwave absorption in glass-coated Co-rich microwires

    Energy Technology Data Exchange (ETDEWEB)

    Valenzuela, Raul; Alvarez, Guillermo [Depto. de Materiales Metalicos y Ceramicos, Universidad Nacional Autonoma de Mexico, Mexico D.F. 04510 (Mexico); Montiel, Herlinda [Depto. de Tecnociencias, Centro de Ciencias Aplicadas y Desarrollo Tecnologico, Universidad Nacional Autonoma de Mexico (Mexico); Zamorano, Rafael [Depto. de Ciencias de Materiales, Escuela Superior de Fisica y Matematicas, Instituto Politecnico Nacional, Mexico D.F. (Mexico)

    2009-04-15

    A study of low-field non-resonant microwave absorption (LFA) at 9.8 GHz, on as-cast amorphous Co-rich CoFeBSi microwires under different measuring geometries is presented. Results confirm that LFA is associated with the magnetization processes from the unmagnetized state (H{sub DC}=0) to the saturated condition, in many aspects similar to Giant Magnetoimpedance (GMI), and clearly different from ferromagnetic resonance (FMR). LFA signal showed large variations in its maximum-minimum separation as a function of the measuring geometry, which is interpreted in terms of the total anisotropy in the process. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  20. Structure and properties of rare earth-rich glassed for nuclear waste immobilisation; Etude des caracteristiques structurales et des proprietes de verres riches en terres rares destines au confinement des produits de fission et elements a vie longue

    Energy Technology Data Exchange (ETDEWEB)

    Bardez, I

    2004-11-15

    A new nuclear glass composition, able to immobilize highly radioactive liquid wastes from high burn-up UO{sub 2} fuel, was established and its structure studied. The composition of the selected rare earth-rich glass is (molar %): 61.79 SiO{sub 2} - 8.94 B{sub 2}O{sub 3} - 3.05 Al{sub 2}O{sub 3} - 14.41 Na{sub 2}O - 6.32 CaO - 1.89 ZrO{sub 2} - 3.60 RE{sub 2}O{sub 3} (with RE = La, Ce, Pr and Nd). The aim of this study was to determine the local environment of the rare earth in this glass and also to glean information about the effect of glass composition on the rare earth neighbouring (influence of Si, B, Al, Na and Ca contents). To this end, several series of glasses, prepared from the baseline glass, were studied by different characterisation methods such as EXAFS spectroscopy at the neodymium LIII-edge, optical absorption spectroscopy, Raman spectroscopy and {sup 29}Si, {sup 27}Al and {sup 11}B MAS-NMR. By coupling all the results obtained, several hypotheses about the nature of the rare earth neighbouring in the glass were proposed. (author)

  1. Platinoids and molybdenum in nuclear waste containment glasses: a structural study

    International Nuclear Information System (INIS)

    This work deals with the structure of borosilicate nuclear glasses and with some relationships between structure and macroscopic properties. Two types of elements which may disturb the industrial process - platinoids (Ru and Pd) and molybdenum - are central to this work. Platinoids induce weak modifications on the structure of the glass, causing a depolymerization of the glassy network, an increase of the [3]B/[4]B ratio and a modification of the medium range order around Si between 3.3 and 4.5 angstrom. The modifications of viscosity and density induced by platinoids in the glass are not due to the structural effect of the platinoids. The increase of viscosity is attributed to needle shaped RuO2. It can be moderated by imposing reducing conditions during the elaboration of the glass. The slight difference between experimental and calculated densities is due to the increase of the volume percentage of bubbles in the glass with increasing platinoid content. Mo is either present in the glass as molybdic groupings, or mobilized in chemically complex molybdic crystalline phases. The chemical composition and mineralogy of these phases has been obtained using electronic microprobe data and XRD with Rietveld analysis. The distribution of the different elements between the crystalline phases and the glass is strongly influenced by the structural role of the various cations in the glass. The Mo present in the glass appears as MoO4 tetrahedra, independent of the borosilicate network. The formation of the crystalline phases can be explained by the existence of a precursor in which the MoO4 tetrahedra are concentrated in rich alkali and earth-alkali bearing areas of the glass. (author)

  2. Platelet-rich plasma plus bioactive glass in the treatment of intra-bony defects: a study in dogs

    Directory of Open Access Journals (Sweden)

    Marcelo Diniz Carvalho

    2011-02-01

    Full Text Available OBJECTIVE: This study was designed to evaluate, histomorphometrically, the association of platelet-rich plasma (PRP and bioactive glass (BG in the treatment of periodontal intrabony defects. MATERIAL AND METHODS: Nine mongrel dogs were included in the study. Three-wall intrabony defects were surgically created at the mesial and distal aspect of first mandibular molar and exposed to plaque accumulation for 1 month. The defects were randomly assigned to the groups: control, BG, PRP, PRP+BG. Dogs were sacrificed 90 days after the surgeries. The histometric parameters evaluated were: length of sulcular and junctional epithelium, connective tissue adaptation, new cementum, new bone, defect extension and area of new bone filling the defect. RESULTS: A superior area of new bone was observed in PRP+BG and BG (13.80±2.32 mm² and 15.63±2.64 mm², respectively when compared to the other groups (8.19±1.46 mm² and 8.81±1.47 mm² for control and PRP, respectively. No statistically significant differences were observed in the remaining parameters. CONCLUSIONS: Within the limits of this study, it may be concluded that PRP failed to provide statistically significant improvements in the histometric parameters.

  3. Solubility of actinides and surrogates in nuclear glasses

    International Nuclear Information System (INIS)

    The nuclear wastes are currently incorporated in borosilicate glass matrices. The resulting glass must be perfectly homogeneous. The work discussed here is a study of actinide (thorium and plutonium) solubility in borosilicate glass, undertaken to assess the extent of actinide solubility in the glass and to understand the mechanisms controlling actinide solubilization. Glass specimens containing; actinide surrogates were used to prepare and optimize the fabrication of radioactive glass samples. These preliminary studies revealed that actinide Surrogates solubility in the glass was enhanced by controlling the processing temperature, the dissolution kinetic of the surrogate precursors, the glass composition and the oxidizing versus reducing conditions. The actinide solubility was investigated in the borosilicate glass. The evolution of thorium solubility in borosilicate glass was determined for temperatures ranging from 1200 deg C to 1400 deg C.Borosilicate glass specimens containing plutonium were fabricated. The experimental result showed that the plutonium solubility limit ranged from 1 to 2.5 wt% PuO2 at 1200 deg C. A structural approach based on the determination of the local structure around actinides and their surrogates by EXAFS spectroscopy was used to determine their structural role in the glass and the nature of their bonding with the vitreous network. This approach revealed a correlation between the length of these bonds and the solubility of the actinides and their surrogates. (author)

  4. Comparative study of seven glasses for solidification of nuclear wastes

    International Nuclear Information System (INIS)

    The relative leaching behavior of seven alkali borosilicate glasses considered for immobilization of high level radioactive wastes was compared using a static 900C leach test. Leaching times studied were 1, 3, 7, 14 and 28 days with ratios of glass surface area (SA) to solution volume (V) being SA/V = 1.0 cm-1 and 0.1 cm-1. With the range of glass compositions studied, it was not possible to determine the effect of each element on leaching behavior, however some conclusions regarding the general influence of the glass network formers can be made: the addition of Al2O3, results in a large increase in the chemical durability of the glass. The presence of Fe2O3, is necessary to develop with Al2O3 a second protective layer on top of the silica-rich film that results from rapid dealkalization. The difference between the results obtained at SA/V = 1.0 cm-1 and 0.1 cm-1 shows the importance of understanding both the effects of glass composition and solution concentrations on the behavior of nuclear waste glasses

  5. Ion Current Rectification Behavior at Novel Borosilicate Glass Capillaries

    Czech Academy of Sciences Publication Activity Database

    Silver, Barry Richard; Holub, Karel; Mareček, Vladimír

    Ústí nad Labem: BEST servis, 2012 - (Navrátil, T.; Fojta, M.), s. 120-124 ISBN 978-80-905221-0-7. [Moderní elektrochemické metody /32./. Jetřichovice (CZ), 21.05.2012-25.05.2012] Institutional support: RVO:61388955 Keywords : ion * rectification * impedance Subject RIV: CG - Electrochemistry

  6. Formulation, testing, and structural characterization of high-zirconium high-level waste glasses

    International Nuclear Information System (INIS)

    A range of compositions of high-zirconia borosilicate glasses were formulated and their structures investigated by a combination of techniques. These compositions have potential applications for high-level nuclear waste storage in combination with advanced reprocessing methods. Raman and Zr EXAFS data were collected for a series of glasses spanning a range of zirconia concentrations. The Raman spectra indicate that Zr acts as a silicate network modifier, where the silicate tetrahedral network depolymerizes as the zirconia content increases. Zr EXAFS analysis indicates that Zr is found in octahedral sites, and to a minor extent, seven-coordinated sites. As the zirconia content increases, the fraction of seven-coordinated Zr-sites increases; this may be the cause of ZrO2 baddeleyite crystallization that was observed in some Zr-rich glasses investigated

  7. Systems approach to nuclear waste glass development

    International Nuclear Information System (INIS)

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

  8. Spent fuel from nuclear research reactors immobilized in sintered glass

    International Nuclear Information System (INIS)

    Different kinds of glasses, borosilicates, Iron borosilicates and Iron phosphates, were tested in order to determine its capability to immobilize calcined uranium silicide in a sintering process. Iron phosphate glass developed in our laboratory showed the best results in SEM analysis. Also its gravimetric leaching rate is less than 0.45 g.m-2 .day-1 for 7 and 10% loading which is lower than any previously studied for us. (author)

  9. Volume changes in glass induced by an electron beam

    International Nuclear Information System (INIS)

    Three glasses (float, borosilicate float and Schott D263 glasses) were irradiated by 50 keV electron beams with doses within the range of 0.21–318.5 kC/m2. Volume changes induced by electron bombarding were monitored by means of Atomic Force Microscopy. Incubation doses, related to mobility of alkali ions, were measured. Low doses showed compaction of all glasses while higher doses revealed volume inflation, except for borosilicate float glass. Both surfaces of float glass were irradiated and significant differences between them were found

  10. Phase Stability Determinations of DWPF Waste Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Marra, S.L.

    1999-10-22

    Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass. To fulfill this requirement, glass samples were heat treated at various times and temperatures. These results will provide guidance to the repository program about conditions to be avoided during shipping, handling and storage of DWPF canistered waste forms.

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

    International Nuclear Information System (INIS)

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

  12. Mantle metasomatism by P- and F-rich melt/fluids:evidence from phosphate glass in spinel lherzolite xenolith in Keluo,Heilongjiang Province

    Institute of Scientific and Technical Information of China (English)

    ZHANG WenLan; SHAO JiAn; XU XiSheng; WANG RuCheng; CHEN LiHui

    2007-01-01

    Spinel lherzolite xenoliths were found in phonolitic alkaline basalt in the Keluo area,Heilongjiang Province. Detailed electron-microprobe study revealed abundant phosphates and associated metasomatic minerals between primary phases in xenolith. The phosphates are considered special residual phases (coagulation) of P- and F-rich mantle melt/fluid,most of which were identified as glass phases based on Raman spectroscopic analyses. Such melt/fluid also further metasomatized primary minerals,thus leading to formation of reaction rims successively composed of Cr-spinel symplectitic zone and olivine + diopside zone. Therefore,the P- and F-rich melt/fluid played an important role in the upper-mantle metasomatism in the Keluo area. It is suggested that this kind of metasomstism may occur in some other places of eastern China. The present results may also have significance in studying types of metasomatic melt/fluid and its evolution in the lithospheric mantle beneath eastern China.

  13. Study of the possibilities of using nuclear methods for characterizing the surface region of glasses

    International Nuclear Information System (INIS)

    Following a review of the different methods used for the analysis of surfaces, we give a detailed description of charged particle elastic backscattering and the experimental devices. We then apply this method to the study of the lixiviation of borosilicate glasses in aqueous media and to the characterization of two heavy elements, cerium and thorium and their possible interaction in simple borosilicates

  14. Luminescence spectroscopy of the Gd-rich Ce3+-, Tb3+- and Mn2+-doped phosphate glasses

    International Nuclear Information System (INIS)

    Absorption, emission and excitation spectra and luminescence decay kinetics of Na(K)GdCe, NaGdTb and NaGdMn phosphate glasses and their dependence on the temperature (in the 1.7-300 K range) and on the glass composition have been studied. The processes of energy migration through the Gd3+ ions and following energy transfer in Gd3+-impurity pairs have been compared for the three types of the glasses studied. It has been suggested that the Gd3+ →Tb3+ energy transfer occurs only in the closest pairs through a very short-range exchange interaction, while the Gd3+ →Ce3+ and Gd3+ →Mn2+ energy transfer is possible also in more separated pairs mainly due to the longer-range multipolar Gd3+-impurity interaction. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

  15. Fabrication of Silicon Nitride Dental Core Ceramics with Borosilicate Veneering material

    Science.gov (United States)

    Wananuruksawong, R.; Jinawath, S.; Padipatvuthikul, P.; Wasanapiarnpong, T.

    2011-10-01

    Silicon nitride (Si3N4) ceramic is a great candidate for clinical applications due to its high fracture toughness, strength, hardness and bio-inertness. This study has focused on the Si3N4 ceramic as a dental core material. The white Si3N4 was prepared by pressureless sintering at relative low sintering temperature of 1650 °C in nitrogen atmosphere. The coefficient of thermal expansion (CTE) of Si3N4 ceramic is lower than that of Zirconia and Alumina ceramic which are popular in this field. The borosilicate glass veneering was employed due to its compatibility in thermal expansion. The sintered Si3N4 specimens represented the synthetic dental core were paintbrush coated by a veneer paste composed of borosilicate glass powder (<150 micrometer, Pyrex) with 5 wt% of zirconia powder (3 wt% Y2O3 - partial stabilized zirconia) and 30 wt% of polyvinyl alcohol (5 wt% solution). After coating the veneer on the Si3N4 specimens, the firing was performed in electric tube furnace between 1000-1200°C. The veneered specimens fired at 1100°C for 15 mins show good bonding, smooth and glossy without defect and crazing. The veneer has thermal expansion coefficient as 3.98×10-6 °C-1, rather white and semi opaque, due to zirconia addition, the Vickers hardness as 4.0 GPa which is closely to the human teeth.

  16. Luminescence of powdered uranium glasses

    Science.gov (United States)

    Eubanks, A. G.; Mcgarrity, J. M.; Silverman, J.

    1974-01-01

    Measurement of cathodoluminescence and photoluminescence efficiencies in powdered borosilicate glasses having different particle size and different uranium content. Excitation with 100 to 350 keV electrons and with 253.7 nm light was found to produce identical absolute radiant exitance spectra in powdered samples. The most efficient glass was one containing 29.4 wt% B2O3, 58.8 wt% SiO2, 9.8 wt% Na2O and 2.0 wt% UO2.

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

    Science.gov (United States)

    Lee, Martin R.; Chatzitheodoridis, Elias

    2016-07-01

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

  18. Feasibility Study for Preparation and Use of Glass Grains as an Alternative to Glass Nodules for Vitrification of Nuclear Waste

    International Nuclear Information System (INIS)

    High level nuclear liquid waste (HLW) is immobilized using borosilicate glass matrix. Presently joule heated ceramic melter is being employed for vitrification of HLW in India. Preformed nodules of base glass are fed to melter along with liquid waste in predetermined ratio. In order to reduce the cost incurred for production of glass nodules of base glass, an alternative option of using glass grains was evaluated for its preparation and its suitability for the melter operation. (author)

  19. Excimer laser-induced material modification to create nanometer high smooth patterns in glass using mask projection

    Energy Technology Data Exchange (ETDEWEB)

    Rudolph, Thomas; Zimmer, Klaus; Boehme, Rico; Ruthe, David [Leibniz-Institut fuer Oberflaechenmodifizierung e.V., Permoserstrasse 15, D-04318 Leipzig (Germany)

    2007-04-15

    Laser swelling of borosilicate and soda-lime glass is shown for wavelengths of 193 and 248 nm. Very smooth patterns up to 45 nm high were generated by KrF laser (248 nm) irradiation of borosilicate glass at a fluence of 1.5 J/cm{sup 2}. At 193 nm laser wavelength, lower heights (up to 13 nm) and lower swelling threshold fluences (0.1 J/cm{sup 2}) were observed due to higher material absorption. For the less absorbing soda-lime glass higher fluences than for the borosilicate glass are needed to establish elevated structures. Gratings in borosilicate glass with sub-micron periodicity demonstrate the high resolution of the method. The results can be explained by a thermo-physical model based on the change of the glass transition temperature due to fast cooling after the pulsed laser irradiation.

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

    International Nuclear Information System (INIS)

    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

  1. Method for making glass

    International Nuclear Information System (INIS)

    A method for making better quality molten (borosilicate and other) glass in a glass melter, the glass having the desired viscosity and, preferably, also the desired resistivity so that the glass melt can be established effectively and the product of the glass melter will have the desired level of quality. The method includes the adjustment of the composition of the a ass constituents that are fed into the melterin accordance with certain correlations that reliably predict the viscosity and resistivity from the melter temperature and the melt composition, then heating the ingredients to the melter's operating temperature until they melt and homogenize. The equations include the calculation of a ''non-bridging oxygen'' term from the numbers of moles of the various ingredients, and then the determination of the viscosity and resistivity from the operating temperature of the melter and the non-bridging oxygen term

  2. Glass viscosity calculation based on a global statistical modeling approach

    International Nuclear Information System (INIS)

    A global statistical glass viscosity model was developed for predicting the complete viscosity curve, based on more than 2200 composition-property data of silicate glasses from the scientific literature, including soda-lime-silica container and float glasses, TV panel glasses, borosilicate fiber wool and E type glasses, low expansion borosilicate glasses, glasses for nuclear waste vitrification, lead crystal glasses, binary alkali silicates, and various further compositions from over half a century. It is shown that within a measurement series from a specific laboratory the reported viscosity values are often over-estimated at higher temperatures due to alkali and boron oxide evaporation during the measurement and glass preparation, including data by Lakatos et al. (1972) and the recently published High temperature glass melt property database for process modeling by Seward et al. (2005). Similarly, in the glass transition range many experimental data of borosilicate glasses are reported too high due to phase separation effects. The developed global model corrects those errors. The model standard error was 9-17 C, with R2 = 0.985-0.989. The prediction 95% confidence interval for glass in mass production largely depends on the glass composition of interest, the composition uncertainty, and the viscosity level. New insights in the mixed-alkali effect are provided

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

    Energy Technology Data Exchange (ETDEWEB)

    Fluegel, Alex

    2007-02-01

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

  4. Sintered glass

    International Nuclear Information System (INIS)

    The authors present an overview of various attempts to sinter high-level matrix. This paper focuses on the development of the porous glass matrix process (PGM process) for the fixation of HLW in a high-silica glass matrix by sintering. In the PGM process a borosilicate-type base glass is phase-separated by heat treatment. The low-silica phase is leached in HC1 and washed out. The remaining fine powder is soaked with HLW, dried under vacuum by gradual heating up to 1123 K, ground or ball-milled and finally sintered at 1473 K to a dense solid, consisting of a matrix of 96% SiO2 and 4% B2O3 in which the waste elements are trapped. The main advantage of the process is the high chemical durability of the final product. The rather complicated process technology, also leading to the generation of secondary waste (e.g. washing solution), is considered a disadvantage

  5. Radiation effects on transport and bubble formation in silicate glasses

    International Nuclear Information System (INIS)

    Advanced Electron Paramagnetic Resonance spectroscopy (pulsed EPR, time-resolved EPR, high-frequency EPR, ENDOR) has been used to structurally characterize metastable point defects in irradiated alkali borate, silicate, and borosilicate glasses and to study mobile interstitial H atoms. In addition, the yield of radiolytic oxygen has been determined by outgassing. Several mechanisms for the defect formation in oxide glasses have been established

  6. Influence of the critical Fe atomic volume on the magnetism of Fe-rich metallic glasses evidenced by pressure-dependent measurements

    Science.gov (United States)

    Kiss, L. F.; Kemény, T.; Bednarčík, J.; Gamcová, J.; Liermann, H.-P.

    2016-06-01

    Despite the intensive studies for decades, it is still not well understood how qualitatively different magnetic behaviors can occur in a narrow composition range for the Fe-rich Fe-transition metal (TM) amorphous alloys. In this study of amorphous F e100 -xZ rx (x =7 , 9, 12) metallic glasses, normal ferromagnetism (FM) is found at 12 % Zr where only the FM-paramagnetic (PM) transition is observed at the Curie temperature, TC. In contrast, spin-glass (SG)-PM transition at a temperature, Tg, called SG temperature, is only observed at 7 % Zr, while in the transient re-entrant composition range (x =8 -11 ) , an SG-FM transition at a temperature, Tf, called spin-freezing temperature, is also observed at low temperature besides the normal FM-PM transition at TC. In order to understand this unusual behavior, a detailed characterization of pressure (atomic volume), composition, and temperature dependence of the magnetic properties is coupled with high pressure synchrotron x-ray diffraction determination of the pressure dependence of the atomic volume. The results on F e100 -xZ rx (x =7 , 9, 12) are compared to those obtained for the FM C o91Z r9 metallic glass not showing any kind of anomalous magnetic properties. It is confirmed that the unusual behavior is caused by a granularlike magnetic structure where weakly coupled magnetic clusters are embedded into a FM bulk matrix. Since the mechanism of the magnetization reversal was found to be of the curling type rather than homogeneous rotation, the energy barrier determining the blocking temperature of the clusters is calculated as AR, where A is the exchange constant and R is the cluster size, in contrast to the usual characterization of the energy barrier by KV where K is the anisotropy energy and V is the cluster volume. The volume fraction of the FM part is a fast changing function of the bulk composition: Almost 100% FM fraction is found at 12 % of Zr while no trace of real FM is observed at 7 at % Zr. The driving

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

    International Nuclear Information System (INIS)

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

  8. Boron nitride nanosheets reinforced glass matrix composites

    Czech Academy of Sciences Publication Activity Database

    Saggar, Richa; Porwal, H.; Tatarko, P.; Dlouhý, Ivo; Reece, M. J.

