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)

Phase separation of cesium from lead borosilicate glass by heat treatment under a reducing atmosphere

Energy Technology Data Exchange (ETDEWEB)

Xu, Zhanglian; Okada, Takashi, E-mail: t-okada@u-fukui.ac.jp; Nishimura, Fumihiro; Yonezawa, Susumu

2016-11-05

Highlights: • Cesium was phase separated from lead borosilicate glass under a reductive atmosphere. • The phase separation occurred on the glass surface that was in contact with the gas. • The leachability of cesium was enhanced by the phase separation. • The degree of such enhancement varied depending on the heat treatment conditions. - Abstract: A phase-separation technique for removing sodium from glass using a heat-treatment method under a reducing atmosphere was previously developed for sodium recovery from waste glass. In this study, this technique was applied to cesium-containing lead borosilicate glass to concentrate the cesium in phase-separated sodium-rich materials for efficient cesium extraction. The theoretical phase-separation temperature of the sodium-rich phase was simulated by thermodynamic equilibrium calculations and was predicted to occur below 700 °C for lead borosilicate glass. Experimentally, a simulated lead borosilicate glass was melted at 1000 °C and subsequently annealed below 700 °C under a CO-containing reducing atmosphere. The phase separation of cesium was found to occur with sodium enrichment on the glass surface that was in contact with the gas phase, promoting cesium extraction from the treated glass using water. The cesium extraction efficiency was affected by the surface area of the treated glass that was in contact with water, and under the examined conditions, the cesium extraction efficiency was up to 66%. Phase separation using reductive heat treatment, combined with a water leaching technique, is suggested to be effective for extracting cesium incorporated in borosilicate glass waste.

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...

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.

X-ray tomography of feed-to-glass transition of simulated borosilicate waste glasses

Czech Academy of Sciences Publication Activity Database

Harris, W.H.; Guillen, D.P.; Kloužek, Jaroslav; Pokorný, P.; Yano, T.; Lee, S.; Schweiger, M. J.; Hrma, P.

2017-01-01

Roč. 100, č. 9 (2017), s. 3883-3894 ISSN 0002-7820 Institutional support: RVO:67985891 Keywords : borosilicate glass * computed tomography * glass melting * morphology * nuclear waste * X-ray Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 2.841, year: 2016

Influence of Glass Property Restrictions on Hanford HLW Glass Volume

International Nuclear Information System (INIS)

Kim, Dong-Sang; Vienna, John D.

2001-01-01

A systematic evaluation of Hanford High-Level Waste (HLW) loading in alkali-alumino-borosilicate glasses was performed. The waste feed compositions used were obtained from current tank waste composition estimates, Hanford's baseline retrieval sequence, and pretreatment processes. The waste feeds were sorted into groups of like composition by cluster analysis. Glass composition optimization was performed on each cluster to meet property and composition constraints while maximizing waste loading. Glass properties were estimated using property models developed for Hanford HLW glasses. The impacts of many constraints on the volume of HLW glass to be produced at Hanford were evaluated. The liquidus temperature, melting temperature, chromium concentration, formation of multiple phases on cooling, and product consistency test response requirements for the glass were varied one- or many-at-a-time and the resultant glass volume was calculated. This study shows clearly that the allowance of crystalline phases in the glass melter can significantly decrease the volume of HLW glass to be produced at Hanford.

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

International Nuclear Information System (INIS)

Plodinec, M.J.; Wicks, G.G.; Bibler, N.E.

1982-01-01

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 1150 0 C. 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

Study of physical properties of strontium based alumino-borosilicate glasses

Science.gov (United States)

Kaur, Mandeep; Kaur, Gurbinder; Kumar, V.

2018-05-01

In the present study, an attempt has been made to study the influence of CaO/Mgo ratio (R) on different physical properties of (10+x)CaO-(10-x)-MgO-10SrO-10B2O3-20Al2O3-40SiO2 glasses. The novel glass series has been synthesized by melt quenching technique. The parameters like reflection loss and dielectric constant have been determined. Also, molar refraction, molar electronic polarizability and oxygen packing density have been calculated on the basis of measured values of density, molar volume and refractive index of the glasses.