    2015-01-01

    Roč. 114, SEP (2015), S26-S32. ISSN 1743-6753 R&D Projects: GA MŠk(CZ) 7AMB14SK155 EU Projects: European Commission(XE) 264526 Institutional support: RVO:68081723 Keywords : Boron nitride nanosheets * Borosilicate glass * Mechanical properties Subject RIV: JL - Materials Fatigue, Friction Mechanics Impact factor: 1.163, year: 2014

  9. Fabrication of Silicon Nitride Dental Core Ceramics with Borosilicate Veneering material

    Energy Technology Data Exchange (ETDEWEB)

    Wananuruksawong, R; Jinawath, S; Wasanapiarnpong, T [Research Unit of Advanced Ceramic, Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok (Thailand); Padipatvuthikul, P, E-mail: raayaa_chula@hotmail.com [Faculty of Dentistry, Srinakharinwirot University, Bangkok (Thailand)

    2011-10-29

    Silicon nitride (Si{sub 3}N{sub 4}) ceramic is a great candidate for clinical applications due to its high fracture toughness, strength, hardness and bio-inertness. This study has focused on the Si{sub 3}N{sub 4} ceramic as a dental core material. The white Si{sub 3}N{sub 4} was prepared by pressureless sintering at relative low sintering temperature of 1650 deg. C in nitrogen atmosphere. The coefficient of thermal expansion (CTE) of Si{sub 3}N{sub 4} ceramic is lower than that of Zirconia and Alumina ceramic which are popular in this field. The borosilicate glass veneering was employed due to its compatibility in thermal expansion. The sintered Si{sub 3}N{sub 4} specimens represented the synthetic dental core were paintbrush coated by a veneer paste composed of borosilicate glass powder (<150 micrometer, Pyrex) with 5 wt% of zirconia powder (3 wt% Y{sub 2}O{sub 3} - partial stabilized zirconia) and 30 wt% of polyvinyl alcohol (5 wt% solution). After coating the veneer on the Si{sub 3}N{sub 4} specimens, the firing was performed in electric tube furnace between 1000-1200 deg. C. The veneered specimens fired at 1100 deg. C for 15 mins show good bonding, smooth and glossy without defect and crazing. The veneer has thermal expansion coefficient as 3.98x10{sup -6} deg. C{sup -1}, rather white and semi opaque, due to zirconia addition, the Vickers hardness as 4.0 GPa which is closely to the human teeth.

  10. Radiolysis of hexane absorbing on borosilicate surface research

    International Nuclear Information System (INIS)

    The radiolysis process of hexane absorbing on borosilicate with various hydration degree is being investigated. Samples of borosilicate were treated by thermal vacuum at and T=493 K and P=1.33·10-4 Pa. The absorption of water and hexane was carried out on manometric equipment at 77 K temperature. An irradiation was conducted by γ-rays from 60Co source in the sealed in ampoules at 77 K with 10 kGy dose. In the irradiated samples the ESR spectrum with wide range that is characteristic for irradiated alkanes in the absorbing condition was observed. With increase of temperature of registration narrowing lines and improved sanction connected to recombination processes of radicals was observed. With increase of a hydration of a surface the redistribution and reduction of intensity separate component of a spectrum was observed. It specifies formation and stabilization bonding of radicals at smaller filling of a surface borosilicate. To reveal structure of radiolysis products IR spectra of desorbed from a borosilicate surface gas products were received at 333 K. In the field of low-frequency deformation of fluctuations CH2-groups the doublet strip with maxima was observed at 790 cm-1 and 770 cm-1 which is referred to low-molecular of radiolysis products

  11. Wetting behavior of lead borosilicates on ceramic substrates

    International Nuclear Information System (INIS)

    Wetting characteristics of several lead silicates. lead borates, and lead borosilicates, on alumina, beryllia, aluminum nitride, silicon nitride and silicon carbide substrates, were investigated. Both polycrystalline and single crystal substrates behavior of the liquids was studied with the sensile drop method, and optical and SEM/EDAX microscopy was used for examining interfaces. The results are discussed in relating to interfacial properties and bonding

  12. Solubility of actinides and surrogates in nuclear glasses; Solubilite des actinides et de leurs simulants dans les verres nucleaires. Limites d'incorporation et comprehension des mecanismes

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, Ch

    2003-07-01

    The nuclear wastes are currently incorporated in borosilicate glass matrices. The resulting glass must be perfectly homogeneous. The work discussed here is a study of actinide (thorium and plutonium) solubility in borosilicate glass, undertaken to assess the extent of actinide solubility in the glass and to understand the mechanisms controlling actinide solubilization. Glass specimens containing; actinide surrogates were used to prepare and optimize the fabrication of radioactive glass samples. These preliminary studies revealed that actinide Surrogates solubility in the glass was enhanced by controlling the processing temperature, the dissolution kinetic of the surrogate precursors, the glass composition and the oxidizing versus reducing conditions. The actinide solubility was investigated in the borosilicate glass. The evolution of thorium solubility in borosilicate glass was determined for temperatures ranging from 1200 deg C to 1400 deg C.Borosilicate glass specimens containing plutonium were fabricated. The experimental result showed that the plutonium solubility limit ranged from 1 to 2.5 wt% PuO{sub 2} at 1200 deg C. A structural approach based on the determination of the local structure around actinides and their surrogates by EXAFS spectroscopy was used to determine their structural role in the glass and the nature of their bonding with the vitreous network. This approach revealed a correlation between the length of these bonds and the solubility of the actinides and their surrogates. (author)

  13. Hafnium in peralkaline and peraluminous boro-aluminosilicate glass, and glass subcomponents: a solubility study

    International Nuclear Information System (INIS)

    A relationship between the solubility of hafnia (HfO2) and the host glass composition was explored by determining the solubility limits of HfO2 in peralkaline and peraluminous borosilicate glasses in the system SiO2-Al2O3-B2O3-Na2O, and in glasses in the system SiO2-Na2O-Al2O3 in air at 1450 C. The only Hf-bearing phase to crystallize in the peralkaline borosilicate melts is hafnia, while in the boron-free melts sodium-hafnium silicates crystallize. All peraluminous borosilicate melts crystallize hafnia, but the slightly peraluminous glasses also have sector-zoned hafnia crystals that contain Al and Si. The more peraluminous borosilicate glasses also crystallize a B-containing mullite. The general morphology of the hafnia crystals changes as peralkalinity (Na2O/(Na2O+Al2O3)) decreases, as expected in melts with increasing viscosity. In all of the glasses with Na2O > Al2O3, the solubility of hafnia is linearly and positively correlated with Na2O/(Na2O + Al2O3) or Na2O - Al2O3 (excess sodium), despite the presence of 5 to 16 mol% B2O3. The solubility of hafnia is higher in the sodium-aluminum borosilicate glasses than in the sodium-aluminosilicate glasses, suggesting that the boron is enhancing the effect that excess sodium has on the incorporation of Hf into the glass structure. The results of this solubility study are compared to other studies of high-valence cation solubility in B-free silicate melts. From this, for peralkaline B-bearing glasses, it is shown that, although the solubility limits are higher, the solution behavior of hafnia is the same as in B-free silicate melts previously studied. By comparison, also, it is shown that in peraluminous melts, there must be a different solution mechanism for hafnia: different than for peralkaline sodium-aluminum borosilicate glasses and different than for B-free silicate melts studied by others

  14. A space imaging concept based on a 4m structured spun-cast borosilicate monolithic primary mirror

    Science.gov (United States)

    West, S. C.; Bailey, S. H.; Bauman, S.; Cuerden, B.; Granger, Z.; Olbert, B. H.

    2010-07-01

    Lockheed Martin Corporation (LMC) tasked The University of Arizona Steward Observatory (UASO) to conduct an engineering study to examine the feasibility of creating a 4m space telescope based on mature borosilicate technology developed at the UASO for ground-based telescopes. UASO has completed this study and concluded that existing launch vehicles can deliver a 4m monolithic telescope system to a 500 km circular orbit and provide reliable imagery at NIIRS 7-8. An analysis of such an imager based on a lightweight, high-performance, structured 4m primary mirror cast from borosilicate glass is described. The relatively high CTE of this glass is used to advantage by maintaining mirror shape quality with a thermal figuring method. Placed in a 290 K thermal shroud (similar to the Hubble Space Telescope), the orbit averaged figure surface error is 6nm rms when earth-looking. Space-looking optical performance shows that a similar thermal conditioning scheme combined with a 270 K shroud achieves primary mirror distortion of 10 nm rms surface. Analysis shows that a 3-point bipod mount will provide launch survivability with ample margin. The primary mirror naturally maintains its shape at 1g allowing excellent end-to-end pre-launch testing with e.g. the LOTIS 6.5m Collimator. The telescope includes simple systems to measure and correct mirror shape and alignment errors incorporating technologies already proven on the LOTIS Collimator. We have sketched a notional earth-looking 4m telescope concept combined with a wide field TMA concept into a DELTA IV or ATLAS 552 EELV fairing. We have combined an initial analysis of launch and space performance of a special light-weighted honeycomb borosilicate mirror (areal density 95 kg/m2) with public domain information on the existing launch vehicles.

  15. Development of a glass matrix for vitrification of sulphate bearing high level radioactive liquid waste

    International Nuclear Information System (INIS)

    High level radioactive liquid waste (HLW) is generated during reprocessing of spent nuclear fuel. In the earlier reprocessing flow sheet ferrous sulphamate has been used for valancy adjustment of Pu from IV to III for effective separation. This has resulted in generation of HLW containing significance amount of sulphate. Internationally borosilicate glass matrix has been adopted for vitrification of HLW. The first Indian vitrification facility at Waste Immobilislition Plant (WIP), Tarapur a five component borosilicate matrix (SiO2 :B2O3 :Na2O : MnO : TiO2) has been used for vitrification of waste. However at Trombay HLW contain significant amount of sulphate which is not compatible with standard borosilicate formulation. Extensive R and D efforts were made to develop a glass formulation which can accommodate sulphate and other constituents of HLW e.g., U, Al, Ca, etc. This report deals with development work of a glass formulations for immobilization of sulphate bearing waste. Different glass formulations were studied to evaluate the compatibility with respect to sulphate and other constituents as mentioned above. This includes sodium, lead and barium borosilicate glass matrices. Problems encountered in different glass matrices for containment of sulphate have also been addressed. A glass formulation based on barium borosilicate was found to be effective and compatible for sulphate bearing high level waste. (author)

  16. Nanogratings formation in multicomponent silicate glasses

    Science.gov (United States)

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

    2016-03-01

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

  17. Structure study and properties of rare earth-rich glassed for the conditioning of nuclear waste; Etude des caracteristiques structurales et des proprietes de verres riches en terres rares destines au confinement des produits de fission et elements a vie longue

    Energy Technology Data Exchange (ETDEWEB)

    Bardez, I

    2004-11-15

    A new nuclear glass composition, able to immobilize highly radioactive liquid wastes from high burn-up UO{sub 2} fuel, was established and its structure studied. The composition of the selected rare earth-rich glass is (molar %): 61.79 SiO{sub 2} - 8.94 B{sub 2}O{sub 3} - 3.05 Al{sub 2}O{sub 3} - 14.41 Na{sub 2}O - 6.32 CaO - 1.89 ZrO{sub 2} - 3.60 RE{sub 2}O{sub 3} (with RE = La, Ce, Pr and Nd) The aim of this study was to determine the local environment of the rare earth in this glass and also to glean information about the effect of glass composition on the rare earth neighbouring (influence of Si, B, Al, Na and Ca contents). To this end, several series of glasses, prepared from the baseline glass, were studied by different characterisation methods such as EXAFS spectroscopy at the neodymium L{sub III}-edge, optical absorption spectroscopy, Raman spectroscopy and {sup 29}Si, {sup 27}Al and {sup 11}B MAS-NMR. By coupling all the results obtained, several hypotheses about the nature of the rare earth neighbouring in the glass were proposed. (author)

  18. Patch electrode glass composition affects ion channel currents.

    OpenAIRE

    Furman, R E; Tanaka, J C

    1988-01-01

    The influence of patch electrode glass composition on macroscopic IV relations in inside-out patches of the cGMP-activated ion channel from rod photoreceptors was examined for a soda lime glass, a Kovar sealing glass, a borosilicate glass, and several soft lead glasses. In several glasses the shape or magnitude of the currents changed as the concentration of EGTA or EDTA was increased from 200 microM to 10 mM. The changes in IV response suggest that, at low concentrations of chelator, divalen...

  19. Development of glass ceramics for the incorporation of fission products

    International Nuclear Information System (INIS)

    Spontaneous devitrification of fission-product-containing borosilicate glasses can be avoided by controlled crystallization after melting. Glass ceramics have been developed from a vitrified simulated waste and further improvement of product properties was achieved. In particular perovskite, h-celsian, diopside and eucryptite glass ceramics were prepared. These contained leach resistant host phases which exhibited considerable enrichment of long-lived fission products. All products showed increased impact resistance, but the thermal expansion was only slightly improved

  20. Glasses and ceramics for immobilisation of radioactive wastes for disposal

    International Nuclear Information System (INIS)

    The U.K. Research Programme on Radioactive Waste Management includes the development of processes for the conversion of high level liquid reprocessing wastes from thermal and fast reactors to borosilicate glasses. The properties of these glasses and their behaviour under storage and disposal conditions have been examined. Methods for immobilising activity from other wastes by conversion to glass or ceramic forms is described. The U.K. philosophy of final solutions to waste management and disposal is presented. (author)

  1. Glasses and nuclear waste vitrification

    International Nuclear Information System (INIS)

    Glass is an amorphous solid material which behaves like an isotropic crystal. Atomic structure of glass lacks long-range order but possesses short and most probably medium range order. Compared to crystalline materials of the same composition glasses are metastable materials however crystallisation processes are kinetically impeded within times which typically exceed the age of universe. The physical and chemical durability of glasses combined with their high tolerance to compositional changes makes glasses irreplaceable when hazardous waste needs immobilisation for safe long-term storage, transportation and consequent disposal. Immobilisation of radioactive waste in glassy materials using vitrification has been used successfully for several decades. Nuclear waste vitrification is attractive because of its flexibility, the large number of elements which can be incorporated in the glass, its high corrosion durability and the reduced volume of the resulting wasteform. Vitrification involves melting of waste materials with glass-forming additives so that the final vitreous product incorporates the waste contaminants in its macro- and micro-structure. Hazardous waste constituents are immobilised either by direct incorporation into the glass structure or by encapsulation when the final glassy material can be in form of a glass composite material. Both borosilicate and phosphate glasses are currently used to immobilise nuclear wastes. In addition to relatively homogeneous glasses novel glass composite materials are used to immobilise problematic waste streams. (author)

  2. Glass matrix composites. I - Graphite fiber reinforced glass

    Science.gov (United States)

    Prewo, K. M.; Bacon, J. F.

    1978-01-01

    An experimental program is described in which graphite fibers of Hercules HMS and HTS, Thornel 300, and Celanese DG-12 were used to reinforce, both uniaxially and biaxially, borosilicate pyrex glass. Composite flexural strength distribution, strength as a function of test temperature, fracture toughness and oxidative stability were determined and shown to be primarily a function of fiber type and the quality of fiber-matrix bond formed during composite fabrication. It is demonstrated that the graphite fiber reinforced glass system offers unique possibilities as a high performance structural material.

  3. Glasses and Glass-Ceramic Components from Inorganic Waste and Novel Processing

    OpenAIRE

    Ponsot, Inès

    2015-01-01

    Thanks to European environmental rules and regulations establishment, waste recycling has become a more and more relevant problematic. For manufacturing plants, especially those producing hazardous wastes, expenses linked to waste production have drastically increased over the last decades. In the proposed work, various hazardous and non-hazardous wastes, among: soda-lime and borosilicate glass cullet, cathode ray tubes glass, exhausted lime from fume abatement systems residues, sludge and sl...

  4. Locale structure around heteroatoms in alumino- and borosilicates for catalysis

    OpenAIRE

    Nagendrachar Garaga, Mounesha

    2013-01-01

    While alumino- and borosilicate materials have paramount importance in catalysis, the molecular origin of their activity is not completely understood. This is mainly because the incorporation of heteroatoms into the silicate framework deteriorates the molecular order by generating local disorder that is particularly difficult to establish. Because of its local vision of ordered and disordered environments, solid-state nuclear magnetic resonance (NMR) can play a key role to solve this long-sta...

  5. Solubility of actinide surrogates in nuclear glasses

    International Nuclear Information System (INIS)

    This paper discusses the results of a study of actinide surrogates in a nuclear borosilicate glass to understand the effect of processing conditions (temperature and oxidizing versus reducing conditions) on the solubility limits of these elements. The incorporation of cerium oxide, hafnium oxide, and neodymium oxide in this borosilicate glass was investigated. Cerium is a possible surrogate for tetravalent and trivalent actinides, hafnium for tetravalent actinides, and neodymium for trivalent actinides. The material homogeneity was studied by optical, scanning electron microscopy. Cerium LIII XANES spectroscopy showed that the Ce3+/Cetotal ratio increased from about 0.5 to 0.9 as the processing temperature increased from 1100 to 1400 deg. C. Cerium LIII XANES spectroscopy also confirmed that the increased Ce solubility in glasses melted under reducing conditions was due to complete reduction of all the cerium in the glass. The most significant results pointed out in the current study are that the solubility limits of the actinide surrogates increases with the processing temperature and that Ce3+ is shown to be more soluble than Ce4+ in this borosilicate glass

  6. Glasses Containing Iron (II, III) Oxides For Immobilization Of Radioactive Technetium

    International Nuclear Information System (INIS)

    Technetium-99 (Tc-99) has posed serious environmental threats as US Department of Energy's high-level waste. This work reports the vitrification of Re, as surrogate for Tc-99, by iron-borosilicate and iron-phosphate glasses, respectively. Iron-phosphate glasses can dissolve Re as high as ∼ 1.2 wt. %, which can become candidate waste forms for Tc-99 disposal, while borosilicate glasses can retain less than 0.1 wt. % of Re due to high melting temperature and long melting duration. Vitrification of Re as Tc-99's mimic was investigated using iron-borosilicate and iron-phosphate glasses. The retention of Re in borosilicate glasses was less than 0.1 wt. % and more than 99 wt. % of Re were volatilized due to high melting temperature and long melting duration. Because the retention of Re in iron-phosphate glasses is as high as 1.2 wt. % and the volatilization is reduced down to ∼50 wt. %, iron-phosphate glasses can be one of the glass waste form candidates for Tc (or Re) disposal. The investigations of chemical durability and leaching test of iron-phosphate glasses containing Re are now underway to test the performance of the waste form.

  7. Effects of neodymium and gadolinium on weathering resistance of ZnO-B2O3-SiO2 glass

    Institute of Scientific and Technical Information of China (English)

    李雄伟; 李梅; 王觅堂; 柳召刚; 胡艳宏; 田俊虎

    2014-01-01

    The ZnO-B2O3-SiO2 glass doped with Nd2O3 and Gd2O3 was prepared by high temperature melt cooling method. The standard sample of the zinc borosilicate glass was placed in the constant temperature and humidity chamber in order to simulate the atmospheric corrosion process. The surface of the weathered glass was analyzed by scanning electron microscope and energy disper-sive spectrometry and the filtrate was analyzed by inductively coupled plasma-atomic emission spectrometry. The results showed that humidity was the most important factor influencing weathering; the morphology of glass surface of altered layer and the product on the surface was observed; the corroding degree of the zinc borosilicate glass doped with Nd or Gd was significantly lighter than that of the base glass.Adding rare earth Nd or Gd in the zinc borosilicate glass could suppress Na, Zn, Si ion release in weathering.

  8. Commercial and Experimental Glass Fibers

    Science.gov (United States)

    Wallenberger, Frederick T.

    Continuous glass fibers can be formed from melts with a wide range of compositions and viscosities. This chapter reviews pure silica fibers which are formed from highly viscous melts, silicate glass fibers with 50-70% SiO2 which are formed from moderately viscous melts, aluminate glass fibers with 50-80% Al2O3, as well as yttria-alumina-garnet (YAG) glass fibers which are formed from inviscid (literally non-viscous) melts. Commercial glass fibers are made for a variety of applications from pure silica rods and from silicate melts containing 50-70% SiO2 and 10-25% Al2O3. Boron-free, essentially boron-free, and borosilicate E-glass are general-purpose fibers. ERC-glass offers high corrosion resistance, HS-glass offers high-strength composites, D-glass offers a low dielectric constant, and A-glass offers the possibility of using waste container glass for less demanding applications.

  9. Contributions of vitreous natural analogs to the investigation of long-term nuclear glass behavior

    International Nuclear Information System (INIS)

    This study assesses the extend of the analogy between the alteration behavior in water and in a moist clay environment of aluminosilicate volcanic glass and alumino-borosilicate nuclear containment glass. Basaltic glass alteration in water initially occurs by hydrolysis processes with an activation energy on the order of 73 kJ.mol-1. As the reaction progresses, the alteration rate drops by over four orders of magnitude from the initial rate r0, The alteration kinetics are not governed by the alteration solution chemistry alone, the glass alteration film appears to have a major role as a diffusion barrier limiting the transfer of reaction species and products. All these aspects highlight the behavioral analogy between basaltic glass and nuclear borosilicate glass in aqueous media. Conversely, the alteration reaction of obsidian-type volcanic glass involves other mechanisms than those governing the dissolution of borosilicate glass. Basaltic glass alteration is also examined in the presence of a clay environmental material, in a study of the natural basaltic glass and argillaceous pelites system of the Salagou basin in southern France, in an approach combining mineralogical, chemical and isotopic data to assess the interactions between a basaltic glass and the argillaceous pelites. Laboratory leach test results with basaltic glass and measured data for the Salagou glass in its natural environment are modeled using a code implementing a kinetic law coupling diffusive transfer of dissolved silica with a reaction affinity law. (author)

  10. Porous glass with high silica content for nuclear waste storage : preparation, characterization and leaching

    International Nuclear Information System (INIS)

    Aqueous solutions simulating radioactive nuclear wastes (like Savanah River Laboratory) were incorporated in porous glass matrix with high silica content prepared by decomposition of borosilicate glass like Na2O - B2O3 - SiO2. After sintering, the samples were submitted, during 28 days, to standard leaching tests MCC1, MCC5 (Soxhlet) and stagnating. The total weight loss, ph, as well as the integral and differential leaching rates and the accumulated concentrations in the leach of Si, Na, B, Ca, Mn, Al, Fe and Ni. The results are compared with the results from reference borosilicate glass, made by fusion, ceramic, synroc, concrets, etc... (E.G.)

  11. High level radioactive waste glass production and product description

    International Nuclear Information System (INIS)

    This report examines borosilicate glass as a means of immobilizing high-level radioactive wastes. Borosilicate glass will encapsulate most of the defense and some of the commercial HLW in the US. The resulting waste forms must meet the requirements of the WA-SRD and the WAPS, which include a short term PCT durability test. The waste form producer must report the composition(s) of the borosilicate waste glass(es) produced but can choose the composition(s) to meet site-specific requirements. Although the waste form composition is the primary determinant of durability, the redox state of the glass; the existence, content, and composition of crystals; and the presence of glass-in-glass phase separation can affect durability. The waste glass should be formulated to avoid phase separation regions. The ultimate result of this effort will be a waste form which is much more stable and potentially less mobile than the liquid high level radioactive waste is currently

  12. DWPF GLASS BEADS AND GLASS FRIT TRANSPORT DEMONSTRATION

    Energy Technology Data Exchange (ETDEWEB)

    Adamson, D; Bradley Pickenheim, B

    2008-11-24

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

  13. Effect of Platelet-Rich Plasma and Bioactive Glass Powder for the Improvement of Rotator Cuff Tendon-to-Bone Healing in a Rabbit Model

    Directory of Open Access Journals (Sweden)

    Yang Wu

    2014-11-01

    Full Text Available To test the hypothesis that a platelet-rich plasma (PRP plus bioactive glass (BG mixture could shorten the tendon-bone healing process in rotator cuff tendon repair, thirty mature male New Zealand white rabbits were randomly divided into three groups, Control, PRP, and PRP + BG. All groups underwent a surgical procedure to establish a rotator cuff tendon healing model. Mechanical examinations and histological assays were taken to verify the adhesion of the tendon-bone. Real-time PCR was adopted to analyze Bone Morphogenetic Protein-2 (BMP-2. The maximum load-to-failure value in mechanical examinations was significantly higher in the PRP + BG group than that in the control group after six weeks (Control 38.73 ± 8.58, PRP 54.49 ± 8.72, PRP + BG 79.15 ± 7.62, p < 0.001, but it was not significantly different at 12 weeks (PRP 74.27 ± 7.74, PRP + BG 82.57 ± 6.63, p = 0.145. In histological assays, H&E (hematoxylin-eosin staining showed that the interface between the tendon-bone integration was much sturdier in the PRP + BG group compared to the other two groups at each time point, and more ordered arranged tendon fibers can be seen at 12 weeks. At six weeks, the mRNA expression levels of BMP-2 in the PRP + BG group were higher than those in the other groups (PRP + BG 0.65 ± 0.11, PRP 2.284 ± 0.07, Control 0.12 ± 0.05, p < 0.05. However, there was no significant difference in the mRNA expression levels of BMP-2 among the three groups at 12 weeks (p = 0.922, 0.067, 0.056. BMP-2 levels in PRP and PRP+BG groups were significantly lower at 12 weeks compared to six weeks (p = 0.006, <0.001.We found that the PRP + BG mixture could enhance tendon-bone healing in rotator cuff tendon repair.

  14. Property Data for Simulated Americium/Curium Glasses

    International Nuclear Information System (INIS)

    The authors studied the properties of mixed lanthanide-alumino-borosilicate glasses. Fifty-five glasses were designed to augment a previous, Phase I, study by systematically varying the composition of Ln2O3 and the concentrations of Ln2O3, SiO2, B2O3, Al2O3, and SrO in glass. These glasses were designed and fabricated at the Savannah River Technology Center and tested at the Pacific Northwest National Laboratory. The properties measured include the high-temperature viscosity (η) as a function of temperature (T) and the liquidus temperature (TL) of Phase II test glasses

  15. Effects of beta/gamma radiation on nuclear waste glasses

    International Nuclear Information System (INIS)

    A key challenge in the disposal of high-level nuclear waste (HLW) in glass waste forms is the development of models of long-term performance based on sound scientific understanding of relevant phenomena. Beta decay of fission products is one source of radiation that can impact the performance of HLW glasses through the interactions of the emitted β-particles and g-rays with the atoms in the glass by ionization processes. Fused silica, alkali silicate glasses, alkali borosilicate glasses, and nuclear waste glasses are all susceptible to radiation effects from ionization. In simple glasses, defects (e.g., non-bridging oxygen and interstitial molecular oxygen) are observed experimentally. In more complex glasses, including nuclear waste glasses, similar defects are expected, and changes in microstructure, such as the formation of bubbles, have been reported. The current state of knowledge regarding the effects of β/γ radiation on the properties and microstructure of nuclear waste glasses are reviewed. (author)

  16. Effects of beta/gamma radiation on nuclear waste glasses

    Energy Technology Data Exchange (ETDEWEB)

    Weber, W.J. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-07-01

    A key challenge in the disposal of high-level nuclear waste (HLW) in glass waste forms is the development of models of long-term performance based on sound scientific understanding of relevant phenomena. Beta decay of fission products is one source of radiation that can impact the performance of HLW glasses through the interactions of the emitted {beta}-particles and g-rays with the atoms in the glass by ionization processes. Fused silica, alkali silicate glasses, alkali borosilicate glasses, and nuclear waste glasses are all susceptible to radiation effects from ionization. In simple glasses, defects (e.g., non-bridging oxygen and interstitial molecular oxygen) are observed experimentally. In more complex glasses, including nuclear waste glasses, similar defects are expected, and changes in microstructure, such as the formation of bubbles, have been reported. The current state of knowledge regarding the effects of {beta}/{gamma} radiation on the properties and microstructure of nuclear waste glasses are reviewed. (author)

  17. Ultraflat-top midinfrared coherent broadband supercontinuum using all normal As2S5-borosilicate hybrid photonic crystal fiber

    Science.gov (United States)

    Ben Salem, Amine; Diouf, Mbaye; Cherif, Rim; Wague, Ahmadou; Zghal, Mourad

    2016-06-01

    We report more than two octave spanning mid-IR flat-top supercontinuum (SC) generation using all normal As2S5-borosilicate hybrid photonic crystal fiber. Our design is based on a chalcogenide As2S5 photonic crystal fiber (PCF), where the first ring composed of six air holes is made by borosilicate glass. By injecting 50-fs pulses with 1.6 nJ energy at 2.5 μm in the all normal dispersion (ANDi) regime, a flat-top broadband SC extending from 1 to 5 μm with high-spectral flatness of 8 dB is obtained in only 4-mm fiber length. To the best of our knowledge, we present the broadest flat mid-IR spectrum generated in the ANDi regime of an optical fiber. The self-phase modulation and the optical wave breaking are identified as the main broadening mechanisms. The obtained broadband light source can be potentially used in the field of spectroscopy and in high-resolution optical coherent tomography owing to the high-spectral SC flatness generated by our designed fiber.

  18. Rhenium volatilization in waste glasses

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Kai; Pierce, David A. [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Hrma, Pavel, E-mail: pavel.hrma@pnnl.gov [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Schweiger, Michael J. [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Kruger, Albert A. [U.S. Department of Energy, Office of River Protection, Richland, WA 99352 (United States)

    2015-09-15

    Highlights: • Re did not volatilize from a HLW feed until 1000 °C. • Re began to volatilize from LAW feeds at ∼600 °C. • The vigorous foaming and generation of gases from salts enhanced Re evaporation in LAW feeds. • The HLW glass with less foaming and salts is a promising medium for Tc immobilization. - Abstract: We investigated volatilization of rhenium (Re), sulfur, cesium, and iodine during the course of conversion of high-level waste melter feed to glass and compared the results for Re volatilization with those in low-activity waste borosilicate glasses. Whereas Re did not volatilize from high-level waste feed heated at 5 K min{sup −1} until 1000 °C, it began to volatilize from low-activity waste borosilicate glass feeds at ∼600 °C, a temperature ∼200 °C below the onset temperature of evaporation from pure KReO{sub 4}. Below 800 °C, perrhenate evaporation in low-activity waste melter feeds was enhanced by vigorous foaming and generation of gases from molten salts as they reacted with the glass-forming constituents. At high temperatures, when the glass-forming phase was consolidated, perrhenates were transported to the top surface of glass melt in bubbles, typically together with sulfates and halides. Based on the results of this study (to be considered preliminary at this stage), the high-level waste glass with less foaming and salts appears a promising medium for technetium immobilization.

  19. Topological Approach for Predicting the Properties of Glasses

    DEFF Research Database (Denmark)

    Smedskjær, Morten Mattrup; Mauro, John C.; Yue, Yuanzheng

    M.F. Thorpe around 1980. By further including the Gupta-Mauro temperature dependence of the constraints, the composition dependence of properties such as hardness and viscosity can be quantitatively predicted for oxide network glasses of industrial interest, such as borates and borosilicates...

  20. Frottement interne des verres de borates et de borosilicates alcalins

    OpenAIRE

    Phalippou, J.; Jabra, R.; Zarzycki, J.

    1980-01-01

    Les spectres de frottement interne des verres de borates alcalins ont été étudiés en fonction de la température. Ces spectres, contrairement à ceux des silicates et phosphates alcalins, ne montrent pas de second maximum (haute température). Il en est de même pour certains borosilicates alcalins. L'étude structurale de ces matériaux et en particulier du type de groupements hydroxyles qui peuvent y être rencontrés, nous incite à penser que le second maximum de frottement interne est dû à la pré...

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

    International Nuclear Information System (INIS)

    In this study, multi-phase silicate-based glass-ceramics were investigated as an alternate waste form for immobilizing non-fissionable products from used nuclear fuel. Currently, borosilicate glass is the waste form selected for immobilization of this waste stream, however, the low thermal stability and solubility of MoO3 in borosilicate glass translates into a maximum waste loading in the range of 15-20 mass%. Glass-ceramics provide the opportunity to target durable crystalline phases, e.g., powellite, oxyapatite, celsian, and pollucite, that will incorporate MoO3 as well as other waste components such as lanthanides, alkalis, and alkaline earths at levels 2X the solubility limits of a single-phase glass. In addition a glass-ceramic could provide higher thermal stability, depending upon the properties of the crystalline and amorphous phases. Glass-ceramics were successfully synthesized at waste loadings of 42, 45, and 50 mass% with the following glass additives: B2O3, Al2O3, CaO and SiO2 by slow cooling form from a glass melt. Glass-ceramics were characterized in terms of phase assemblage, morphology, and thermal stability. The targeted phases: powellite and oxyapatite were observed in all of the compositions along with a lanthanide borosilicate, and cerianite. Results of this initial investigation of glass-ceramics show promise as a potential waste form to replace single-phase borosilicate glass.

  2. 3.3. The kinetics of sulfuric acid decomposition of calcined borosilicate ore

    International Nuclear Information System (INIS)

    Present article is devoted to kinetics of sulfuric acid decomposition of calcined borosilicate ore. The experimental data of kinetics of extraction of boron oxide from calcined borosilicate ore at sulfuric acid decomposition were obtained at 30-95 deg C temperature ranges and process duration from 15 to 60 minutes.

  3. Chapter 3. Sulfuric acid decomposition of borosilicate ores. 3.1. Decomposition of borosilicate ores by sulfuric acid

    International Nuclear Information System (INIS)

    Present article is devoted to decomposition of borosilicate ores by sulfuric acid. The sulfuric acid decomposition of borate ores of Ak-Arkhar Deposit was studied. The possibility of multipurpose utilization of borate ores was shown. The influence of process duration on the rate of oxides (B2O3, Fe2O3 and Al2O3) extraction was studied as well. In order to reach the complete decomposition of oxides from danburite ore the dependence of rate of oxides decomposition on concentration of sulfuric acid was studied. The optimal conditions of sulfuric acid decomposition of danburite ores were proposed.

  4. Glass melter off-gas system pluggages: Cause, significance, and remediation

    International Nuclear Information System (INIS)

    Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass. Experimental glass melters, used to develop the vitrification process, have occasionally experienced problems with pluggage of the off-gas line with solid deposits. The deposits were determined to be mixtures of alkali rich chlorides, sulfates, borates, and fluorides with entrained insoluble particles of Fe2O3 spinel, and frit. The distribution and location of the alkali deposits throughout the off-gas system indicate that the deposits form by vapor-phase transport and condensation. Condensation of the alkali-rich phases cements the entrained particulates causing the off-gas system pluggages. The identification of vapor phase transport as the operational mechanism causing off-gas system pluggages indicates that deposition can be effectively eliminated by increasing the off-gas velocity. The cementitious alkali borates, halides, and sulfates comprising the off-gas line deposits were determined to be water soluble. Thus pluggage can be effectively removed with water and/or steam

  5. Long term corrosion of glasses in salt brines

    OpenAIRE

    Roggendorf, Hans; Schmidt, Helmut K.

    1989-01-01

    Borosilicate glasses are supposed to be a suitable matrix for the fixation of calcined radioactive wastes. For the safety assessment of the disposal of these glasses in geological formations like carnallite or rock salt, their chemical durability in saturated salt brines has been investigated. Temperatures up to 200° C, pressures up to 130 bar, and corrosion times up to 5 years were applied. Special attention was given to the long term corrosion which is mainly characterized by the saturation...

  6. Leaching behavior of glass ceramic nuclear waste forms

    Science.gov (United States)

    Lokken, R. O.

    1981-11-01

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

  7. Silicate Glass Corrosion Mechanism revisited

    Science.gov (United States)

    Geisler, Thorsten; Lenting, Christoph; Dohmen, Lars

    2015-04-01

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

  8. Raman signature modification induced by copper nanoparticles in silicate glass

    OpenAIRE

    Colomban, Philippe; D. Screiber, Henry

    2005-01-01

    Composite materials formed by metal nanoclusters embedded in glasses/glazes have been produced for centuries (Roman hematinum and Renaissance alassonti, Coptic lustre-painted glass and Islamic lustre ceramics). Comparisons were drawn from Raman analyses of alkali borosilicate glasses coloured by copper as “blue” Cu2+ (peak absorption at 750 nm), as “colourless” Cu+, and as “opaque red” Cu0 (peak absorptions at ~420 and 570 nm). In particular, Raman analyses of copper-ruby glasses containing C...

  9. Mechanical Strength and Broadband Transparency Improvement of Glass Wafers via Surface Nanostructures.

    Science.gov (United States)

    Kumar, Amarendra; Kashyap, Kunal; Hou, Max T; Yeh, J Andrew

    2016-01-01

    In this study, we mechanically strengthened a borosilicate glass wafer by doubling its bending strength and simultaneously enhancing its transparency using surface nanostructures for different applications including sensors, displays and panels. A fabrication method that combines dry and wet etching is used for surface nanostructure fabrication. Specifically, we improved the bending strength of plain borosilicate glass by 96% using these surface nanostructures on both sides. Besides bending strength improvement, a limited optical transmittance enhancement of 3% was also observed in the visible light wavelength region (400-800 nm). Both strength and transparency were improved by using surface nanostructures of 500 nm depth on both sides of the borosilicate glass without affecting its bulk properties or the glass manufacturing process. Moreover, we observed comparatively smaller fragments during the breaking of the nanostructured glass, which is indicative of strengthening. The range for the nanostructure depth is defined for different applications with which improvements of the strength and transparency of borosilicate glass substrate are obtained. PMID:27322276

  10. Mechanical Strength and Broadband Transparency Improvement of Glass Wafers via Surface Nanostructures

    Science.gov (United States)

    Kumar, Amarendra; Kashyap, Kunal; Hou, Max T.; Yeh, J. Andrew

    2016-01-01

    In this study, we mechanically strengthened a borosilicate glass wafer by doubling its bending strength and simultaneously enhancing its transparency using surface nanostructures for different applications including sensors, displays and panels. A fabrication method that combines dry and wet etching is used for surface nanostructure fabrication. Specifically, we improved the bending strength of plain borosilicate glass by 96% using these surface nanostructures on both sides. Besides bending strength improvement, a limited optical transmittance enhancement of 3% was also observed in the visible light wavelength region (400–800 nm). Both strength and transparency were improved by using surface nanostructures of 500 nm depth on both sides of the borosilicate glass without affecting its bulk properties or the glass manufacturing process. Moreover, we observed comparatively smaller fragments during the breaking of the nanostructured glass, which is indicative of strengthening. The range for the nanostructure depth is defined for different applications with which improvements of the strength and transparency of borosilicate glass substrate are obtained. PMID:27322276

  11. Synthesis and characterization of acidic mesoporous borosilicate thin films.

    Science.gov (United States)

    Xiu, Tongping; Liu, Qian; Wang, Jiacheng

    2009-02-01

    Work on the synthesis and characterization of acidic wormhole-like ordered mesoporous borosilicate thin films (MBSTFs) on silicon wafers is described in this paper. The MBSTFs coated by the dip-coating method were prepared through an evaporation-induced self-assembly (EISA) process using nonionic block copolymers as structure-directing agents. Fourier transform infrared (FT-IR) spectroscopy confirmed the formation of borosiloxane bonds (Si-O-B). High-resolution transmission electron microscopy (HRTEM) and N2 sorption evidenced a wormhole-like mesoporous structure in the MBSTFs obtained. Scanning electron microscopy (SEM) images of the cross sections and surfaces of the samples showed that MBSTFs on silicon wafers were continuous, homogeneous and did not crack. The acidic properties of the MBSTFs were characterized by FT-IR spectra of chemisorbed pyridine. The MBSTFs thus prepared may find their future applications in many fields including chemical sensors, catalysis, optical coating, molecule separation, etc. PMID:19441565

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

    International Nuclear Information System (INIS)

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

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

    International Nuclear Information System (INIS)

    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

  14. The Silicon-To-Silicon Anodic Bonding Using Sputter Deposited Intermediate Glass Layer

    OpenAIRE

    TIWARI, R; Chandra, S.

    2011-01-01

    Glass-to-silicon anodic bonding is an attractive process for packaging of microelectronics devices and Micro-electro-mechanical Systems (MEMS). Silicon to silicon anodic bonding can also be accomplished by incorporating an intermediate glass layer. In the present work, silicon-to-silicon anodic bonding has been studied with an intermediate borosilicate glass layer deposited by RF magnetron sputtering process. The bonding was carried out at low dc voltage of about 48 V at 400 °C. Surface rough...

  15. UK program: glasses and ceramics for immobilization of radioactive wastes for disposal

    International Nuclear Information System (INIS)

    The UK Research Program on Radioactive Waste Management includes the development of processes for the conversion of high-level-liquid-reprocessing wastes from thermal and fast reactors to borosilicate glasses. The properties of these glasses and their behavior under storage and disposal conditions have been examined. Methods for immobilizing activity from other wastes by conversion to glass or ceramic forms are described. The UK philosophy of final solutions to waste management and disposal is presented

  16. Challenges in commercial manufacture of radiation shielding glasses

    International Nuclear Information System (INIS)

    Radioactive hot-cells employ Radiation Shielding Windows (RSWs), assembled from specialty glasses, developed exclusively for nuclear industry. RSWs serve the twin purpose of direct viewing and shielding protection to the operator and use various types of radiation resistant and optically compatible glasses, such as low-density borosilicate glass; medium-density glass with up to 45% Lead and high-density glass with over 70% lead. Some glasses are Ceria-doped for enhancing their resistance threshold to radiation browning. A clear view of future requirement, capital and environmental costs could be the driving force towards bringing about changes in melting practices, encourage melting development, and enhancing collaboration. With DAE and CGCRI working in tandem, production of the entire range of RSW glasses by an Indian glass industry participant may no longer be a distant dream

  17. Glass packages in interim storage

    International Nuclear Information System (INIS)

    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 % SiO2. 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

  18. Immobilization of Uranium Silicide in Sintered Iron-Phosphate Glass

    International Nuclear Information System (INIS)

    This work is a continuation of a previous one performed in vitrification of uranium silicide in borosilicate and iron-silicate glasses, by sintering.We present the results obtained with an iron-phosphate glass developed at our laboratory and we compare this results with those obtained with the above mentioned glasses. The main objective was to develop a method as simple as possible, so as to get a monolithic glass block with the appropriate properties to be disposed in a deep geological repository.The thermal transformation of the uranium silicide was characterized by DTA/TG analysis and X-ray diffraction.We determined the evolution of the crystalline phases and the change in weight.Calcined uranium silicide was mixed with natural U3O8, the amount of U3O8 was calculated to simulate an isotopic dilution of 4%.This material was mixed with powdered iron-phosphate glass (in wt.%: 64,9 P2O5; 22,7 Fe2O3; 8,1 Al2O3; 4,3 Na2O) in different proportions (in wt%): 7%, 10% y 15%.The powders were pressed and sintered at temperatures between 585 y 670 °C. Samples of the sintered pellet were prepared for the lixiviation tests (MCC-1P: monolithic samples; deionised water; 90° C; 7, 14 and 28 days).The samples showed a quite good durability (0,6 g.m-2.day-1), similar to borosilicate glasses.The microstructure of the glass samples showed that the uranium particles are much better integrated to the glass matrix in the iron-phosphate glasses than in the borosilicate or iron-silicate glasses.We can conclude that the sintered product obtained could be a good alternative for the immobilization of nuclear wastes with high content of uranium, as the ones arising from the conditioning of research reactors spent fuels

  19. Adsorption of uranyl in SiO2 porous glass

    International Nuclear Information System (INIS)

    Vitreous SiO2 porous matrices can be used in many applications involving the uptake of chemical species on its solid surface. In this work, vitreous silica sponges were prepared from a sodium borosilicate glass manufactured in our laboratory. The product obtained was then separated into phases with subsequent leaching of the soluble phase rich in B and Na. The resulting porous matrices have a specific surface of 35 m2/gr. Adsorption of uranyl ions onto the SiO2 porous surface was studied to evaluate the use of this material as a filter for treatment of uranium containing water. The effects of contact time, adsorbent mass and equilibrium concentration of solution were studied. The porous adsorbent exhibits a pseudo-second-order kinetic behavior. The sponges with adsorbed uranium were thermally sealed as a way of U immobilization. Retention of uranium was confirmed during the matrix sealing by TGA. Uranium concentration before and after adsorption tests were made by means of ICP-OES. For uranium concentration of 800 ppm, 72 hours contact time and pH of 3.5, the amount of uranium adsorbed was 21.06 ± 0.02 mg U per gram of vitreous porous SiO2. (author)

  20. 3.6. The kinetics of sulfuric acid decomposition of calcined concentrate of borosilicate ore

    International Nuclear Information System (INIS)

    Present article is devoted to kinetics of sulfuric acid decomposition of calcined concentrate of borosilicate ore. The experimental data of kinetics of extraction of boron oxide from danburite at sulfuric acid decomposition were obtained at 20-90 deg C temperature range and process duration 15-90 minutes. The flowsheet of obtaining of boric acid from borosilicate ores of Ak-Arkhar Deposit by sulfuric acid method was proposed.

  1. 2.2. The kinetics of hydrochloric-acid decomposition of calcined borosilicate ore

    International Nuclear Information System (INIS)

    Present article is devoted to kinetics of hydrochloric-acid decomposition of calcined borosilicate ore. The experimental data of dependence of hydrochloric-acid decomposition of calcined borosilicate ore for boron oxide extraction on temperature (30-95 deg C) and process duration (15-60 min) were considered. It was defined that at temperature increasing the boron oxide extraction increases from 28.9 till 53.2%. The constants of decomposition rate of calcined ore were calculated.

  2. Petrochemistry of coal ash slags. I. Formation of melilite and a high temperature glass from a calcium-rich, silica-deficient slag

    Energy Technology Data Exchange (ETDEWEB)

    Schobert, H.H.; Barbie, D.L.; Christensen, O.D.; Kerner, F.R.

    1977-01-01

    Pilot plant studies are being conducted of a fixed-bed slagging coal gasification process. Lignite from the Indianhead mine is reacted with steam and oxygen in a gasifier at hearth zone temperatures over 1650/sup 0/C. Slag samples were subjected to chemical and petrographic analysis. Layers of layered slag modules were analyzed; the inner layers contain abundant melilite while the outer core is a glass. Results show that the characteristics of the coal ash slag can be affected by temperature fluctuations in the gasifier hearth, and that chemical, flow, and heat transfer behavior are all susceptible to change as a result. 8 figs., 3 tables. (DLC)

  3. Control of high-level radioactive waste-glass melters

    International Nuclear Information System (INIS)

    The Defense Waste Processing Facility (DWPF) will immobilize Savannah River Site High Level Waste as a durable borosilicate glass for permanent disposal in a repository. The DWPF will be controlled based on glass composition. The following discussion is a preliminary analysis of the capability of the laboratory methods that can be used to control the glass composition, and the relationships between glass durability and glass properties important to glass melting. The glass durability and processing properties will be controlled by controlling the chemical composition of the glass. The glass composition will be controlled by control of the melter feed transferred from the Slurry Mix Evaporator (SME) to the Melter Feed Tank (MFT). During cold runs, tests will be conducted to demonstrate the chemical equivalence of glass sampled from the pour stream and glass removed from cooled canisters. In similar tests, the compositions of glass produced from slurries sampled from the SME and MFT will be compared to final product glass to determine the statistical relationships between melter feed and glass product. The total error is the combination of those associated with homogeneity in the SME or MFT, sampling, preparation of samples for analysis, instrument calibration, analysis, and the composition/property model. This study investigated the sensitivity of estimation of property data to the combination of variations from sampling through analysis. In this or a similar manner, the need for routine glass product sampling will be minimized, and glass product characteristics will be assured before the melter feed is committed to the melter

  4. Liquidus temperature and chemical durability of selected glasses to immobilize rare earth oxides waste

    Energy Technology Data Exchange (ETDEWEB)

    Mohd Fadzil, Syazwani Binti; Hrma, Pavel R.; Schweiger, Michael J.; Riley, Brian J.