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

International Nuclear Information System (INIS)

Trotignon, Laurent

1990-01-01

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

Chemical durability of borosilicate glasses containing simulated high-level nuclear wastes, 1

International Nuclear Information System (INIS)

Hara, Shigeo; Terai, Ryohei; Yamanaka, Hiroshi

1983-01-01

The Soxhlet-type leaching test apparatus has been developed to evaluate the chemical durability of some borosilicate glasses containing simulated High-Level nuclear Wastes, HLW. After the leaching over the temperature range of 50 0 -95 0 C, the weight loss of specimens with time was determined on both the samples of blocks and grains, and various components dissolved into water were analyzed by atomic absorption and colorimetry technique. It was found that Soxhlet-type test method was more useful than JIS test method, because the specimens in Soxhlet type apparatus were forced always to react with pure water and the mechanism of leaching could be evaluate accurately. The chemical durability of commercial glasses decreases generally with increasing of alkali contents in glasses. In the case of these borosilicate glasses containing HLW, however, the leachability was apparently independent on the alkali contents because of the complexity of these glass compositions. The variation of leaching rate with temperature suggests that dissolution mechanism changes with temperature. (author)

Crystallisation mechanism of a multicomponent lithium alumino-silicate glass

International Nuclear Information System (INIS)

Wurth, R.; Pascual, M.J.; Mather, G.C.; Pablos-Martín, A.; Muñoz, F.; Durán, A.; Cuello, G.J.; Rüssel, C.

2012-01-01

A base glass of composition 3.5 Li 2 O∙0.15 Na 2 O∙0.2 K 2 O∙1.15 MgO∙0.8 BaO∙1.5 ZnO∙20 Al 2 O 3 ∙67.2 SiO 2 ∙2.6 TiO 2 ∙1.7 ZrO 2 ∙1.2 As 2 O 3 (in wt.%), melted and provided by SCHOTT AG (Mainz), was used to study the crystallisation mechanism of lithium alumino-silicate glass employing X-ray diffraction combined with neutron diffraction and non-isothermal differential scanning calorimetry (DSC). A high-quartz solid solution of LiAlSi 2 O 6 with nanoscaled crystals forms at 750 °C. Quantitative Rietveld refinement of samples annealed at 750 °C for 8 h determined a crystallised fraction of around 59 wt.%. The room temperature crystallised phase adopts an ordered, β-eucryptite-like structure (2 × 2 × 2 cell) with Li ordered in the structural channels. The Avrami parameter (n ∼ 4), calculated from DSC data using different theoretical approaches, indicates that bulk crystallisation occurs and that the number of nuclei increases during annealing. The activation energy of the crystallisation is 531 ± 20 kJ mol −1 . - Highlights: ► Nanoscaled high-quartz crystals from a multicomponent lithium alumino-silicate glass. ► Combined X-ray and neutron diffraction structural refinement. ► β-Eucryptite-like structure (2 × 2×2 cell) with Li ordered in the structural channels. ► 3-Dimensional bulk crystallisation mechanism with an increasing number of nuclei. ► Usage and validation of an alternative approach to calculate the Avrami parameter.

Rutherford backscattering investigation of the corrosion of borosilicate glass

International Nuclear Information System (INIS)

Sales, B.C.; Boatner, L.A.; Naramoto, H.; White, C.W.

1981-10-01

The RBS spectra from Frit 21 borosilicate glasses doped with 5 wt % UO 2 , SrO, or Cs 2 O show that: during the initial stages of leaching (0 to 3 h) there is a substantial (300 to 500%) enhancement in the concentration of U, Sr, Ca, and Ti in the outer surface layer and that this enhancement is accompanied by a large depletion of Na, Si, and Cs; and upon further leaching under static conditions (24 h) the leached surface layer composition is indistinguishable from the unleached surface. Other borosilicate glasses such as PNL 76-68 may eventually show the same behavior if the final equilibrium pH value is greater than 9. The technique of Rutherford backscattering depth profile analysis can be a powerful tool for investigating the initial stages of glass corrosion

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

Directory of Open Access Journals (Sweden)

Jayesh A Bafna

Full Text Available 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.

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

International Nuclear Information System (INIS)

Kaushik, C.P.; Mishra, R.K.; Sengupta, P.; Kumar, Amar; Das, D.; Kale, G.B.; Raj, Kanwar

2006-01-01

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 (SiO 2 : 30.5 wt%, B 2 O 3 : 20.0 wt%, Na 2 O: 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

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

International Nuclear Information System (INIS)

Cunnane, J.C.

1994-03-01

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

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

International Nuclear Information System (INIS)

Harrison, M. T.; Scales, C. R.