    2015-06-30

    Pyroprocessing is a reprocessing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl-KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the matrix at high loadings. Crystallization that occurs in waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (TL): the International Simple Glass designed by the International Working Group, sodium borosilicate glass developed by Korea Hydro and Nuclear Power, and the lanthanide aluminoborosilicate (LABS) glass established in the United States. The LABS glass allows the highest waste loadings (over 50 mass% RE2O3) while possessing an acceptable chemical durability.

  5. Defense Waste Processing Facility (DWPF) startup test program: Glass characterization

    International Nuclear Information System (INIS)

    Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass. The glass will be processed in the Defense Waste Processing Facility (DWPF) and poured into stainless steel canisters for eventual geologic disposal. Six simulated glass compositions will be processed in the DWPF during initial startup. The glass in 86 of the first 106 full sized canisters will be sampled and characterized. Extensive glass characterization will determine the following: (1) sampling frequency for radioactive operation, (2) verification of the compositionally dependent process-product models, (3) verification of melter mixing, (4) representativeness of the glass from the canister throat sampler, and (5) homogeneity of the canister glass

  6. Glasses for nuclear waste immobilization

    International Nuclear Information System (INIS)

    Vitrification of nuclear wastes is attractive because of its flexibility, the large number of elements which can be incorporated in the glass, its high corrosion durability and the reduced volume of the resulting waste form. Vitrification is a mature technology and has been used for high level nuclear waste (HLW) immobilisation for more than 40 years in France, Germany and Belgium, Russia, UK, Japan and the USA. Vitrification involves melting of waste materials with glass-forming additives so that the final vitreous product incorporates the waste contaminants in its macro- and micro-structure. Hazardous waste constituents are immobilised either by direct incorporation into the glass structure or by encapsulation when the final glassy material can be in form of a glass composite material (GCM). Both borosilicate and phosphate glasses are currently used to immobilise nuclear wastes, moreover in addition to relatively homogeneous glasses novel GCM are used to immobilise problematic waste streams. The spectrum of wastes which are currently vitrified increases from HLW to low and intermediate wastes (LILW) such as legacy wastes in Hanford, USA and nuclear power plant operational wastes in Russia and Korea. (authors)

  7. Transparent glass coatings incorporated with upconversion nanocrystals by laser cladding method

    International Nuclear Information System (INIS)

    To develop β-NaYF4 as bulk luminescence material, transparent glass coatings incorporated with β-NaYF4:20%Yb3+,2%Er3+ nanocrystals were fabricated by laser cladding method for the first time. The composite films on quartz glasses were characterized by optical microscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM), which showed that β-NaYF4 nanocrystals were introduced into the borosilicate glass and formed to glass composites with highly efficient upconversion (UC) luminescence. It is highly promising to achieve the preparation of crystals-glass composites through this novel method.

  8. RAPID COMMUNICATION: Studies of the magnetostriction of as-prepared and annealed glass-coated Co-rich amorphous microwires by SAMR method

    Science.gov (United States)

    Zhukova, V.; Blanco, J. M.; Zhukov, A.; Gonzalez, J.

    2001-11-01

    The saturation magnetostriction constant, λs, of as-prepared and current annealed glass-covered Co57Fe6.1Ni10B15.9Si11, Co67.5Fe4Ni1.5B14Si12Mo1, Co69.1Fe5.2Ni1B14.8Si9.9 and Co69.5Fe3.9Ni1B12.8Si10.8Mo2 amorphous microwires has been measured by the small angle magnetization rotation method. As-prepared samples exhibit negative λs ranging between -0.9×10-6 and -0.3×10-6. Current annealing results in a significant change of λs, that is, a general tendency to increase towards zero.

  9. Immobilization on nuclear wastes in sintered glasses:

    International Nuclear Information System (INIS)

    As an alternative to fussed glasses, the laboratory worked in the immobilization of high active wastes (HAW) by means of a sintering process. Previous results using this technique with sinthetic borosilicate glasses were highly successful. The work deals with a natural volcanic glass coming from Rio Negro province (Argentine Republic). The sintering behaviour of the raw material and the addition of 10 wt.% of simulated wastes were studied, using two different techniques: 1) Cold pressing and sintering and 2) In-can hot pressing. In addition to macro- and microscopic examinations, leaching behaviour experiments were done in order to evaluate water corrosion resistance of the samples. Comparison with other glasses previously used were made. (Author)

  10. Initial Examination of Low Velocity Sphere Impact of Glass Ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Morrissey, Timothy G [ORNL; Fox, Ethan E [ORNL; Wereszczak, Andrew A [ORNL; Ferber, Mattison K [ORNL

    2012-06-01

    This report summarizes US Army TARDEC sponsored work at Oak Ridge National Laboratory (ORNL) involving low velocity (< 30 m/s or < 65 mph) sphere impact testing of two materials from the lithium aluminosilicate family reinforced with different amounts of ceramic particulate, i.e., glass-ceramic materials, SCHOTT Resistan{trademark}-G1 and SCHOTT Resistan{trademark}-L. Both materials are provided by SCHOTT Glass (Duryea, PA). This work is a follow-up to similar sphere impact studies completed by the authors on PPG's Starphire{reg_sign} soda-lime silicate glass and SCHOTT BOROFLOAT{reg_sign} borosilicate glass. A gas gun or a sphere-drop test setup was used to produce controlled velocity delivery of silicon nitride (Si{sub 3}N{sub 4}) spheres against the glass ceramic tile targets. Minimum impact velocities to initiate fracture in the glass-ceramics were measured and interpreted in context to the kinetic energy of impact and the elastic property mismatch between sphere and target material. Quasistatic spherical indentation was also performed on both glass ceramics and their contact damage responses were compared to those of soda-lime silicate and borosilicate glasses. Lastly, variability of contact damage response was assessed by performing spherical indentation testing across the area of an entire glass ceramic tile. The primary observations from this low velocity (< 30 m/s or < 65 mph) testing were: (1) Resistan{trademark}-L glass ceramic required the highest velocity of sphere impact for damage to initiate. Starphire{reg_sign} soda-lime silicate glass was second best, then Resistan{trademark}-G1 glass ceramic, and then BOROFLOAT{reg_sign} borosilicate glass. (2) Glass-ceramic Resistan{trademark}-L also required the largest force to initiate ring crack from quasi-static indentation. That ranking was followed, in descending order, by Starphire{reg_sign} soda-lime silicate glass, Resistan{trademark}-G1 glass ceramic, and BOROFLOAT{reg_sign} borosilicate glass

  11. Comparison of costs for solidification of high-level radioactive waste solutions: glass monoliths vs metal matrices

    International Nuclear Information System (INIS)

    A comparative economic analysis was made of four solidification processes for liquid high-level radioactive waste. Two processes produced borosilicate glass monoliths and two others produced metal matrix composites of lead and borosilicate glass beads and lead and supercalcine pellets. Within the uncertainties of the cost (1979 dollars) estimates, the cost of the four processes was about the same, with the major cost component being the cost of the primary building structure. Equipment costs and operating and maintenance costs formed only a small portion of the building structure costs for all processes

  12. Graphite fiber reinforced glass matrix composites for aerospace applications

    Science.gov (United States)

    Prewo, K. M.; Bacon, J. F.; Dicus, D. L.

    1979-01-01

    The graphite fiber reinforced glass matrix composite system is described. Although this composite is not yet a mature material, it possesses low density, attractive mechanical properties at elevated temperatures, and good environmental stability. Properties are reported for a borosilicate glass matrix unidirectionally reinforced with 60 volume percent HMS graphite fiber. The flexural strength and fatigue characteristics at room and elevated temperature, resistance to thermal cycling and continuous high temperature oxidation, and thermal expansion characteristics of the composite are reported. The properties of this new composite are compared to those of advanced resin and metal matrix composites showing that graphite fiber reinforced glass matrix composites are attractive for aerospace applications.

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

    International Nuclear Information System (INIS)

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

  14. Mechanisms of dissolution of radioactive waste storage glasses and cesium migration from a granite repository

    International Nuclear Information System (INIS)

    Experimental and theoretical data are used to compare the effect of three possible leach mechanisms for borosilicate glass waste buried in a granite host-rock on the release and subsequent migration of 135Cs. Protracted release episodes and variations of up to an order of magnitude in groundwater transport times and five orders in output concentrations are possible. 4 figures

  15. Effect of different glasses in glass bonded zeolite

    International Nuclear Information System (INIS)

    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

  16. Impact of DC Joule anneal treatment on the high-frequency magnetoimpedance response of Fe-rich FeCo ribbons with varying glass former content

    Science.gov (United States)

    Eggers, Tatiana; Leary, Alex; McHenry, Michael; Skorvanek, Ivan; Srikanth, Hariharan; Phan, Manh-Huong

    The Magnetoimpedance (MI) effect in 2 mm wide (Fe65Co35)83.5- x B13NbxSi2Cu1.5 rapidly quenched ribbons with varying glass former content(x = 0 and x = 4) has been studied in the frequency range of 1-1000 MHz. Two measurement techniques were used: auto-balancing bridge method in the frequency range of 1-110 MHz and transmission line technique for 20-1000 MHz. The impact of DC Joule heating treatments of varying current amplitude and annealing time on the MI effect of the amorphous ribbons was evaluated by examining the field and frequency dependence on the resistive and reactive components of the MI. To interpret the MI behavior, the domain structure of the ribbons in their as-quenched state and after heating treatment was imaged by magneto-optical Kerr effect microscopy. A significant improvement in the MI response from the as-quenched state was found for both compositions of ribbon with a 3 hour-500 mA Joule anneal treatment. The improvement is attributed to the development of a low anisotropy domain structure longitudinally and at an oblique angle between the longitudinal and transverse directions for the 0% and 4% Nb content, respectively.

  17. High-Temperature Viscosity Of Commercial Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Hrma, Pavel R; See, Clem A; Lam, Oanh P; Minister, Kevin B

    2005-01-01

    Viscosity was measured for six types of commercial glasses: low-expansion-borosilicate glasses, E glasses, fiberglass wool glasses, TV panel glasses, container glasses, and float glasses. Viscosity data were obtained with rotating spindle viscometers within the temperature range between 900°C and 1550°C; the viscosity varied from 1 Pa∙s to 750 Pa∙s. Arrhenius coefficients were calculated for individual glasses and linear models were applied to relate them to the mass fractions of 11 major components (SiO2, CaO, Na2O, Al2O3, B2O3, BaO, SrO, K2O, MgO, PbO, and ZrO2) and 12 minor components (Fe2O3, ZnO, Li2O, TiO2, CeO2, F, Sb2O3, Cr2O3, As2O3, MnO2, SO3, and Co3O4). The models are recommended for glasses containing 42 to 84 mass% SiO2 to estimate viscosities or temperatures at a constant viscosity for melts within both the temperature range from 1100°C to 1550°C and viscosity range from 10 to 400 Pas.

  18. Crystallization of a barium-aluminosilicate glass

    Science.gov (United States)

    Drummond, C. H., III; Lee, W. E.; Bansal, N. P.; Hyatt, M. J.

    1989-01-01

    The crystallization of a celsian glass composition was investigated as a possible high-temperature ceramic matrix material. Heat treatments invariably resulted in crystallization of the hexaclesian phase unless a flux, such as lithia, was added or a nucleating agent used (e.g., celsian seeds). TEM analysis revealed complex microstructures. Glasses with Mo additions contained hexacelsian, mullite, and an Mo-rich glass. Li2O additions stabilized celsian but mullite and Mo-rich glass were still present.

  19. Understanding the origin of the fracture toughness evolution of nuclear glasses under irradiation

    International Nuclear Information System (INIS)

    In the nuclear industry, complex borosilicate glasses are used for the confinement of fission products and long-life minor actinides. Under irradiations, the structure and the mechanical properties of these glasses evolve. In this work, atomistic and multi-scale simulations of three simplified borosilicate glasses were run to understand the origin of their fracture behavior change under irradiation. Under the radiation effects, elasticity decreases and plasticity increases. Fracture happens due to the formation and coalescence of nano-cavities. The structural modifications under the radiation effects lead to a delay of the coalescence and of the irradiated glass rupture. Several phenomena overlay to explain this behavior, especially the cavities distribution modifications, the sodium mobility, and the borate and silicate entities organization in the glassy network. Depending on the nature of the more important mechanism, the fracture toughness can increase or decrease under radiation. (author)

  20. SON68 glass dissolution driven by magnesium silicate precipitation

    International Nuclear Information System (INIS)

    Experimental results are reported on the effect of magnesium silicate precipitation on the mechanisms and rate of borosilicate glass dissolution. Leaching experiments with SON68 glass, a borosilicate containing no Mg, were carried out in initially deionized water at 50 °C with a glass-surface-area-to-solution-volume ratio of 20,000 m−1. After 29 days of alteration the experimental conditions were modified by the addition of Mg to trigger the precipitation of Mg-silicate. Additional experiments were conducted to investigate the importance of other parameters such as pH or dissolved silica on the mechanisms of precipitation of Mg-silicates and their consequences on the glass dissolution rate. Mg-silicates precipitate immediately after Mg is added. The amount of altered glass increases with the quantity of added Mg, and is smaller when silicon is added in solution. A time lag is observed between the addition of magnesium and the resumption of glass alteration because silicon is first provided by partial dissolution of the previously formed alteration gel. It is shown that nucleation does not limit Mg-silicate precipitation. A pH above 8 is necessary for the phase to precipitate under the investigated experimental conditions. On the other hand the glass alteration kinetics limits the precipitation if the magnesium is supplied in solution at a non-limiting rate

  1. Decontamination of DWPF canisters by glass frit blasting

    International Nuclear Information System (INIS)

    High-level radioactive waste at the Savannah River Plant will be incorporated in borosilicate glass for permanent disposal. The waste glass will be encapsulated in a 304L stainless steel canister. During the filling operation the outside of the canister will become contaminated. This contamination must be reduced to an accepable level before the canister leaves the Defense Waste Processing Facility (DWPF). Tests with contaminated coupons have demonstrated that this decontamination can be accomplished by blasting the surface with glass frit. The contaminated glass frit byproduct of this operation is used as a feedstock for the waste glass process, so no secondary waste is created. Three blasting techniques, using glass frit as the blasting medium, were evaluated. Air-injected slurry blasting was the most promising and was chosen for further development. The optimum parametric values for this process were determined in tests using coupon weight loss as the output parameter. 1 reference, 13 figures, 3 tables

  2. Brine chemistry effects on the durability of a simulated nuclear waste glass

    International Nuclear Information System (INIS)

    The effects of various solution chemistry parameters on the alteration and leaching characteristics of a copper borosilicate simulated waste glass have been determined under hydrothermal conditions. Results are presented which demonstrate that leachant salinity, volume/glass surface area ratio, pH, cation content, and dissolved SiO2 concentration effects are important. A brief explanation of these results is given which is based on ion exchange and solution saturation equilibria

  3. Femtosecond laser direct written diffractive optical elements and their integration in oxide glass

    Science.gov (United States)

    Choi, Jiyeon; Richardson, Martin

    2009-02-01

    Femtosecond laser direct writing was applied to fabricate 3D diffractive optical elements in oxide glass. Here we report our initial results. We describe the consequences of fabricating Fresnel Zone Plates (FZPs) with various femtosecond laser parameters. Single or multiple layers of laser written FZPs were produced in borosilicate glasses. We are investigating the diffraction efficiencies as a function of laser and writing parameters such as pulse energy, writing speed and repetition rate.

  4. Conversion of ion-exchange resins, catalysts and sludges to glass with optional noble metal recovery using the GMODS process

    International Nuclear Information System (INIS)

    Chemical processing and cleanup of waste streams (air and water) typically result in products, clean air, clean water, and concentrated hazardous residues (ion exchange resins, catalysts, sludges, etc.). Typically, these streams contain significant quantities of complex organics. For disposal, it is desirable to destroy the organics and immobilize any heavy metals or radioactive components into stable waste forms. If there are noble metals in the residues, it is desirable to recover these for reuse. The Glass Material Oxidation and Dissolution System (GMODS) is a new process that directly converts radioactive and hazardous chemical wastes to borosilicate glass. GMODS oxidizes organics with the residue converted to glass; converts metals, ceramics, and amorphous solids to glass; converts halides (eg chlorides) to borosilicate glass and a secondary sodium halide stream; and recovers noble metals. GMODS has been demonstrated on a small laboratory scale (hundreds of grams), and the equipment needed for larger masses has been identified

  5. Glass: a candidate engineered material for management of high level nuclear waste

    International Nuclear Information System (INIS)

    While the commercial importance of glass is generally recognized, a few people are aware of extremely wide range of glass formulations that can be made and of the versatility of this engineered material. Some of the recent developments in the field of glass leading to various technological applications include glass fiber reinforcement of cement to give new building materials, substrates for microelectronics circuitry in form of semiconducting glasses, nuclear waste immobilization and specific medical applications. The present paper covers fundamental understanding of glass structure and its application for immobilization of high level radioactive liquid waste. High level radioactive liquid waste (HLW) arising during reprocessing of spent fuel are immobilized in sodium borosilicate glass matrix developed indigenously. Glass compositions are modified according to the composition of HLW to meet the criteria of desirable properties in terms. These glass matrices have been characterized for different properties like homogeneity, chemical durability, thermal stability and radiation stability. (author)

  6. Contributions of vitreous natural analogs to the investigation of long-term nuclear glass behavior; Apports des analogues naturels vitreux a la validation des codes de prediction du comportement a long terme des verres nucleaires

    Energy Technology Data Exchange (ETDEWEB)

    Techer, I

    1999-07-01

    This study assesses the extend of the analogy between the alteration behavior in water and in a moist clay environment of aluminosilicate volcanic glass and alumino-borosilicate nuclear containment glass. Basaltic glass alteration in water initially occurs by hydrolysis processes with an activation energy on the order of 73 kJ.mol{sup -1}. As the reaction progresses, the alteration rate drops by over four orders of magnitude from the initial rate r{sub 0}, The alteration kinetics are not governed by the alteration solution chemistry alone, the glass alteration film appears to have a major role as a diffusion barrier limiting the transfer of reaction species and products. All these aspects highlight the behavioral analogy between basaltic glass and nuclear borosilicate glass in aqueous media. Conversely, the alteration reaction of obsidian-type volcanic glass involves other mechanisms than those governing the dissolution of borosilicate glass. Basaltic glass alteration is also examined in the presence of a clay environmental material, in a study of the natural basaltic glass and argillaceous pelites system of the Salagou basin in southern France, in an approach combining mineralogical, chemical and isotopic data to assess the interactions between a basaltic glass and the argillaceous pelites. Laboratory leach test results with basaltic glass and measured data for the Salagou glass in its natural environment are modeled using a code implementing a kinetic law coupling diffusive transfer of dissolved silica with a reaction affinity law. (author)

  7. Survey of glass plutonium contents and poison selection

    Energy Technology Data Exchange (ETDEWEB)

    Plodinec, M.J.; Ramsey, W.G. [Westinghouse Savannah River Company, Aiken, SC (United States); Ellison, A.J.G.; Shaw, H. [Lawrence Livermore National Laboratory, CA (United States)

    1996-05-01

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

  8. Aluminum elution and precipitation in glass vials: effect of pH and buffer species.

    Science.gov (United States)

    Ogawa, Toru; Miyajima, Makoto; Wakiyama, Naoki; Terada, Katsuhide

    2015-02-01

    Inorganic extractables from glass vials may cause particle formation in the drug solution. In this study, the ability of eluting Al ion from borosilicate glass vials, and tendencies of precipitation containing Al were investigated using various pHs of phosphate, citrate, acetate and histidine buffer. Through heating, all of the buffers showed that Si and Al were eluted from glass vials in ratios almost the same as the composition of borosilicate glass, and the amounts of Al and Si from various buffer solutions at pH 7 were in the following order: citrate > phosphate > acetate > histidine. In addition, during storage after heating, the Al concentration at certain pHs of phosphate and acetate buffer solution decreased, suggesting the formation of particles containing Al. In citrate buffer, Al did not decrease in spite of the high elution amount. Considering that the solubility profile of aluminum oxide and the Al eluting profile of borosilicate glass were different, it is speculated that Al ion may be forced to leach into the buffer solution according to Si elution on the surface of glass vials. When Al ions were added to the buffer solutions, phosphate, acetate and histidine buffer showed a decrease of Al concentration during storage at a neutral range of pHs, indicating the formation of particles containing Al. In conclusion, it is suggested that phosphate buffer solution has higher possibility of forming particles containing Al than other buffer solutions. PMID:24261406

  9. Natural analogue study of volcanic glass

    International Nuclear Information System (INIS)

    A considerable range in alteration rates of basaltic glasses in various environments has been reported in previous studies. However, these studies paid only cursory attention to the environmental conditions under which the glass had been altered. In this study, the alteration of basaltic glasses was investigated and the environmental conditions and the alteration rate were discussed. Two sample ages were represented: 280 years and 2800 years. Basaltic glasses and their alteration layers were analyzed by electron probe microanalyzer (EMPA) and the thickness of the alteration layers were measured by scanning electron microscope (SEM). The ground water collected near the sampling point of Zunazawa Scoria (2800 years) and the pore water of both samples were analyzed. The alteration temperature and flow rate of water are estimated to be about 13degC and 0.2 l/cm2/y respectively on the basis of meteorological data. The alteration layers of young aged basaltic glasses in freshwater conditions are similar to those of leached borosilicate glasses. The alteration rates of these basaltic glasses are estimated to be several μm/1000y. The elemental concentrations in the ground water can be roughly explained as the result of leaching of the glasses. (author)

  10. Basaltic glass: alteration mechanisms and analogy with nuclear waste glasses

    International Nuclear Information System (INIS)

    A synthetic basaltic glass was dissolved experimentally at 90 deg. C under static conditions in initially pure water. The basaltic glass dissolution rates measured near and far from equilibrium were compared with those of SON 68 nuclear waste glass. Experimental and literature data notably suggested that the alteration mechanisms for the two glasses are initially similar. Under steady-state concentration conditions, the alteration rate decreased of four orders of magnitude below the initial rate (r0). The same alteration rate decrease was observed for basaltic and nuclear glass. These findings tend to corroborate the analogy of the two glasses alteration kinetics. The effect of dissolved silica in solution, observed through dynamic leach tests with silicon-rich solutions, cannot account for the significant drop in the basaltic glass kinetics. Hence, a protective effect of the glass alteration film was assumed and experimentally investigated. Moreover, modeling with LIXIVER argue for a significant effect of diffusion in the alteration gel

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

    Energy Technology Data Exchange (ETDEWEB)

    Vojtech, O.; Sussmilch, J.; Urbanec, Z. [and others

    1996-02-01

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

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

    International Nuclear Information System (INIS)

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

  13. Iron Phosphate Glass Development and Demonstration (AJHM and CCIM)

    International Nuclear Information System (INIS)

    Iron phosphate glasses retain high concentrations of some waste components that are difficult to dissolve into borosilicate melts - Sulfates, phosphates, heavy metals (Cr, Bi, Mo) and halides (F, Cl). This translates into significant increases in waste loading (WL) or reduced canister counts for specific waste streams. Programmatic objectives are: (1) Develop phosphate glass systems at high waste loadings for Hanford LAW and other DOE HLWs (Hanford and INL); (2) Develop and demonstrate a process flowsheet for implementation of phosphate based glasses in melters (JHM or AJHM) similar to those currently employed at Hanford - Determine if an alternative melter (e.g., CCIM) could be used; (3) Determine potential benefits and costs for implementation of iron phosphate glasses into WTP; and (4) Begin the effort to qualify LAW-based iron phosphate glasses for disposal on site at Hanford. FY10 activities primarily focused on developing iron phosphate glasses for Hanford LAW immobilization. Iron phosphate glasses have been shown to retain high concentrations of some waste components that are difficult to dissolve into borosilicate melts - Sulfates, phosphates, heavy metals (Cr, Bi, Mo) and halides (F, Cl). FeP glasses may offer significant increases in waste loading (reduced canister counts) for specific waste streams. EM-31 FeP Team has developed an integrated program to assess the impact of implementing the FeP glass system on Hanford LAW/HLW vitrification facilities: (a) Glass formulation and optimization → high WLs for various waste streams, Hanford AZ-102 LAW primary focus of FY10; (b) Systems analysis → glass volumes or mass; (c) WTP flowsheet impacts → storage and transport issues; and (d) Long-term performance → support PA.

  14. Simulation of Self-Irradiation of High-Sodium Content Nuclear Waste Glasses

    International Nuclear Information System (INIS)

    Alkali-borosilicate glasses are widely used in nuclear industry as a matrix for immobilisation of hazardous radioactive wastes. Durability or corrosion resistance of these glasses is one of key parameters in waste storage and disposal safety. It is influenced by many factors such as composition of glass and surrounding media, temperature, time and so on. As these glasses contain radioactive elements most of their properties including corrosion resistance are also impacted by self-irradiation. The effect of external gamma-irradiation on the short-term (up to 27 days) dissolution of waste borosilicate glasses at moderate temperatures (30 deg. to 60 deg. C) was studied. The glasses studied were Magnox Waste glass used for immobilisation of HLW in UK, and K-26 glass used in Russia for ILW immobilisation. Glass samples were irradiated under γ-source (Co-60) up to doses 1 and 11 MGy. Normalised rates of elemental release and activation energy of release were measured for Na, Li, Ca, Mg, B, Si and Mo before and after irradiation. Irradiation up to 1 MGy results in increase of leaching rate of almost all elements from both MW and K-26 with the exception of Na release from MW glass. Further irradiation up to a dose of 11 MGy leads to the decrease of elemental release rates to nearly initial value. Another effect of irradiation is increase of activation energies of elemental release. (authors)

  15. Evolution of mechanical properties of silicate glasses: Impact of the chemical composition and effects of irradiation

    International Nuclear Information System (INIS)

    This thesis examines: (1) how the chemical composition changes the hardness, toughness, and stress corrosion cracking behavior in model pristine and (2) how external irradiation impact these properties. It is to be incorporated in the context of the storage of nuclear waste in borosilicate glass matrix, the structural integrity of which should be assessed. Eight simplified borosilicate glasses made of 3 oxides with modulated proportions (SiO2-B2O3-Na2O (SBN) have been selected and their hardness, toughness, and stress corrosion cracking behavior have been characterized prior and after irradiation. The comparative study of the non-irradiated SBN glasses provides the role played by the chemical composition. The sodium content is found to be the key parameter: As it increases, the glass plasticity increases, leading to changes in the mechanical response to strain. Hardness (Hv) and toughness (Kc) decrease since the flow under indenter increases. The analysis of the stress corrosion behavior evidences a clear shift of the SCC curves linked also to the glass plasticity. Four of the 8 simplified SBN glass systems highlight the influence of electron, light and heavy ions irradiations on the mechanical properties. Once again, the sodium content is a key parameter. It is found to inhibit the glass modification: Glasses with high sodium content are more stable. Ions irradiations highlight the predominant role of nuclear interaction in changing the glass properties. Finally, electronic interaction induced by helium and electron irradiation does not lead to the same structural/mechanical glasses variations. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-04-01

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

  17. Estimation of FPs solubility in glass melt states by method of multi-phase chemical equilibrium calculation

    International Nuclear Information System (INIS)

    In order to study the segregation or phase-separation of fission products in alkaline borosilicate glasses, the experiments for MoO3 and RuO2 have been done. In this paper, the primary theoretical approach to the inhomogeneity has been attempted, based on multi-phase equilibrium theory

  18. Formation of alteration products during dissolution of vitrified ILW in a high-pH calcium-rich solution

    International Nuclear Information System (INIS)

    To simulate the possible disposition of a vitrified intermediate-level waste (ILW) in a cementitious environment within a geological disposal facility (GDF), the durability of a laboratory simulant ILW vitrified in a borosilicate glass in a saturated Ca(OH)2 solution (pH ∼12.5) was measured. Both a low surface area to volume (SA/V) ratio (∼10 m−1) Materials Characterisation Center test 1 (MCC-1) and a high SA/V ratio (∼10,000 m−1) product consistency test type B (PCT-B) were used at 50 °C for up to 170 days. The formation of alteration layers and products was followed. The surfaces of the monoliths were analysed using SEM/EDX and showed the formation of magnesium-rich precipitates and distinct calcium silicate hydrate (CSH) precipitates. Cross sections showed the development of a calcium-rich alteration layer, which was observed from 14 days. The altered layer was up to 5 μm thick after 170 days and showed accumulation of zirconium, iron and magnesium and to a lesser extent aluminium, along with calcium and silicon. Based on comparison of the rate data, it is suggested that the presence of this layer may offer some protection to the underlying glass. However, the high SA/V ratio experiments showed resumed alteration after 56 days, indicating that the altered layer may not be protective in the long term (under accelerated conditions). The formation of a magnesium-containing smectite clay (likely saponite) in addition to CSH(II), a jennite-like CSH phase, were identified in the high SA/V experiment by X-ray diffraction after 170 days. These results suggest that calcium and magnesium have important roles in both the long and shorter-term durability of vitrified wastes exposed to high pH

  19. Atomic layer deposition of alternative glass microchannel plates

    International Nuclear Information System (INIS)

    The technique of atomic layer deposition (ALD) has enabled the development of alternative glass microchannel plates (MCPs) with independently tunable resistive and emissive layers, resulting in excellent thickness uniformity across the large area (20 × 20 cm), high aspect ratio (60:1 L/d) glass substrates. Furthermore, the use of ALD to deposit functional layers allows the optimal substrate material to be selected, such as borosilicate glass, which has many benefits compared to the lead-oxide glass used in conventional MCPs, including increased stability and lifetime, low background noise, mechanical robustness, and larger area (at present up to 400 cm2). Resistively stable, high gain MCPs are demonstrated due to the deposition of uniform ALD resistive and emissive layers on alternative glass microcapillary substrates. The MCP performance characteristics reported include increased stability and lifetime, low background noise (0.04 events cm−2 s−1), and low gain variation (±5%)

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

    International Nuclear Information System (INIS)

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

  1. Investigation of crystallization in glasses containing fission products

    International Nuclear Information System (INIS)

    Five potential solidification products for high-level waste (four borosilicate glasses and one celsian glass ceramic) have been investigated in terms of crystallization. In all glasses and in the glass ceramic, crystallization, and recrystallization, respectively, were observed by heating above 7730K, however, at very different periods of time (0.1d greater than or equal to 100d). The noble metals precipitated into various phases. Crystal growth proceeded at the phase boundary glass-noble metal. In all products rare earth phases crystallized. Silicate phases rarely formed. The leach resistance (by the grain titration and Soxhlet tests) decreased after heat treatment in all cases. The changes were found to be within one order of magnitude for all products. 2 figures, 4 tables

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

    Science.gov (United States)

    Wang, Fu; Liao, Qilong; Dai, Yunya; Zhu, Hanzhen

    2016-08-01

    Immobilization of gadolinium (Gd), a nonradioactive surrogate for Pu3+, in iron borophosphate glasses/glass-ceramics (IBP glasses/glass-ceramics) has been investigated. The IBP glass containing 4 mol% Gd2O3 is homogeneously amorphous. At higher Gd2O3 concentrations, additional Gd is retained in the glasses as crystalline inclusions of monazite GdPO4 crystalline phase detected with X-ray diffraction. Moreover, Gd2O3 addition increases the Tg of the IBP glasses in glass formation range, which is consistent with the structural modification of the glasses. The structure of the Gd2O3-loaded IBP glasses/glass-ceramics is mainly based on pyrophosphate units. The chemical durability of Gd2O3-loaded IBP glasses/glass-ceramics is comparable to widely used borosilicate glass waste forms and the existence of monazite GdPO4 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 Pu3+ if the formed crystalline phase(s) have high chemical durability.

  3. Sulphate solubility and sulphate diffusion in oxide glasses: implications for the containment of sulphate-bearing nuclear wastes

    International Nuclear Information System (INIS)

    The thesis deals with sulphate solubility and sulphate diffusion in oxide glasses, in order to control sulphate incorporation and sulphate volatilization in nuclear waste glasses. It was conducted on simplified compositions, in the SiO2-B2O3-R2O (R = Li, Na, K, Cs), SiO2-B2O3-BaO and V2O5-B2O3-BaO systems. These compositions allowed us to study the influence of the nature of network-modifying ions (Li+, Na+, K+, Cs+ or Ba2+) and also of former elements (Si, B, V), on structure and properties of glasses. Sulphate volatility is studied in sodium borosilicate melts using an innovative technique of sulphate quantitation with Raman spectroscopy. This technique is useful to obtain kinetic curves of sulphate volatilization. The establishment of a model to fit these curves leads to the determination of diffusion coefficients of sulphate. These diffusion coefficients can thus be compared to diffusion coefficients of other species, determined by other techniques and presented in the literature. They are also linked to diffusion coefficients in relation with the viscosity of the melts. Concerning sulphate solubility in glasses, it depends on glass composition and on the nature of sulphate incorporated. Sulphate incorporation in alkali borosilicate glasses leads to the formation of a sulphate layer floating on top of the melt. Sulphate incorporation in barium borosilicate and boro-vanadate glasses leads to the crystallization of sulphate species inside the vitreous matrix. Moreover, sulphate solubility is higher in these glasses than in alkali borosilicates. Finally, exchanges between cations present in glasses and cations present in the sulphate phase are also studied. (author)

  4. Crystallization study of a glass used for fission product storage

    International Nuclear Information System (INIS)

    The vitreous matrix used in France is a borosilicate glass of low melting point allowing introduction of volatil fission products and of good chemical stability. However, like any glass, if storage temperature is higher than transformation temperature a partial crystallization can occur. Before final storage, it is important to determine of leaching by water eventually occuring on the choosen site is modified by crystalline phases. The aim of this study is the determination of the leaching rate and the identification of crystalline phases formed during thermal treatment and evaluation of its volumic fraction

  5. Ion implantation induced microstructural damage in a nuclear waste glass

    International Nuclear Information System (INIS)

    Borosilicate glasses are presently the matrix accepted worldwide to solidify high-level radioactive waste from reprocessing fuel elements of nuclear power stations. The glass will experience radiation damage from alpha particles and their associated alpha-recoil atoms, from beta particles (electrons) and from gamma rays. From the viewpoint of the wasteform stability, the most serious radiation effects are expected to be phase separation, pore and/or bubble formation and micro fracturing. These types of microstructural damage may significantly increase the leachability of the primary waste-storage material. (authors). 3 figs., 7 refs

  6. Critical review of glass performance modeling

    International Nuclear Information System (INIS)

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

  7. Fractionnement chimique au sein d'une vitrocéramique borosilicate enrichie en molybdène et comportement sous irradiation de powellite monocristalline

    OpenAIRE

    Wang, Xiaochun

    2013-01-01

    Ce travail porte sur le fractionnement des produits de fission et les actinides mineurs (simulées par des terres rares) dans une vitrocéramique borosilicate riche en molybdène contenant des cristallites de powellite (CaMoO4) étudié par techniques d'analyse élémentaire (LIBS, LA-ICP-MS, et l'EMPA). Il a été montré que des terres rares et Sr (émetteur bêta) sont incorporés préférentiellement dans la phase powellite, tandis que Al, Fe, Zr, Zn et Cs (sources bêta-decay) restent dans le verre. Le ...

  8. Characterization of projected DWPF glasses heat treated to simulate canister centerline cooling

    International Nuclear Information System (INIS)

    Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass. The glass will be produced and poured into stainless steel canisters in the Defense Waste Processing Facility (DWPF). Eventually these canistered waste forms will be sent to a geologic repository for final disposal. In order to assure acceptability by the repository, the Department of Energy has defined requirements which DWPF canistered waste forms must meet. These requirements are the Waste Acceptance Product Specifications (WAPS). The WAPS require DWPF to identify the crystalline phases expected to be present in the final glass product. Knowledge of the thermal history of the borosilicate glass during filling and cooldown of the canister is necessary to determine the amount and type of crystalline phases present in the final glass product. Glass samples of seven projected DWPF compositions were cooled following the same temperature profile as that of glass at the centerline of the full scale DWPF canister. The glasses were characterized by X-ray diffraction and scanning electron microscopy to identify the crystalline phases present. The volume percents of each crystalline phase present were determined by quantitative x-ray diffraction. The Product Consistency Test (PCT) was used to determine the durability of the heat treated glasses

  9. Nanoscale topographic changes on sterilized glass surfaces affect cell adhesion and spreading.

    Science.gov (United States)

    Wittenburg, Gretel; Lauer, Günter; Oswald, Steffen; Labudde, Dirk; Franz, Clemens M

    2014-08-01

    Producing sterile glass surfaces is of great importance for a wide range of laboratory and medical applications, including in vitro cell culture and tissue engineering. However, sterilization may change the surface properties of glass and thereby affect its use for medical applications, for instance as a substrate for culturing cells. To investigate potential effects of sterilization on glass surface topography, borosilicate glass coverslips were left untreated or subjected to several common sterilization procedures, including low-temperature plasma gas, gamma irradiation and steam. Imaging by atomic force microscopy demonstrated that the surface of untreated borosilicate coverslips features a complex landscape of microislands ranging from 1000 to 3000 nm in diameter and 1 to 3 nm in height. Steam treatment completely removes these microislands, producing a nanosmooth glass surface. In contrast, plasma treatment partially degrades the microisland structure, while gamma irradiation has no effect on microisland topography. To test for possible effects of the nanotopographic structures on cell adhesion, human gingival fibroblasts were seeded on untreated or sterilized glass surfaces. Analyzing fibroblast adhesion 3, 6, and 24 h after cell seeding revealed significant differences in cell attachment and spreading depending on the sterilization method applied. Furthermore, single-cell force spectroscopy revealed a connection between the nanotopographic landscape of glass and the formation of cellular adhesion forces, indicating that fibroblasts generally adhere weakly to nanosmooth but strongly to nanorough glass surfaces. Nanotopographic changes induced by different sterilization methods may therefore need to be considered when preparing sterile glass surfaces for cell culture or biomedical applications. PMID:24027204

  10. DEVELOPMENT OF GLASS MATRICES FOR HLW RADIOACTIVE WASTES

    Energy Technology Data Exchange (ETDEWEB)

    Jantzen, C.

    2010-03-18

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

  11. Glass Composite Materials for Nuclear Waste Immobilisation

    International Nuclear Information System (INIS)

    Glass composite materials (GCM) are discussed as flexible waste forms for immobilising various types of wastes. Compared to homogeneous glassy materials, GCMs can incorporate larger amounts of toxic elements. GCMs can be produced at higher capacity and lower processing temperatures. In this work, simulated spent clinoptilolite was immobilised in a monolithic glass composite wasteform (GCM) produced by a pressureless sintering for 2 hours at relative low temperatures 750 degree C. The GCM utilises the high durability of alkali borosilicate glass to encapsulate the Cs-impregnated clinoptilolite (Cs-Clino). With this approach mobile radionuclides are retained by a multi-barrier system, comprising the crystalline form of the clinoptilolite and the borosilicate glass wastes loading ranging from 1:1 up to 1:10 glass to Cs-clino volume ratios corresponding to 37-88 mass % were studied. Water durability of GCM was assessed in 7 days leaching tests in deionised water at 40 degree C based on ASTM C1220-98 standard. It was found that the normalised leaching rates of Cs remain below 6.35 x 10-6g/cm2day in a GCM with 73 mass % waste during a leaching test for 7 days. However at higher waste loading of 80 mass % the normalised leaching rate of Cs was as high as 9.06 10-4g/cm2day. This drastic change can be explained by formation of clusters made of inter-connected clinoptilolite particle leading to percolation threshold phenomena. (Author)

  12. Glass composite materials for nuclear waste immobilisation

    International Nuclear Information System (INIS)

    Glass composite materials (GCM) are discussed as flexible waste forms for immobilising various types of wastes. Compared to homogeneous glassy materials, GCMs can incorporate larger amounts of toxic elements. GCMs can be produced at higher capacity and lower processing temperatures. In this work, simulated spent clinoptilolite was immobilised in a monolithic glass composite wasteform (GCM) produced by a pressureless sintering for 2 hours at relative low temperatures 750 degree Celsius. The GCM utilises the high durability of alkali borosilicate glass to encapsulate the Cs-impregnated clinoptilolite (Cs-Clino). With this approach mobile radionuclides are retained by a multi-barrier system, comprising the crystalline form of the clinoptilolite and the borosilicate glass. Wastes loading ranging from 1:1 up to 1:10 glass to Cs-clino volume ratios corresponding to 37-88 mass % were studied. Water durability of GCM was assessed in 7 days leaching tests in deionised water at 40 degree Celsius based on ASTM C1220-98 standard. It was found that the normalised leaching rates of Cs remain below 6.35 x 10-6g/ cm2 day in a GCM with 73 mass % waste during a leaching test for 7 days. However, at higher waste loading of ≥80 mass % the normalised leaching rate of Cs was as high as 9.06 x 10-4 g/ cm2 day. This drastic change can be explained by formation of clusters made of inter-connected clinoptilolite particle leading to percolation threshold phenomena. (author)

  13. 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.

  14. Reaction of Inconel 690 and 693 in Iron Phosphate Melts: Alternative Glasses for Waste Vitrification

    International Nuclear Information System (INIS)

    The corrosion resistance of candidate materials used for the electrodes (Inconel 690 and 693) and the melt contact refractory (Monofrax K-3) in a Joule Heated Melter (JHM) has been investigated at the University of Missouri-Rolla (UMR) during the period from June 1, 2004 to August 31, 2005. This work was supported by the U.S. Department of Energy (DOE) Office of Biological and Environmental Research (DE-FG02-04ER63831). The unusual properties and characteristics of iron phosphate glasses, as viewed from the standpoint of alternative glasses for vitrifying nuclear and hazardous wastes which contain components that make them poorly suited for vitrification in borosilicate glass, were recently discovered at UMR. The expanding national and international interest in iron phosphate glasses for waste vitrification stems from their rapid melting and chemical homogenization which results in higher furnace output, their high waste loading that varies from 32 wt% up to 75 wt% for the Hanford LAW and HLW, respectively, and the outstanding chemical durability of the iron phosphate wasteforms which meets all present DOE requirements (PCT and VHT). The higher waste loading in iron phosphate glasses, compared to the baseline borosilicate glass, can reduce the time and cost of vitrification considerably since a much smaller mass of glass will be produced, for example, about 43% less glass when the LAW at Hanford is vitrified in an iron phosphate glass according to PNNL estimates. In view of the promising performance of iron phosphate glasses, information is needed for how to best melt these glasses on the scale needed for practical use. Melting iron phosphate glasses in a JHM is considered the preferred method at this time because its design could be nearly identical to the JHM now used to melt borosilicate glasses at the Defense Waste Processing Facility (DWPF), Westinghouse Savannah River Co. Therefore, it is important to have information for the corrosion of candidate electrode

  15. 3.4. Sulfuric acid decomposition of borosilicate ores (concentrate) of Ak-Arkhar Deposit of Tajikistan

    International Nuclear Information System (INIS)

    Present article is devoted to sulfuric acid decomposition of borosilicate ores (concentrate) of Ak-Arkhar Deposit of Tajikistan. The reaction of borosilicate ores decomposition by sulfuric acid was studied at 20-120 deg C temperature ranges at concentration of H2SO4 from 45 to 50 mass %. It was defined that at temperature increasing the extraction rate of oxides increases: B2O3 - 30.02% and Fe2O3 - 50.58%. The dependence of extraction rate of components from borosilicate ores (concentrate) at sulfuric acid decomposition on temperature, process duration, sulfuric acid concentration was studied as well. The optimal conditions of sulfuric acid decomposition of borosilicate ores (concentrate) were proposed.

  16. SEM/EDS analysis of boron in waste glasses with ultrathin window detector and digital pulse processor

    International Nuclear Information System (INIS)

    Analysis of boron in waste glasses and in the reaction products that form during the reaction of glass is important for understanding the reaction kinetics and mechanism of glass corrosion. Two borosilicate waste glasses (1.55 and 3.47 wt% B) have been analyzed by SEM/EDS. The 1.55 wt% is the lowest B concentration detected with EDS. However, the B peaks severely overlap with the C peaks due to the carbon films used for conductive layers, but this problem can be solved by subtracting the C peaks, and possibly even lower B content could be detected by EDS with the digital pulse processor

  17. Glass sealing

    Energy Technology Data Exchange (ETDEWEB)

    Brow, R.K.; Kovacic, L.; Chambers, R.S. [Sandia National Labs., Albuquerque, NM (United States)

    1996-04-01

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

  18. Parametric testing of a DWPF glass

    International Nuclear Information System (INIS)

    A series of tests has been performed to characterize the chemical stability of a DWPF borosilicate glass sample as part of the Waste Package Task of the Nevada Nuclear Waste Storage Investigations (NNWSI) Project. This material was prepared at the Savannah River Laboratory for the purpose of testing the 165-frit matrix doped with a simulated nonradioactive waste. All tests were conducted at 900C using deionized water and J-13 water (a tuffaceous formation ground water). In the deionized water tests, both monoliths and crushed glass were tested at various ratios of surface area of the sample to volume of water in order to compare leach rates for different sample geometries or leaching times. Effects on the leach rates as a result of the presence of crushed tuff and stainless steel material were also investigated in the tests with J-13 water. 3 refs., 12 figs., 7 tabs

  19. Surface analysis of Borkron glass for neutron optics applications

    International Nuclear Information System (INIS)

    Grazing Angle Neutron Reflectometry, Optical and Mechanical Roughness Profilometry techniques have been used to study the effects of the polishing operations on the surface of Borkron Schott glass (special borosilicate glass for neutron optics applications) as the polishing tool pressure P and the mean grain size of the polishing powder Φ. The neutron reflectivity investigations have shown that there is formation of a layer at the surface glass substrate. This layer is less dense than the bulk substrate and its thickness is around 60A. The optical and mechanical profilometry measurements have shown that both roughness and waviness decrease with P and Φ. All the experimental results show a good correlation between the neutron refractive index, the thickness and the roughness of the surface layer and the waviness of the glass surface with the two mechanical polishing parameters. The previous techniques have been completed by Secondary Ion Mass Spectroscopy and Atomic Force Microscopy measurements

  20. RETENTION OF SULFATE IN HIGH LEVEL RADIOACTIVE WASTE GLASS

    Energy Technology Data Exchange (ETDEWEB)

    Fox, K.

    2010-09-07

    High level radioactive wastes are being vitrified at the Savannah River Site for long term disposal. Many of the wastes contain sulfate at concentrations that can be difficult to retain in borosilicate glass. This study involves efforts to optimize the composition of a glass frit for combination with the waste to improve sulfate retention while meeting other process and product performance constraints. The fabrication and characterization of several series of simulated waste glasses are described. The experiments are detailed chronologically, to provide insight into part of the engineering studies used in developing frit compositions for an operating high level waste vitrification facility. The results lead to the recommendation of a specific frit composition and a concentration limit for sulfate in the glass for the next batch of sludge to be processed at Savannah River.

  1. Influence of Composition of Sm2O3-Containing Rare Earth Glass on Its Absorption Spectrum

    Institute of Scientific and Technical Information of China (English)

    Zhang Qitu; Wang Tingwei; Meng Xianfeng; Shan Xiaobing; Xu Zhongzi

    2005-01-01

    Borosilicate glass with high rare earth content was fabricated by traditional method. The influence of glass compositions and rare earth content on absorption spectra was examined and discussed. With increasing Sm2O3 content, the intensity of characteristic absorption peak is increased and the absorption peak is broadened. With increasing of the ratios of SiO2/B2O3 and Al2O3/SiO2, the broadening degree of absorption peak is increased. The experimental results provide basis for making special optical glasses which have the characteristics of high absorption for special wavelength laser and high transparence for visible light.

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

    Directory of Open Access Journals (Sweden)

    S. Gin

    2013-06-01

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

  3. Reaction of glass during gamma irradiation in a saturated tuff environment. Part 1. SRL 165 glass

    International Nuclear Information System (INIS)

    The influence of gamma irradiation on the reaction of actinide-doped borosilicate glass (SRL 165) in a saturated tuff environment has been studied in a series of tests lasting up to 56 days. The following conclusions were reached. The reaction of, and subsequent actinide release from, the glass depends on the dynamic interaction between radiolysis effects, which cause the solution pH to become more acidic; glass reaction, which drives the pH more basic; and test component interactions that may extract glass components from solution. The use of large gamma irradiation dose rates to accelerate reactions that may occur in an actual repository radiation field may affect this dynamic balance by unduly influencing the mechanism of the glass-water reaction. Comparisons between the present results and data obtained by reacting similar glasses using MCC-1 and NNWSI rock cup procedures indicate that the irradiation conditions used in the present experiments do not dramatically influence the reaction rate of the glass. 8 figs., 9 tabs

  4. 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.

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

    International Nuclear Information System (INIS)

    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

  6. Development and radiation stability of glasses for highly radioactive wastes

    International Nuclear Information System (INIS)

    The variation of formation temperature, crystallizing behaviour and leach resistance with composition changes for sodium-lithium borosilicate glasses suitable for vitrifying Magnox waste are discussed. Viscosities have been measured between 400 and 10500C. The principal crystal phases which occur have been identified as magnesium silicate, magnesium borate and ceria. The leach rate of polished discs in pure water at 1000C does not decrease with time if account is taken of the fragile siliceous layer that is observed to occur. The effect of 100 years' equivalent α- and β-irradiation on glass properties is discussed. Stored energy release experiments demonstrated that energy is released over a wide temperature range so that it cannot be triggered catastrophically. Temperatures required to release energy are dependent upon the original storage temperature. Helium release is by Fick's diffusion law up to at least 30% of the total inventory, with diffusion coefficients similar to those for comparable borosilicate glasses. Leach rates were not measurably affected by α-radiation. β-radiation in a Van de Graaff accelerator did not change physical properties, but irradiation in an electron microscope caused minute bubbles in lithium-containing glasses above 2000C. (author)

  7. Comparison of U.S. and international glass/metal interactions after five years burial in salt

    International Nuclear Information System (INIS)

    The objective of this paper is to summarize the five year glass/metal interactions data from the WIPP/MIIT burial study. Laboratory and early data from the Stripa burial experiment indicated that some materials may affect the leaching performance of the borosilicate glass. To examine this phenomenon in more detail, U.S. (SR 165-TDS) and international glass samples were placed in contact with several proposed canister/overpack materials during the MIIT experiment. Thus far, results from SIMS, SEM/EDS and FTIRRS analysis on SR 165-TDS/metal interfaces reveal that the metals do not significantly affect the performance of the glass and that the total extent of G/M interaction was small and was consistent with glass/glass and glass/salt interactions. Results from similar analysis for the international glasses/metal interactions will also be discussed. 13 refs., 6 figs., 3 tabs

  8. Performance evaluation of vitrified waste product based on barium-borosilicate matrix deployed for vitrification of sulphate bearing high level radioactive liquid waste

    International Nuclear Information System (INIS)

    Aqueous waste of various categories (viz., low, intermediate and high level depending on the concentration of radionuclides) is generated at different stages of the nuclear fuel cycle. Most of the radioactivity generated in entire nuclear fuel cycle is concentrated in high level radioactive liquid waste (HLW). Since the radioactivity of the waste is to be isolated from the human-environment for extended period of time, a three stage approach has been adopted for management of HLW. This involves (i) immobilization of waste oxides in stable and inert solid matrices, (ii) interim retrievable storage of conditioned waste packages under cooling and surveillance and (iii) deep underground disposal in suitable geological formulations. Composition of HLW depends on various factors like type of fuel and its cladding, off reactor cooling, reprocessing flow sheet etc. Compositional changes in HLW necessitate modification in glass formulations, so as to get the conditioned product of desired characteristics. This report describes the experimental studies and results obtained for performance evaluation of the vitrified waste product made from barium borosilicate glass matrix accommodating sulphate bearing chemically simulated HLW. Product characteristics like chemical durability, homogeneity, phase separation, thermal conductivity, impact strength etc have been evaluated and discussed in the report. (author)

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

    International Nuclear Information System (INIS)

    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 129I, 85Kr and 14C. (author). 104 refs., 9 tabs., 5 figs

  10. Leaching behavior of glass ceramic nuclear waste forms

    International Nuclear Information System (INIS)

    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 900C for 3 to 28 days in deionized water and silicate water. The results, expressed in normalized elemental mass loss, (g/m2), 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/m2 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

  11. Annual progress report to Battelle Pacific Northwest National Laboratories on prediction of phase separation of simulated nuclear waste glasses

    International Nuclear Information System (INIS)

    The objective of this research is to predict the immiscibility boundaries of multi-component borosilicate glasses, on which many nuclear waste glass compositions are based. The method used is similar to the prediction method of immiscibility boundaries of multi-component silicate glass systems successfully made earlier and is based upon the superposition of immiscibility boundaries of simple systems using an appropriate parameter. This method is possible because many immiscibility boundaries have similar shapes and can be scaled by a parameter. In the alkali and alkaline earth binary silicate systems, for example, the critical temperature and compositions were scaled using the Debye-Hueckel theory. In the present study on borosilicate systems, first, immiscibility boundaries of various binary alkali and alkaline borate glass systems (e.g. BaO-B2O3) were examined and their critical temperatures were evaluated in terms of Debye-Hueckel theory. The mixing effects of two alkali and alkaline-earth borate systems on the critical temperature were also explored. Next immiscibility boundaries of ternary borosilicate glasses (e.g. Na2O-SiO2-B2O3, K2O-SiO2-B2O3, Rb2O-SiO2-B2O3, and Cs2O-SiO2-B2O3) were examined. Their mixing effects are currently under investigation

  12. Morphology of altered layers of glasses

    International Nuclear Information System (INIS)

    The alteration of the french nuclear waste glass R7T7 has been studied through chemical analysis, thermo-poro-metry and X-ray scattering. Pseudo-dynamic leaching was used, with daily renewal of the leaching solution. The behavior of the R77 glass has been compared to cesium borosilicate glasses with small amounts of Ca and Zr added. As compared to these simplified compositions, the R7T7 glass has a quasi-congruent leaching of Na, B and Si and strongly retains Ca and Zr. The altered layers are very porous (porosity > 40% ). The pore size increases with time to reach a constant value that is independent of the nature of the glass but that strongly depends on the method used for leaching. The pore radii are about 4 nm in pseudo-dynamic mode and 2 nm in static conditions. X-ray scattering indicate that the pores are compact with a sharp interface. Their origin is related to the quasi-equilibrium reaction of hydrolysis redeposition of silica. (authors)

  13. Survey of Potential Glass Compositions for the Immobilisation of the UK's Separated Plutonium Stocks

    International Nuclear Information System (INIS)

    The Nuclear Decommissioning Authority (NDA) has taken over ownership of the majority of the UK's separated civil plutonium stocks, which are expected to exceed 100 metric tons by 2010. Studies to technically underpin options development for the disposition of these stocks, for example by immobilization or re-use as fuel, are being carried out by Nexia Solutions on behalf of NDA. Three classes of immobilization matrices have been selected for investigation by means of previous studies and stakeholder dialogue: ceramic or crystalline waste-forms, storage MOx, and vitreous or glass-based waste-forms. This paper describes the preliminary inactive experimental program for the vitrification option, with results from a wide range of glass compositions along with conclusions on their potential use for plutonium immobilization. Following review, four glass systems were selected for preliminary investigation: borosilicate, lanthanide borosilicate, aluminosilicate and phosphate glasses. A broad survey of glass properties was completed in order to allow meaningful evaluation, e.g. glass formulation, waste loading, chemical durability, thermal properties, and viscosity. The program was divided into two parts, with silicate and phosphate glasses being investigated by Nexia Solutions and the Immobilisation Science Laboratory (ISL) at the University of Sheffield respectively. (authors)

  14. The Influence of Waste Glass Slurry on the Properties of Concrete

    OpenAIRE

    Kara, P.

    2013-01-01

    The grinding of glass waste chips in a wet environment for 120 minutes gives possibility to obtain particles finer in size in comparison to glass waste chips ground in dry environment. The particle distribution analysis showed that borosilicate glass lamp waste slurry has particle size in the range of 0.713 μm to 8.088 μm, fluorescent lamp glass waste slurry - from 2.473 μm to 20.088 μm, amber glass cullet slurry - from 1.435 μm to 21.118 μm, green glass cullet slurry - from 0.903 μm to 23.12...

  15. Coupling of fluid flow with stepwise alteration of glass waste forms

    International Nuclear Information System (INIS)

    This paper reports the effect of flow of a basalt groundwater on the alteration of a borosilicate glass at 150 degrees C was investigated. The first observable effect is that glass dissolution rates increased appreciably with increasing flow rate. Such effects promote a more rapid alteration of glass to solids that will initially control the release rate of many radionuclides. The second effect is that solution supersaturations are progressively suppressed with increasing flow rate. Under favorable circumstances, this could prevent the formation of some metastable alteration solids and promote the formation of more stable solids. In this way, the progressive stepwise alteration of glass radionuclide release from glass waste forms. Failure to demonstrate such high initial solution supersaturations developed from non-flow-related factors or to diffusional constraints to continued chemical reaction processes at the glass surface

  16. Canonical correlation of waste glass compositions and durability, including pH

    International Nuclear Information System (INIS)

    Control of waste glass durability is a major concern in the immobilization of radioactive and mixed wastes. Leaching rate in standardized laboratory tests is being used as a demonstration of consistency of the response of waste glasses in the final disposal environment. The leaching of silicate and borosilicate glasses containing alkali or alkaline earth elements is known to be autocatalytic, in that the initial ion exchange of alkali in the glass for hydrogen ions in water results in the formation of OH and increases the pH of the leachate. The increased pH then increases the rate of silicate network attack, accelerating the leaching effect. In well formulated glasses this effect reaches a thermodynamic equilibrium when leachate saturation of a critical species, such as silica, or a dynamic equilibrium is reached when the pH shift caused by incremental leaching has negligible effect on pH. This report analyzes results of a seven leach test on waste glasses

  17. Chemical durability of soda-lime-aluminosilicate glass for radioactive waste vitrification

    International Nuclear Information System (INIS)

    Vitrification has been identified as one of the most viable waste treatment alternatives for nuclear waste disposal. Currently, the most popular glass compositions being selected for vitrification are the borosilicate family of glasses. Another popular type that has been around in glass industry is the soda-lime-silicate variety, which has often been characterized as the least durable and a poor candidate for radioactive waste vitrification. By replacing the boron constituent with a cheaper substitute, such as silica, the cost of vitrification processing can be reduced. At the same time, addition of network intermediates such as Al2O3 to the glass composition increases the environmental durability of the glass. The objective of this study is to examine the ability of the soda-lime-aluminosilicate glass as an alternative vitrification tool for the disposal of radioactive waste and to investigate the sensitivity of product chemical durability to variations in composition

  18. Crystallization of a barium-aluminosilicate glass

    Energy Technology Data Exchange (ETDEWEB)

    Drummond, C.H. III; Lee, W.E.; Bansal, N.P.; Hyatt, M.J.

    1989-10-01

    The crystallization of a celsian glass composition was investigated as a possible high-temperature ceramic matrix material. Heat treatments invariably resulted in crystallization of the hexaclesian phase unless a flux, such as lithia, was added or a nucleating agent used (e.g., celsian seeds). TEM analysis revealed complex microstructures. Glasses with Mo additions contained hexacelsian, mullite, and an Mo-rich glass. Li{sub 2}O additions stabilized celsian but mullite and Mo-rich glass were still present. 15 refs.

  19. The effects of the glass surface area/solution volume ratio on glass corrosion: A critical review

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-03-01

    This report reviews and summarizes the present state of knowledge regarding the effects of the glass surface area/solution volume (SA/V) ratio on the corrosion behavior of borosilicate waste glasses. The SA/V ratio affects the rate of glass corrosion through the extent of dilution of corrosion products released from the glass into the leachate solution: glass corrosion products are diluted more in tests conducted at low SA/V ratios than they are in tests conducted at high SA/V ratios. Differences in the solution chemistries generated in tests conducted at different SA/V ratios then affect the observed glass corrosion behavior. Therefore, any testing parameter that affects the solution chemistry will also affect the glass corrosion rate. The results of static leach tests conducted to assess the effects of the SA/V are discussed with regard to the effects of SA/V on the solution chemistry. Test results show several remaining issues with regard to the long-term glass corrosion behavior: can the SA/V ratio be used as an accelerating parameter to characterize the advanced stages of glass corrosion relevant to long disposal times; is the alteration of the glass surface the same in tests conducted at different SA/V, and in tests conducted with monolithic and crushed glass samples; what are the effects of the SA/V and the extent of glass corrosion on the disposition of released radionuclides? These issues will bear on the prediction of the long-term performance of waste glasses during storage. The results of an experimental program conducted at ANL to address these and other remaining issues regarding the effects of SA/V on glass corrosion are described. 288 refs., 59 figs., 16 tabs.

  20. The effects of the glass surface area/solution volume ratio on glass corrosion: A critical review

    International Nuclear Information System (INIS)

    This report reviews and summarizes the present state of knowledge regarding the effects of the glass surface area/solution volume (SA/V) ratio on the corrosion behavior of borosilicate waste glasses. The SA/V ratio affects the rate of glass corrosion through the extent of dilution of corrosion products released from the glass into the leachate solution: glass corrosion products are diluted more in tests conducted at low SA/V ratios than they are in tests conducted at high SA/V ratios. Differences in the solution chemistries generated in tests conducted at different SA/V ratios then affect the observed glass corrosion behavior. Therefore, any testing parameter that affects the solution chemistry will also affect the glass corrosion rate. The results of static leach tests conducted to assess the effects of the SA/V are discussed with regard to the effects of SA/V on the solution chemistry. Test results show several remaining issues with regard to the long-term glass corrosion behavior: can the SA/V ratio be used as an accelerating parameter to characterize the advanced stages of glass corrosion relevant to long disposal times; is the alteration of the glass surface the same in tests conducted at different SA/V, and in tests conducted with monolithic and crushed glass samples; what are the effects of the SA/V and the extent of glass corrosion on the disposition of released radionuclides? These issues will bear on the prediction of the long-term performance of waste glasses during storage. The results of an experimental program conducted at ANL to address these and other remaining issues regarding the effects of SA/V on glass corrosion are described. 288 refs., 59 figs., 16 tabs

  1. Immobilization of high level nuclear wastes in sintered glasses. Devitrification evaluation produced with different thermal treatments

    International Nuclear Information System (INIS)

    This work describes immobilization of high level nuclear wastes in sintered glass, as alternative way to melting glass. Different chemical compositions of borosilicate glass with simulate waste were utilized and satisfactory results were obtained at laboratory scale. As another contribution to the materials studies by X ray powder diffraction analysis, the devitrification produced with different thermal treatments, was evaluated. The effect of the thermal history on the behaviour of fission products containing glasses has been studied by several working groups in the field of high level waste fixation. When the glass is cooled through the temperature range from 800 deg C down to less than 400 deg C (these temperatures are approximates) nucleation and crystal growth can take place. The rate of crystallization will be maximum near the transformation point but through this rate may be low at lower temperatures, devitrification can still occur over long periods of time, depending on the glass composition. It was verified that there can be an appreciable increase in leaching in some waste glass compositions owing to the presence of crystalline phases. On the other hand, other compositions show very little change in leachability and the devitrified product is often preferable as there is less tendency to cracking, particularly in massive blocks of glass. A borosilicate glass, named SG7, which was developed specially in the KfK for the hot pressing of HLW with glass frit was studied. It presents a much enhanced chemical durability than borosolicate glass developed for the melting process. The crystallization behaviour of SG7 glass products was investigated in our own experiments by annealing sintered samples up to 3000 h at temperatures between 675 and 825 deg C. The samples had contained simulated waste with noble metals, since these might act as foreign nuclei for crystallization. Results on the extent of devitrification and time- temperature- transformation curves are

  2. Impact of a boron rich layer on minority carrier lifetime degradation in boron spin-on dopant diffused n-type crystalline silicon solar cells

    International Nuclear Information System (INIS)

    In the production of n-type crystalline silicon solar cells with boron diffused emitters, the formation of a boron rich layer (BRL) is a common phenomenon and is largely responsible for bulk lifetime degradation. The phenomenon of BRL formation during diffusion of boron spin-on dopant and its impact on bulk lifetime degradation are investigated in this work. The BRL formed beneath the borosilicate glass layer has thicknesses varying from 10 nm–150 nm depending on the diffusion conditions. The effective and bulk minority carrier lifetimes, measured with Al2O3 deposited layers and a quinhydron–methanol solution, show that carrier lifetime degradation is proportional to the BRL thicknesses and their surface recombination velocities. The controlled diffusion processes and different oxidation techniques used in this work can partially reduce the BRL thickness and improve carrier lifetime by more than 10%. But for BRL thicknesses higher than 50 nm, different etching techniques further lower the carrier lifetime and the degradation in the device cannot be recovered. (paper)

  3. Role of the pore fluid in crack propagation in glass

    Science.gov (United States)

    Mallet, Céline; Fortin, Jérôme; Guéguen, Yves; Bouyer, Fréric

    2015-05-01

    We investigate pore fluid effects due to surface energy variation or due to chemical corrosion in cracked glass. Both effects have been documented through experimental tests on cracked borosilicate glass samples. Creep tests have been performed to investigate the slow crack propagation behavior. We compared the dry case (saturated with argon gas), the nonreactive water saturated case (commercial mineralized water), and the distilled and deionized water saturated case (pure water). Chemical corrosion effects have been observed and evidenced from pH and water composition evolution of the pure water. Then, the comparison of the dry case, the mineral water saturated case, and the corrosion case allow to (i) evidence the mechanical effect of the presence of a pore fluid and (ii) show also the chemical effect of a glass dissolution. Both effects enhance subcritical crack propagation.

  4. Actinide speciation in glass leach-layers: An EXAFS study

    International Nuclear Information System (INIS)

    Uranium L3 X-ray absorption data were obtained from two borosilicate glasses, which are considered as models for radioactive wasteforms, both before and after leaching. Surface sensitivity to uranium speciation was attained by a novel application of simultaneous fluorescence and electron-yield detection. Changes in speciation are clearly discernible, from U(VI) in the bulk to (UO2)2+-uranyl in the leach layer. The leach-layer uranium concentration variations with leaching times are also determined from the data

  5. 5.3. The kinetics of acetic acid decomposition of calcined borosilicate concentrate

    International Nuclear Information System (INIS)

    Present article is devoted to kinetics of acetic acid decomposition of calcined borosilicate concentrate. The experimental data of kinetics of boron oxide extraction from the calcined danburite concentrate at acetic acid decomposition was obtained at 30-90 deg C temperature ranges and 15-60 minutes process duration. It was defined that at temperature increasing the extraction rate of boron oxide from the calcined danburite concentrate significantly increases. The influence of extraction rate of boron oxide on process duration at acetic acid decomposition was studied.

  6. The precision of product consistency tests conducted with a glass-bonded ceramic waste form

    International Nuclear Information System (INIS)

    The product consistency test (PCT) that is used for qualification of borosilicate high-level radioactive waste (HLW) glasses for disposal can be used for the same purpose in the qualification of the glass-bonded sodalite ceramic waste form (CWF). The CWF was developed to immobilize radioactive salt wastes generated during the electrometallurgical treatment of spent sodium-bonded nuclear fuels. An interlaboratory study was conducted to measure the precision of PCTs conducted with the CWF for comparison with the precision of PCTs conducted with HLW glasses. The six independent sets of triplicate PCT results generated in the study were used to calculate the intralaboratory and interlaboratory consistency based on the concentrations of Al, B, Na, and Si in the test solutions. The results indicate that PCTs can be conducted as precisely with the CWF as with HLW glasses. For example, the values of the reproducibility standard deviation for Al, B, Na, and Si were 1.36, 0.347, 3.40, and 2.97 mg/l for PCT with CWF. These values are within the range of values measured for borosilicate glasses, including reference HLW glasses

  7. Plutonium immobilization in glass and ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Knecht, D.A. [Lockheed Martin Idaho Technologies, Idaho Falls (United States); Murphy, W.M. [Southwest Research Institute, San Antonio, TX (United States)

    1996-05-01

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

  8. Photo-induced processes in silicate glasses exposed to IR femotosecond pulses

    International Nuclear Information System (INIS)

    The optical properties variation in silicate glasses (fused silica, boro-silicate crowns K8 (Russia) and BK7 (USA), and high purity alkali-silicate glass) after exposure to high-power femtosecond laser radiation at 0.85 μm have been studied. The laser spectral line broadening leading to the supercontinuum generation in visible and UV spectral regions was observed in all studied glasses. Color center generation and intrinsic luminescence were found in boro- and alkali-silicate glasses. It is believed that these processes result from linear and/or two-photon absorption of the short-wavelength part of this supercontinuum which causes glass matrix ionization. No color center absorption in the visible region was observed in fused silica at irradiances up to the laser damage threshold. It was concluded that there is no significant ionization of fused silica under exposure to IR femtosecond laser pulses with irradiance below laser induced damage threshold

  9. Chemical effects of lanthanides and actinides in glasses determined with electron energy loss spectroscopy

    International Nuclear Information System (INIS)

    Chemical and structural environments of f-electron elements in glasses are the origin of many of the important properties of materials with these elements; thus oxidation state and chemical coordination of lanthanides and actinides in host materials is an important design consideration in optically active glasses, magnetic materials, perovskite superconductors, and nuclear waste materials. We have made use of the line shapes of Ce to determine its oxidation state in alkali borosilicate glasses being developed for immobilization of Pu. Examination of several prototype waste glass compositions with EELS shows that the redox state of Ce doped to 7 wt% could be varied by suitable choice of alkali elements. EELS for a Pu-doped glass illustrate the small actinide N4/N5 intensity ratio and show that the Pu-N4,5 white line cross section is comparable to that of Gd M4,5

  10. Technical glasses: electrical properties and behaviour in nuclear reactor WWR-S

    International Nuclear Information System (INIS)

    Samples of SIMAX, SIAL, PN, UNIHOST, KS-80 and KS-90 were irradiated in a WWR-S reactor and their electric conductivity was studied. A decrease in conductivity was found following the irradiation with thermal neutron fluence of 2.0x1023 n.m-2, which is characteristic of the individual types of glass. In the reactor channel heat generation was compared for glass containing boron (SIMAX, SUPREMAX) and boron-free glass (UNIHOST). Boron-free glass showed an increase within the limits of the temperature measurement error while both borosilicate types of glass showed a local increase of temperature of 39 K and 33 K, respectively, at temperatures of 350 to 390 degC. (author)

  11. Immobilization of nuclear waste: Raman Spectroscopic probing of structural changes in glass matrix

    International Nuclear Information System (INIS)

    Barium borosilicate glass used for immobilization of sulphate containing simulated high level radioactive liquid waste was prepared using conventional melt and quench method. Conventional leach test under total reflux method was used for the assessment of chemical durability of waste glass. The leaching was carried out using a conventional boiling water unit wherein powdered and screened glass sample of -16+25 BSS (850 micron) grain size was exposed to boiling distilled water for 2 years. Exposed glass specimens were subjected to Raman spectroscopic investigations to understand the structural modifications, if any, during leaching experiments. The results revealed that the leaching leads to a redistribution of bridged and non-bridged oxygen in glass. The redistribution is tentatively assigned to the possible release of structure breaking ions/atoms from the vitreous waste. (author)

  12. Decontamination glass

    International Nuclear Information System (INIS)

    Glass for the decontamination of the furnace for vitrification of radioactive wastes contains 50 to 60 wt.% of waste glass, 15 to 30 wt.% of calcium oxide, 1 to 6 wt.% sodium oxide, 1 to 5 wt.% phosphorus pentoxide and 5 to 20 wt.% boron oxide. The melting furnace is flushed with the glass such that it melts in the furnace for at least 60 mins and is then poured out of the furnace. After the furnace has cooled down the settled glass spontaneously cracks and peels off the walls leaving a clean surface. The glass may be used not only for decontamination of the furnace but also for decontamination of melting crucibles and other devices contaminated with radioactive glass. (J.B.)

  13. Recycle Glass in Foam Glass Production

    OpenAIRE

    Petersen, Rasmus Rosenlund; König, Jakob; Yue, Yuanzheng

    2014-01-01

    The foam glass industry turn recycle glass into heat insulating building materials. The foaming process is relative insensitive to impurities in the recycle glass. It is therefore considered to play an important role in future glass recycling. We show and discuss trends of use of recycled glasses in foam glass industry and the supply sources and capacity of recycle glass.

  14. Recycle Glass in Foam Glass Production

    DEFF Research Database (Denmark)

    Petersen, Rasmus Rosenlund; König, Jakob; Yue, Yuanzheng

    The foam glass industry turn recycle glass into heat insulating building materials. The foaming process is relative insensitive to impurities in the recycle glass. It is therefore considered to play an important role in future glass recycling. We show and discuss trends of use of recycled glasses...... in foam glass industry and the supply sources and capacity of recycle glass....

  15. The role of ceramics, cement and glass in the immobilization of radioactive wastes

    International Nuclear Information System (INIS)

    A brief account is given of the constitution and origin of nuclear waste. The immobilization of wastes is discussed: borosilicate glasses are considered as possible matrices; ceramic forms are dealt with in more detail. The principles of the use of ceramics are explained, with examples of different ceramic structures; cements are mentioned as being suitable for wet, medium- to low-active wastes. The effects of radiation on cement, ceramic and glass waste forms are indicated. The account concludes with 'summary and future progress'. (U.K.)

  16. Melting Hanford LAW into Iron-Phosphate Glass in a CCIM

    Energy Technology Data Exchange (ETDEWEB)

    Nick Soelberg; Sharna Rossberg

    2011-09-01

    A vitrification test has been conducted using the cold crucible induction melter (CCIM) test system at the Idaho National Laboratory. The test was conducted to demonstrate the vitrification of a Hanford low activity waste (LAW) that contains relatively large amounts of sulfate and sodium, compared to other radioactive Hanford waste streams. The high sulfate content limits the potential loading of this waste stream in conventional borosilicate glass, so this test demonstrated how this waste stream could be vitrified in an iron-phosphate glass that can tolerate higher levels of sulfate.

  17. Spin-polarized lithium diffusion in a glass hot-vapor cell

    Science.gov (United States)

    Ishikawa, Kiyoshi

    2016-08-01

    We report diffusion coefficients of optically pumped lithium atoms in helium buffer gas. The free-induction decay and the spin-echo signals of ground-state atoms were optically detected in an external magnetic field with the addition of field gradient. Lithium hot vapor was produced in a borosilicate-glass cell at a temperature between 290 and 360°C. The simple setup using the glass cells enabled lithium atomic spectroscopy in a similar way to other alkali-metal atoms and study of the collisional properties of lithium atoms in a hot-vapor phase.

  18. Nuclear glass durability: new insight into alteration layer properties

    International Nuclear Information System (INIS)

    We have performed TEM, Raman microspectroscopy, and Nano-SIMS characterization of borosilicate glass samples altered for nearly 26 years at 90 degrees C in a confined granitic medium in order to better understand the rate-limiting mechanisms under conditions representative of a deep geological repository for vitrified radioactive waste. For the first time, we show a thick interphase that behaves like a diffusion barrier between the pristine glass and the other alteration products (porous gel and crystalline phases). Our findings indicate that the glass undergoes two distinct irreversible reactions: (i) hydration of the pristine glass controlled by water diffusion with a diffusion coefficient of 2 * 10-21 m2/s and (ii) transformation of the hydrated glass into a macroporous gel with major structural changes. Both materials are nonstoichiometric and metastable. A final reversible reaction leads to the formation of crystalline phases that consume elements forming the gel layer and the hydrated glass. All these reactions must be combined in a model to predict long-term rates of nuclear glass in natural environments. (authors)

  19. The current status of glass leaching studies in France

    International Nuclear Information System (INIS)

    Glass has been selected in France as the material used to confine the activity of fission product solutions, and a continuous vitrification process has been developed at the Marcoule Vitrification Facility (AVM), the first industrial plant. Borosilicate glass was chosen in various compositions for its properties: it is a homogeneous, non-porous material that incorporates appreciable quantities of most of the fission product oxides, and is only alterable at the surface interface layer. Glass thus constitutes the primary radioactivity containment barrier, and it is essential to determine its long-term behavior. Water constitutes the principal hazard during temporary or definitive storage of the glass blocks. Two types of inherent material properties are studied from the standpoint of glass stability under leaching conditions: - chemical durability; - radioactive containability with regard to the various radionuclides, fission products and especially the actinides. Durability tests are carried out in SOXHLET devices and the alteration rates are measured by the weight loss. The containability is measured by the leach rate, i.e. by the rate of activity loss into the water. Leaching tests are conducted for several major objectives: - selection of glass compositions (leach rates); - leaching mechanism studies (hydrolyzed layer characteristics, effects of temperature, pressure, pH, etc.); - long-term behavior studies (glass specimens doped with alpha-emitters); - simulation of geological repository environments

  20. Neural network analysis of nuclear waste glass composition vs durability

    International Nuclear Information System (INIS)

    The relationship between the chemical composition of oxide glasses and their physical properties is poorly understood, but it is becoming more important as vitrification (transformation into glass) of high-level nuclear waste becomes the favored method for long-term storage. The vitrified waste will be stored deep in geologic repositories where it must remain intact for at least 10,000 years. A strong resistance to groundwater exposure; i.c. a slow rate of glass dissolution, is of great importance. This project deals specifically with glass samples developed and tested for the nuclear fuel reprocessing facility near West Valley, New York. This facility needs to dispose of approximately 2.2 million liters of high-level radioactive liquid waste currently stored in stainless steel tanks. A self-organizing, artificial neural network was used to analyze the trends in the glass dissolution data for the effects of composition and the resulting durability of borosilicate glasses in an aqueous environment. This durability data can be used to systematically optimize the properties of the complex nuclear glasses and slow the dissolution rate of radionuclides into the environment

  1. Iron phosphate glass for immobilization of 99Tc

    International Nuclear Information System (INIS)

    Highlights: •99Tc (surrogated by Re) was immobilized in an iron phosphate glass. •∼1.1 mass% Re was retained, possibly dissolved, in the iron phosphate glass. •The 7-day PCT normalized release of Re was −2 g/m2. •Re concentration in the glass rapidly decreased with increasing melting temperature and duration. -- Abstract: Technetium-99 (99Tc) can bring serious environmental threats because of its long half-life (τ1/2 = ∼2.1 × 105 years), high fission yield (∼6%), and high solubility and mobility in the ground water. The high volatility makes it difficult to immobilize 99Tc in continuous melters vitrifying 99Tc-containing nuclear wastes in borosilicate glasses. This work explores a possibility of incorporating a high concentration of 99Tc, surrogated by the non-radioactive Re, in an iron phosphate glass by melting mixtures of iron phosphate glass frits with 1.5–6 mass% KReO4 at ∼1000 °C. The retention of Re achieved was ∼1.1 mass%. The normalized Re release by the 7-day Product Consistency Test was −2 g/m2. Surprisingly, the Re escaped from the melt within a short time of heating, especially when the temperature was increased. Therefore, 99Tc volatilization would still be a challenging task for its immobilization in iron phosphate glasses

  2. Strength Improvement of Glass Substrates by Using Surface Nanostructures.

    Science.gov (United States)

    Kumar, Amarendra; Kashyap, Kunal; Hou, Max T; Yeh, J Andrew

    2016-12-01

    Defects and heterogeneities degrade the strength of glass with different surface and subsurface properties. This study uses surface nanostructures to improve the bending strength of glass and investigates the effect of defects on three glass types. Borosilicate and aluminosilicate glasses with a higher defect density than fused silica exhibited 118 and 48 % improvement, respectively, in bending strength after surface nanostructure fabrication. Fused silica, exhibited limited strength improvement. Therefore, a 4-μm-deep square notch was fabricated to study the effect of a dominant defect in low defect density glass. The reduced bending strength of fused silica caused by artificial defect increased 65 % in the presence of 2-μm-deep nanostructures, and the fused silica regained its original strength when the nanostructures were 4 μm deep. In fragmentation tests, the fused silica specimen broke into two major portions because of the creation of artificial defects. The number of fragments increased when nanostructures were fabricated on the fused silica surface. Bending strength improvement and fragmentation test confirm the usability of this method for glasses with low defect densities when a dominant defect is present on the surface. Our findings indicate that nanostructure-based strengthening is suitable for all types of glasses irrespective of defect density, and the observed Weibull modulus enhancement confirms the reliability of this method. PMID:27194443

  3. Glass packages in interim storage; Les verres dans les stockages

    Energy Technology Data Exchange (ETDEWEB)

    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{sub 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.

  4. MoO3 incorporation in magnesium aluminosilicate glasses

    International Nuclear Information System (INIS)

    Molybdate has a very low solubility in silicate and borosilicate glass systems and its excess presence in nuclear waste glass can cause the formation of a readily soluble “yellow phase”. In this study, the incorporation of molybdenum oxide (MoO3) in a magnesium aluminosilicate glass system has been investigated. The prepared glasses show a higher than 90% molybdenum retention rate and up to 5.34 mol% (12.28 wt%) MoO3 can be incorporated into these glasses without causing visible phase separation. The incorporation of MoO3 increases glass density, decreases glass transition and crystallisation temperatures and intensifies Raman bands assigned to vibrations of MoO42− units. When excess molybdate is added liquid–liquid phase separation and crystallisation occurs. The separated phase is spherical, 200–400 nm in diameter and randomly dispersed. Based on powder X-ray diffraction, Raman spectroscopy and transmission electron microscopy, the separated phase is identified as MgMoO4

  5. Thermochemical study of rare earth and nitrogen incorporation in glasses

    Science.gov (United States)

    Zhang, Yahong

    Rare earth containing aluminosilicate, borosilicate, aluminate and nitrogen containing aluminosilicate glasses are technically important materials. They have extraordinary physical and chemical properties such as high glass transition temperature, very low electrical conductivity, and excellent chemical stability. These unique properties lead to applications as coatings on metals and ceramics, optical fibers, semiconductors, and nuclear waste containment materials. In addition, such systems contain the most widely used additives for sintering of Si3N4, SiAlON and SiC ceramics for high temperature applications. Thermodynamic properties and the relations among energetics, structure and bonding are essential to controlling processing parameters to synthesize, at lower cost, materials having better properties. Earlier investigations mainly pertained to specific physical properties of rare-earth doped oxide and oxynitride glasses. Work on the thermodynamic stability and materials compatibility has been very sparse. High temperature solution calorimetry in molten oxide solvents is a powerful tool for the thermodynamic study of refractory materials. With implementation and improvement, this technique has been applied to the first measurement of enthalpies of formation of RE-Si-Al-O glasses, REAlO3 glasses, RE-Si-Al-O-N glasses, and Si3N 4 and Ge3N4 with high pressure spinel structure. The first successful synthesis of REAlO3 glasses has been achieved by containerless melting. Their large enthalpies of crystallization confirm that they are reluctant glass formers. For glasses along the 2REAlO3 -3SiO2 join, the strongly negative heats of mixing support the absence of miscibility gaps except possibly at very high silica content. Energetic evidence has been presented for incipient phase-ordered regions in Gd- or Hf-containing sodium alumino-borosilicate glasses for plutonium immobilization. Linear relations between enthalpies of formation of RESiAlON glasses from elements and

  6. The formation of crystals in glasses containing rare earth oxides

    International Nuclear Information System (INIS)

    Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd2O3–22.7CeO2–11.7La2O3–10.9PrO2–1.3Eu2O3–1.3Gd2O3–8.1Sm2O3–4.8Y2O3 with a baseline glass of composition 60.2SiO2–16.0B2O3–12.6Na2O–3.8Al2O3–5.7CaO–1.7ZrO2. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La2O3 and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO5) and oxyapatite (Ca2La8Si6O26) were found in glasses containing La2O3, while oxyapatite (Ca2La8Si6O26 and NaNd9Si6O26) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (TL) of the glasses containing 5%, 10% and 15% La2O3 were 800°C, 959°C and 986°C, respectively; while TL was 825°C, 1059°C and 1267°C for glasses with 5%, 10% and 15% addition of mixed rare earth oxides. The component coefficients TB2O3, TSiO2, TCaO, and TRE2O3 were also evaluated using a recently published study

  7. Physical and chemical characteristics of lead-iron phosphate nuclear waste glasses

    International Nuclear Information System (INIS)

    Experimental determinations of the properties of lead-iron phosphate glasses pertinent to their application to the problem of permanently disposing of high-level nuclear wastes have been carried out. These investigations included studies of the composition and physical properties of nuclear waste glasses (NWG), as well as the effect of preparation conditions. Lead-iron phosphate nuclear waste glasses were prepared by dissolving simulated US defense wastes or simulated commercial power reactor wastes in molten lead-iron phosphate melts at temperatures between 900 and 10500C. The measured physical and chemical properties of the nuclear waste glasses formed by cooling these melts and annealing included the following: (1) aqueous corrosion resistance as a function of the solution pH, solution temperature, and glass composition, (2) glass density, (3) thermal expansion coefficient, (4) glass transition temperature and softening point, (5) heat capacity, (6) critical cooling rate, (7) temperature for the maximum crystallization rate, (8) relative solubility of waste oxides in the glass melt, (9) reactions between the molten glass and the melting crucible (Pt, ZrO2, Al2O3), and (10 studies of possible metal cannister materials. Experimental results for the lead-iron phosphate NWG are compared to available data for borosilicate NWG. Relative to borosilicate NWG, the lead-iron phosphate glasses have several distinct advantages which include a much lower aqueous corrosion rate, a lower preparation temperature, and the ability to immobilize many types of commercial and defense-related high-level radioactive wastes. 34 refs., 18 figs., 10 tabs

  8. Glass Durability Modeling, Activated Complex Theory (ACT)

    International Nuclear Information System (INIS)

    The most important requirement for high-level waste glass acceptance for disposal in a geological repository is the chemical durability, expressed as a glass dissolution rate. During the early stages of glass dissolution in near static conditions that represent a repository disposal environment, a gel layer resembling a membrane forms on the glass surface through which ions exchange between the glass and the leachant. The hydrated gel layer exhibits acid/base properties which are manifested as the pH dependence of the thickness and nature of the gel layer. The gel layer has been found to age into either clay mineral assemblages or zeolite mineral assemblages. The formation of one phase preferentially over the other has been experimentally related to changes in the pH of the leachant and related to the relative amounts of Al+3 and Fe+3 in a glass. The formation of clay mineral assemblages on the leached glass surface layers ,lower pH and Fe+3 rich glasses, causes the dissolution rate to slow to a long-term steady state rate. The formation of zeolite mineral assemblages ,higher pH and Al+3 rich glasses, on leached glass surface layers causes the dissolution rate to increase and return to the initial high forward rate. The return to the forward dissolution rate is undesirable for long-term performance of glass in a disposal environment. An investigation into the role of glass stoichiometry, in terms of the quasi-crystalline mineral species in a glass, has shown that the chemistry and structure in the parent glass appear to control the activated surface complexes that form in the leached layers, and these mineral complexes ,some Fe+3 rich and some Al+3 rich, play a role in whether or not clays or zeolites are the dominant species formed on the leached glass surface. The chemistry and structure, in terms of Q distributions of the parent glass, are well represented by the atomic ratios of the glass forming components. Thus, glass dissolution modeling using simple atomic

  9. Effect of Kovar alloy oxidized in simulated N2/H2O atmosphere on its sealing with glass

    Institute of Scientific and Technical Information of China (English)

    Dawei Luo; Wenbo Leng; Zhuoshen Shen

    2008-01-01

    The effect of Kovar alloy oxidized in simulated field atmosphere on its sealing with glass was studied in this article. After Kovar plates and pins were preoxidized in N2 with 0℃, 10℃ and 20℃ dew points at 1000℃ for different times, Fe3O4 and Fe2O3 existed in the oxidation products on Kovar surface, and the quantity of Fe2O3 increased with increasing dew point and oxidation time.Then they were sealed with borosilicate glass insulator at 1030℃ for 20 min. The results indicated that the type and quantity of oxidation products would directly influence the quality of glass-to-metal seals. With the increase of oxidation products, gas bubbles in the glass insulator were more serious, the climbing height of glass along the pins was higher, and corrosion of Kovar pins caused from the molten glass was transformed from uniform to the localized.

  10. R7T7-type HLW glass alteration under irradiation. Study of the residual alteration rate regime

    International Nuclear Information System (INIS)

    In France, fission products and minor actinides remaining after reprocessing of spent nuclear fuel are confined in a borosilicate glass matrix, named R7T7, for disposal in a geological repository. However, in these conditions, after several thousand years, water could arrive in contact with glass and be radio-lysed. In this work, we investigated the irradiation influence and especially the influence of the energy deposition on the residual glass alteration rate regime in pure water. Two types of leaching tests have been carried out. The first were performed on radioactive glass and the second on a SON68 glass (nonradioactive surrogate of R7T7 glass) under external irradiation γ. (author)

  11. Glass Glimpsed

    DEFF Research Database (Denmark)

    Lock, Charles

    2015-01-01

    Glass in poetry as it reflects the viewer and as its power of reflection are both reduced and enhanced by technology.......Glass in poetry as it reflects the viewer and as its power of reflection are both reduced and enhanced by technology....

  12. Cosmos & Glass

    DEFF Research Database (Denmark)

    Beim, Anne

    1996-01-01

    The article unfolds the architectural visions of glass by Bruno Taut. It refers to inspirations by Paul Sheerbart and litterature and the Crystal Chain, also it analyses the tectonic univers that can be found in the glass pavillion for the Werkbund exposition in Cologne....

  13. Glass Dissolution Parameters: Update for Entsorgungsnachweis

    International Nuclear Information System (INIS)

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

  14. Glass Dissolution Parameters: Update for Entsorgungsnachweis

    Energy Technology Data Exchange (ETDEWEB)

    Curti, E

    2003-11-01

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

  15. Spin glasses

    CERN Document Server

    Bovier, Anton

    2007-01-01

    Spin glass theory is going through a stunning period of progress while finding exciting new applications in areas beyond theoretical physics, in particular in combinatorics and computer science. This collection of state-of-the-art review papers written by leading experts in the field covers the topic from a wide variety of angles. The topics covered are mean field spin glasses, including a pedagogical account of Talagrand's proof of the Parisi solution, short range spin glasses, emphasizing the open problem of the relevance of the mean-field theory for lattice models, and the dynamics of spin glasses, in particular the problem of ageing in mean field models. The book will serve as a concise introduction to the state of the art of spin glass theory, usefull to both graduate students and young researchers, as well as to anyone curious to know what is going on in this exciting area of mathematical physics.

  16. Glasses, ceramics, and composites from lunar materials

    Science.gov (United States)

    Beall, George H.

    1992-02-01

    A variety of useful silicate materials can be synthesized from lunar rocks and soils. The simplest to manufacture are glasses and glass-ceramics. Glass fibers can be drawn from a variety of basaltic glasses. Glass articles formed from titania-rich basalts are capable of fine-grained internal crystallization, with resulting strength and abrasion resistance allowing their wide application in construction. Specialty glass-ceramics and fiber-reinforced composites would rely on chemical separation of magnesium silicates and aluminosilicates as well as oxides titania and alumina. Polycrystalline enstatite with induced lamellar twinning has high fracture toughness, while cordierite glass-ceramics combine excellent thermal shock resistance with high flexural strengths. If sapphire or rutile whiskers can be made, composites of even better mechanical properties are envisioned.

  17. Glasses, ceramics, and composites from lunar materials

    Science.gov (United States)

    Beall, George H.

    1992-01-01

    A variety of useful silicate materials can be synthesized from lunar rocks and soils. The simplest to manufacture are glasses and glass-ceramics. Glass fibers can be drawn from a variety of basaltic glasses. Glass articles formed from titania-rich basalts are capable of fine-grained internal crystallization, with resulting strength and abrasion resistance allowing their wide application in construction. Specialty glass-ceramics and fiber-reinforced composites would rely on chemical separation of magnesium silicates and aluminosilicates as well as oxides titania and alumina. Polycrystalline enstatite with induced lamellar twinning has high fracture toughness, while cordierite glass-ceramics combine excellent thermal shock resistance with high flexural strengths. If sapphire or rutile whiskers can be made, composites of even better mechanical properties are envisioned.

  18. The influence of glass composition on crystalline phase stability in glass-ceramic wasteforms

    International Nuclear Information System (INIS)

    Highlights: • Crystalline phase formation shown to depend on glass matrix composition. • Zirconolite forms as the sole crystalline phase only for most aluminous glasses. • Thermodynamics indicate that low silica activity glasses stabilise zirconolite. - Abstract: Zirconolite glass-ceramic wasteforms were prepared using a suite of Na2O–Al2O3–B2O3–SiO2 glass matrices with variable Al:B ratios. Zirconolite was the dominant crystalline phase only for the most alumina rich glass compositions. As the Al:B ratio decreased zirconolite was replaced by sphene, zircon and rutile. Thermodynamic data were used to calculate a silica activity in the glass melt below which zirconolite is the favoured crystalline phase. The concept of the crystalline reference state of glass melts is then utilised to provide a physical basis for why silica activity varies with the Al:B ratio

  19. The influence of glass composition on crystalline phase stability in glass-ceramic wasteforms

    Energy Technology Data Exchange (ETDEWEB)

    Maddrell, Ewan, E-mail: ewan.r.maddrell@nnl.co.uk [National Nuclear Laboratory, Sellafield, Seascale, Cumbria CA20 1PG (United Kingdom); Thornber, Stephanie; Hyatt, Neil C. [Department of Materials Science and Engineering, The University of Sheffield, Mappin Street, Sheffield S1 3JD (United Kingdom)

    2015-01-15

    Highlights: • Crystalline phase formation shown to depend on glass matrix composition. • Zirconolite forms as the sole crystalline phase only for most aluminous glasses. • Thermodynamics indicate that low silica activity glasses stabilise zirconolite. - Abstract: Zirconolite glass-ceramic wasteforms were prepared using a suite of Na{sub 2}O–Al{sub 2}O{sub 3}–B{sub 2}O{sub 3}–SiO{sub 2} glass matrices with variable Al:B ratios. Zirconolite was the dominant crystalline phase only for the most alumina rich glass compositions. As the Al:B ratio decreased zirconolite was replaced by sphene, zircon and rutile. Thermodynamic data were used to calculate a silica activity in the glass melt below which zirconolite is the favoured crystalline phase. The concept of the crystalline reference state of glass melts is then utilised to provide a physical basis for why silica activity varies with the Al:B ratio.

  20. Chemical analysis of simulated high level waste glasses to support stage III sulfate solubility modeling

    International Nuclear Information System (INIS)

    The U.S. Department of Energy (DOE), Office of Environmental Management (EM) is sponsoring an international, collaborative project to develop a fundamental model for sulfate solubility in nuclear waste glass. The solubility of sulfate has a significant impact on the achievable waste loading for nuclear waste forms within the DOE complex. These wastes can contain relatively high concentrations of sulfate, which has low solubility in borosilicate glass. This is a significant issue for low-activity waste (LAW) glass and is projected to have a major impact on the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Sulfate solubility has also been a limiting factor for recent high level waste (HLW) sludge processed at the Savannah River Site (SRS) Defense Waste Processing Facility (DWPF). The low solubility of sulfate in glass, along with melter and off-gas corrosion constraints, dictate that the waste be blended with lower sulfate concentration waste sources or washed to remove sulfate prior to vitrification. The development of enhanced borosilicate glass compositions with improved sulfate solubility will allow for higher waste loadings and accelerate mission completion.The objective of the current scope being pursued by SHU is to mature the sulfate solubility model to the point where it can be used to guide glass composition development for DWPF and WTP, allowing for enhanced waste loadings and waste throughput at these facilities. A series of targeted glass compositions was selected to resolve data gaps in the model and is identified as Stage III. SHU fabricated these glasses and sent samples to SRNL for chemical composition analysis. SHU will use the resulting data to enhance the sulfate solubility model and resolve any deficiencies. In this report, SRNL provides chemical analyses for the Stage III, simulated HLW glasses fabricated by SHU in support of the sulfate solubility model development.

  1. Chemical analysis of simulated high level waste glasses to support stage III sulfate solubility modeling

    Energy Technology Data Exchange (ETDEWEB)

    Fox, K. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-03-17

    The U.S. Department of Energy (DOE), Office of Environmental Management (EM) is sponsoring an international, collaborative project to develop a fundamental model for sulfate solubility in nuclear waste glass. The solubility of sulfate has a significant impact on the achievable waste loading for nuclear waste forms within the DOE complex. These wastes can contain relatively high concentrations of sulfate, which has low solubility in borosilicate glass. This is a significant issue for low-activity waste (LAW) glass and is projected to have a major impact on the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Sulfate solubility has also been a limiting factor for recent high level waste (HLW) sludge processed at the Savannah River Site (SRS) Defense Waste Processing Facility (DWPF). The low solubility of sulfate in glass, along with melter and off-gas corrosion constraints, dictate that the waste be blended with lower sulfate concentration waste sources or washed to remove sulfate prior to vitrification. The development of enhanced borosilicate glass compositions with improved sulfate solubility will allow for higher waste loadings and accelerate mission completion.The objective of the current scope being pursued by SHU is to mature the sulfate solubility model to the point where it can be used to guide glass composition development for DWPF and WTP, allowing for enhanced waste loadings and waste throughput at these facilities. A series of targeted glass compositions was selected to resolve data gaps in the model and is identified as Stage III. SHU fabricated these glasses and sent samples to SRNL for chemical composition analysis. SHU will use the resulting data to enhance the sulfate solubility model and resolve any deficiencies. In this report, SRNL provides chemical analyses for the Stage III, simulated HLW glasses fabricated by SHU in support of the sulfate solubility model development.

  2. DURABLE GLASS FOR THOUSANDS OF YEARS

    Energy Technology Data Exchange (ETDEWEB)

    Jantzen, C.

    2009-12-04

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

  3. GLASSFORM-Version 1: A spreadsheet or an algorithm for generating preliminary glass formulations for waste streams

    International Nuclear Information System (INIS)

    GLASSFORM-Version 1, a spreadsheet or an algorithm software package, was developed for generating preliminary glass formulations for waste streams. A spreadsheet program on Microsoft Excel 97 for Windows 95 was also developed for predicting key glass properties for laboratory scale vitrification studies of simulated waste streams. The algorithm version based on Modula 2, which can be run on Windows-95 or NT, was developed to plot the glass component ratios versus the waste loading. At this time the algorithm was not developed for predicting the key glass properties. The spreadsheet or the algorithm version is an effective tool for developing preliminary glasses with a potential to be chemically durable, dense for volume reduction, of low viscosity for glass pouring, redox controlled, and resistant to corrosion of melter components such as Inconel 690. For a given solid waste stream oxide composition in wt.% or in grams or in ppm and waste loading in wt.%, the spreadsheet or the algorithm calculates glass component ratios that provide an empirical indication of the quality of a candidate glass. In addition to the component ratios for glass quality indicators, glass property composition relationships for glass durability and processability were incorporated into the spreadsheet version. These spreadsheet or algorithm versions can also be used for studying the effects of such actions as varying waste loadings or of varying individual waste components on glass properties and glass component ratios, provided specific glass property models are incorporated. As an example, the software was applied to candidate phosphate-containing glasses at the Idaho Nuclear Technology and Engineering Center (INTEC, previously Idaho Chemical Processing Plant) and also the borosilicate glasses such as the Savannah River Laboratory Environmental Assessment (EA) glass, the Hanford standard (ARM-1) glass, and the French R7T7 glass. Application of the software to new waste streams such as at

  4. Photonic glasses

    CERN Document Server

    Gan, Fuxi

    2006-01-01

    This book introduces the fundamental mechanism of photonic glasses - the linear and nonlinear optical effects in glass under intense light irradiation: phot-induced absorption, refraction, polarization, frequency, coherence and monochromaticity changes. Emphasis is placed on new developments in the structure, spectroscopy and physics of new glassy materials for photonics applications, such as optical communication, optical data storage, new lasers and new photonic components and devices. The book presents the research results of the authors in new glasses for photonics over the last decade. Sa

  5. Chemical states of molybdenum in radioactive waste glass

    International Nuclear Information System (INIS)

    In order to confirm an expectation that the chemical state of molybdenum in glass reflects the phase separation tendency of the yellow solid from the melt of borosilicate glass, simulated waste glasses were prepared, and ESCA analysis was performed using a commercially available electron spectrometer (PHI550 E) with an excitation source consisting of Mg Kα-ray. The effects of the concentration of Mo and FE2O3 and the melting atmosphere (oxidizing or reducing) in which the samples were prepared on the chemical state of Mo and the solubility of MoO3 were examined. From the observation of Mo spectra, it was shown that Mo in waste glass had several valencies, e.g., Mo(3), Mo(4), Mo(5) and Mo(6), while Mo in the yellow solid separated from the melts exhibited hexa-valent state, the peak intensity of higher valencies increased relatively with the increase of MoO3 concentration, but the chemical state of Mo did not change remarkably around the solubility limit of MoO3, the melting atmosphere influenced on the Mo state in the waste glass, the peak intensity of Mo(6) increased relatively with the increasing Fe2O3 concentration, and Mo in devitrified glass exhibited hexa-valent state. (Yoshitake, I.)

  6. Rare earth impact on glass structure and alteration kinetics

    International Nuclear Information System (INIS)

    This work is related to the question of the geological deep repository of high-level waste glass. These wastes include fission products and minor actinides, elements which can be simulated by rare earths. As new glass compositions could enable increased rare earth concentrations, it is crucial to know and understand rare earth impact on glass structure on the one hand, and on glass alteration kinetics or their incorporation into an altered layer. This work studied simplified borosilicate glasses in order to limit synergetic effects between rare earths and other elements. Various complementary techniques were used to characterize pristine and altered glasses (solid-high resolution NMR, Raman spectroscopy, fluorescence, SIMS, SAXS). Firstly, the structural role of a rare earth is discussed and is compared to a calcium cation. The local environment of rare earths is also probed. Secondly, rare earth (nature and concentration) impact on several alteration regimes was studied (initial rate, rate drop). Then, after alteration, rare earth elements being retained within the altered layer, the structural impact of rare earth elements (and their local environment) in this alteration layer was also investigated. (author)

  7. Modeling of Glass Making Processes for Improved Efficiency

    Energy Technology Data Exchange (ETDEWEB)

    Thomas P. Seward III

    2003-03-31

    The overall goal of this project was to develop a high-temperature melt properties database with sufficient reliability to allow mathematical modeling of glass melting and forming processes for improved product quality, improved efficiency and lessened environmental impact. It was initiated by the United States glass industry through the NSF Industry/University Center for Glass Research (CGR) at Alfred University [1]. Because of their important commercial value, six different types/families of glass were studied: container, float, fiberglass (E- and wool-types), low-expansion borosilicate, and color TV panel glasses. CGR member companies supplied production-quality glass from all six families upon which we measured, as a function of temperature in the molten state, density, surface tension, viscosity, electrical resistivity, infrared transmittance (to determine high temperature radiative conductivity), non-Newtonian flow behavior, and oxygen partial pres sure. With CGR cost sharing, we also studied gas solubility and diffusivity in each of these glasses. Because knowledge of the compositional dependencies of melt viscosity and electrical resistivity are extremely important for glass melting furnace design and operation, these properties were studied more fully. Composition variations were statistically designed for all six types/families of glass. About 140 different glasses were then melted on a laboratory scale and their viscosity and electrical resistivity measured as a function of temperature. The measurements were completed in February 2003 and are reported on here. The next steps will be (1) to statistically analyze the compositional dependencies of viscosity and electrical resistivity and develop composition-property response surfaces, (2) submit all the data to CGR member companies to evaluate the usefulness in their models, and (3) publish the results in technical journals and most likely in book form.

  8. Physicochemical Properties of Gold Nanostructures Deposited on Glass

    Directory of Open Access Journals (Sweden)

    Zdenka Novotna

    2014-01-01

    Full Text Available Properties of gold films sputtered onto borosilicate glass substrate were studied. UV-Vis absorption spectra were used to investigate optical parameters. XRD analysis provided information about the gold crystalline nanostructure, the texture, and lattice parameter and biaxial tension was also determined by the XRD method. The surface morphology was examined by atomic force microscopy (AFM; chemical structure of sputtered gold nanostructures was examined by X-ray photoelectron spectroscopy (ARXPS. The gold crystallites are preferentially [111] oriented on the sputtered samples. Gold deposition leads to dramatic changes in the surface morphology in comparison to pristine glass substrate. Oxygen is not incorporated into the gold layer during gold deposition. Experimental data on lattice parameter were also confirmed by theoretical investigations of nanoclusters using tight-binding potentials.

  9. Optically transparent, mechanically durable, nanostructured superhydrophobic surfaces enabled by spinodally phase-separated glass thin films

    International Nuclear Information System (INIS)

    We describe the formation and properties of atomically bonded, optical quality, nanostructured thin glass film coatings on glass plates, utilizing phase separation by spinodal decomposition in a sodium borosilicate glass system. Following deposition via magnetron sputtering, thermal processing and differential etching, these coatings are structurally superhydrophilic (i.e., display anti-fogging functionality) and demonstrate robust mechanical properties and superior abrasion resistance. After appropriate chemical surface modification, the surfaces display a stable, non-wetting Cassie–Baxter state and exhibit exceptional superhydrophobic performance, with water droplet contact angles as large as 172°. As an added benefit, in both superhydrophobic and superhydrophilic states these nanostructured surfaces can block ultraviolet radiation and can be engineered to be anti-reflective with broadband and omnidirectional transparency. Thus, the present approach could be tailored toward distinct coatings for numerous markets, such as residential windows, windshields, specialty optics, goggles, electronic and photovoltaic cover glasses, and optical components used throughout the US military. (paper)

  10. Microstructural characterization of halite inclusions in a glass-bonded ceramic waste form

    International Nuclear Information System (INIS)

    A glass-bonded ceramic waste form is being developed to immobilize high-level chloride waste salts generated during the conditioning of spent sodium-bonded nuclear fuel for disposal. The waste salt is loaded into zeolite cavities, mixed with a borosilicate glass, and consolidated at 800--900 C by hot isostatic pressing. During this process, small amounts of halite are generated, whereas the zeolite converts to the mineral sodalite, which retains most of the waste salt. In this work, optical microscopy, scanning electron microscopy, and transmission electron microscopy were used to characterize the halite inclusions in the final waste form. The halite inclusions were detected within micron- to submicron-sized pores that form within the glass phase in the vicinity of the sodalite/glass interface. The chemical nature and distribution of the halite inclusions were determined. The particular microstructure of the halite inclusions has been related to the corrosion of the ceramic waste form

  11. Effects of alteration product precipitation on glass dissolution

    International Nuclear Information System (INIS)

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

  12. Development and adoption of low sodium glass frit for vitrification of high level radioactive liquid waste at Tarapur

    International Nuclear Information System (INIS)

    High level Liquid Waste (HLW) is generated during the reprocessing of spent nuclear fuel which is used to recover uranium and plutonium. More than 99% of the fission product activity generated during the burning of nuclear fuel in the reactor is present in HLW. For the efficient management of HLW by vitrification, sodium borosilicate glass has been adopted worldwide. Sodium oxide acts as modifier in glass matrix and variation in its concentration may vary the properties of the glass and hence the melter parameters. The HLW presently used for vitrification has higher concentration of sodium. As the composition of the base glass is fixed the concentration of Na in the HLW is one of the limiting factors for the waste loading for the vitrification process. Present article gives a brief account of the formulation of a base glass frit with lower sodium content and the feedback after implementing in the vitrification plant. (author)

  13. Fabrication and characterization of MCC [Materials Characterization Center] approved testing material---ATM-2, ATM-3, and ATM-4 glasses

    International Nuclear Information System (INIS)

    Materials Characterization Center glasses ATM-2, ATM-3, and ATM-4 are designed to simulate high-level waste glasses that are likely to result from the reprocessing of commercial nuclear reactor fuels. The three Approved Testing Materials (ATMs) are borosilicate glasses based upon the MCC-76-68 glass composition. One radioisotope was added to form each ATM. The radioisotopes added to form ATM-2, ATM-3, and ATM-4 were 241Am, 237Np, and 239Pu, respectively. Each of the ATM lots was produced in a nominal lot size of 450 g from feed stock melted in a nitrogen-atmosphere glove box at 1200/degree/C in a platinum crucible. Each ATM was then cast into bars. Analyzed compositions of these glasses are listed. The nonradioactive elements were analyzed by inductively coupled argon plasma atomic emission spectroscopy (ICP), and the radioisotope analyses were done by alpha energy analysis. Results are discussed. 7 refs., 3 figs., 5 tabs

  14. Qualification of a Radioactive High Aluminum Glass for Processing in the Defense Waste Processing Facility at the Savannah River Site

    International Nuclear Information System (INIS)

    At the Savannah River Site (SRS) the Defense Waste Processing Facility (DWPF) has been immobilizing SRS's radioactive high level waste (HLW) sludge into a borosilicate glass for approximately eleven years. Currently the DWPF is immobilizing HLW sludge in Sludge Batch 4 (SB4). Each sludge batch is nominally two million liters of HLW and produces nominally five hundred stainless steel canisters 0.6 meters in diameter and 3 meters tall filled with the borosilicate glass. In SB4 and earlier sludge batches, the Al concentration has always been rather low, (less than 9.5 weight percent based on total dried solids). It is expected that in the future the Al concentrations will increase due to the changing composition of the HLW. Higher Al concentrations could introduce problems because of its known effect on the viscosity of glass melts and increase the possibility of the precipitation of nepheline in the final glass and decrease its durability. In 2006 Savannah River National Laboratory (SRNL) used DWPF processes to immobilize a radioactive HLW slurry containing 14 weight percent Al to ensure that this waste is viable for future DWPF processing. This paper presents results of the characterization of the high Al glass prepared in that demonstration. At SRNL, a sample of the processed high Al HLW slurry was mixed with an appropriate glass frit as performed in the DWPF to make a waste glass containing nominally 30% waste oxides. The glass was prepared by melting the frit and waste remotely at 1150 deg. C. The glass was then characterized by - determining the chemical composition of the glass including the concentrations of several actinide and U-235 fission products, - calculating the oxide waste loading of the glass based on the chemical composition and comparing it to that of the target - determining if the glass composition met the DWPF processing constraints such as glass melt viscosity and liquidus temperature along with a waste form affecting constraint that prevents

  15. Reactive cluster model of metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Travis E. [Molecular Theory Group, Colorado School of Mines, Golden, Colorado 80401 (United States); School of Physics, The University of Sydney, Sydney, New South Wales 2006 (Australia); Miorelli, Jonathan; Eberhart, Mark E. [Molecular Theory Group, Colorado School of Mines, Golden, Colorado 80401 (United States)

    2014-02-28

    Though discovered more than a half century ago metallic glasses remain a scientific enigma. Unlike crystalline metals, characterized by short, medium, and long-range order, in metallic glasses short and medium-range order persist, though long-range order is absent. This fact has prompted research to develop structural descriptions of metallic glasses. Among these are cluster-based models that attribute amorphous structure to the existence of clusters that are incommensurate with crystalline periodicity. Not addressed, however, are the chemical factors stabilizing these clusters and promoting their interconnections. We have found that glass formers are characterized by a rich cluster chemistry that above the glass transformation temperature promotes exchange as well as static and vibronic sharing of atoms between clusters. The vibronic mechanism induces correlated motions between neighboring clusters and we hypothesize that the distance over which these motions are correlated mediates metallic glass stability and influences critical cooling rates.

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

    International Nuclear Information System (INIS)

    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 (SiO2 + Al2O3), and between the initial rate and the (Na2O + Li2O + B2O3) / (SiO2 + Al2O3) 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

  17. Effects of β-irradiation in multicomponent glasses simulating the matrix of the French nuclear waste glass (R7T7)

    International Nuclear Information System (INIS)

    4-, 5- and 6-oxide components alumino-borosilicate glasses, with compositions closed to the matrix of the french nuclear glass 'R7T7' have been irradiated with electrons (β) at 2.5 MeV with a Van de Graff accelerator. These glasses have been studied after irradiation with different spectroscopic methods: Electron Paramagnetic Resonance for the study of defects, Raman Micro-spectroscopy for the study of amorphous network evolution under irradiation, and by 11B MAS NMR. The results of these studies are presented here. It shows in particular a great sensibility to the irradiation conditions like dose rate and irradiation temperature, who are therefore important parameters for the representativeness of such experiments. (authors)

  18. Evaluation of glass vitrification techniques on iron ratio determinations

    International Nuclear Information System (INIS)

    High-level liquid waste at the Savannah River Site (SRS) will be processed into borosilicate glass at the Defense Waste Processing Facility (DWPF). Waste glass will be transported to a geologic repository for permanent disposal. Control of the redox properties of the melter feed is necessary for smooth operation of the melter. The Fe(II)/total Fe ratio in glass is a measure of the redox conditions in the melter. To simulate final glass product conditions, melter feed samples will be vitrified at the DWPF laboratory. A colorimetric method was used to determine the Fe(II)/total Fe ratio on vitrified melter feed samples. Because the crucible vitrification technique can have a large effect on the Fe(II)/total Fe ratio, crucible sealing during vitrification of the waste feed sample, and the type of heating applied during vitrification, were the variables investigated for Fe(II)/total Fe ratio measurement effects. Various lid sealants were used for determining crucible sealing effects. Microwave and conventional heating were tested for glass vitrifications. Microwave heating and a nepheline gel sealant, to exclude oxygen from the alumina crucibles during vitrification, was adopted for use at the DWPF laboratory. This paper discusses microwave vitrification and crucible sealing techniques

  19. Blue light emission from a glass/liquid interface for real-time monitoring of a laser-induced etching process

    International Nuclear Information System (INIS)

    An organic dye, Oil-Red-O, dissolved in p-xylene was used for laser-induced backside wet etching using a visible laser (visible-LIBWE) for the first time. Blue light (360–500 nm) emission from the glass/liquid interface was observed during the etching of borosilicate glass using a nanosecond Q-switched green laser. The emission was confirmed to accompany the etching process. The UV–visible spectrum consists of characteristic peaks of metals, which are the components of the glass. The maximal emission intensity occurs when the laser focusing is at the glass/liquid interface. The etching threshold measured by observing the blue light emission is comparable to that determined by the traditional method. We concluded that the emission is the plasma emission of the etched glass. By measuring the plasma emission, the occurrence of the etching and the crack formation in the glass can be monitored in real time

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

    Energy Technology Data Exchange (ETDEWEB)

    Ellison, A.J.G.; Mazer, J.J.; Ebert, W.L. [Argonne National Lab., IL (United States). Chemical Technology Div.

    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.