2008-01-01

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% HfO 2 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)

Investigation on neptunium in a borosilicate glass

International Nuclear Information System (INIS)

Poirot, I.

1988-03-01

The oxidization state and coordination of neptunium, introduced as dopant in borosilicate glasses were studied through optical, Mossbauer spectroscopies and magnetic measurements. The neptunium oxide, introduced previously as NpO 2 is reduced during the melting process of the glass. This leads to an equilibrium in which the ratio of Np 4+ to Np 3+ valences depends on experimental conditions. Spectroscopic analysises conduct to postulate the presence of different sites for each of the oxydation states of neptunium [fr

Investigation of alumino-phosphate glasses for iodine conditioning

International Nuclear Information System (INIS)

Lemesle, T.

2013-01-01

Iodine 129 is a long-lived intermediate level radioactive waste, which is currently managed by isotopic dilution. In view of an alternative management by geological disposal, we aimed at developing phosphate glasses of the AgI-Ag 2 O-P 2 O 5 -Al 2 O 3 system, elaborated at low temperature and without iodine volatilization. Alumina is expected to induce crosslinking of the phosphate network and thus to improve the thermal and chemical properties. To define a glass composition that meets the specifications, we varied the level of iodine, the Ag 2 O/P 2 O 5 ratio and alumina content. For 1 g.cm -3 of iodine, SEM-EDS observations indicate that alumina solubility is limited to 0.5% mol., independently of Ag 2 O/P 2 O 5 ratio. The structural study by 31 P, 27 Al and 109 Ag MAS NMR, shows that aluminum adopts an octahedral coordination that effectively contributes to the crosslinking of the glassy network and iodine is incorporated without clustering. 31 P- 27 Al NMR correlations confirmed the presence of an alumino-phosphate network, and 31 P- 31 P correlations indicate that iodine does not change the connectivity of the glass network. The glass composition 28,8AgI-44,2Ag 2 O-26,5P 2 O 5 -0,5Al 2 O 3 presents the best compromise between the level of incorporation of iodine and the chemical durability, has a glass transition temperature of 123 C and an initial alteration rate in pure water at 50 C of 6 g.m -2 .d -1 . The long-term behavior of this glass is controlled by a post-alteration structure based on pyrophosphate, which holds nearly 80% of the initial iodine. (author) [fr

Mechanical behavior of cellular borosilicate glass with pressurized Ar-filled closed pores

International Nuclear Information System (INIS)

Wang Bo; Matsumaru, Koji; Yang Jianfeng; Fu Zhengyi; Ishizaki, Kozo

2012-01-01

High strength borosilicate foams were fabricated by melting glass powder under high-pressure argon gas and subsequent heat treatment of the glass bulk at atmospheric pressure. In the first step, borosilicate glass powder was melted at 1100 °C for 1 h by capsule-free hot isostatic pressing (HIPing) under a high gas pressure of 10–70 MPa. Pressurized Ar-filled spherical pores were introduced into the glass, and argon atoms were dissolved in the glass network structure. The expansion of argon-filled pores and the release of the dissolved Ar gas resulted in the formation of pressurized Ar-filled closed pores by isothermal heat treatment at 800 °C for 10 min. A high porosity of up to 80% with a bimodal distribution of micro-size cells was obtained for the resultant cellular borosilicate glass. By increasing the total gas pressure from 10 to 70 MPa, the compressive strength and the Young’s modulus were increased considerably from 15 to 52 MPa and from 4.1 to 12.6 GPa, respectively, which can be substantially attributed to the high collapse stress from the high enclosed gas pressure. The cellular glass with a high porosity showed a large failure strain under uniaxial compression.

Design and test of the borosilicate glass burnable poison rod for Qinshan nuclear power plant core

International Nuclear Information System (INIS)

Huang Jinhua; Sun Hanhong

1988-08-01

Material for the burnable poison of Qinshan Nuclear Power Plant core is GG-17 borosilicate glass. The chemical composition and physico-chemical properties of GG-17 is very close to Pyrex-7740 glass used by Westinghouse. It is expected from the results of the experiments that the borosilicate glass burnable poison rod can be successfully used in Qinshan Nuclear Power Plant due to good physical, mechanical, corrosion-resistant and irradiaton properties for both GG-17 glass and cold-worked stainless steel cladding. Change of material for burnable poison from boron-bearing stainless steel to borosilicate glass will bring about much more economic benefit to Qinshan Naclear Power Plant

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

Energy Technology Data Exchange (ETDEWEB)

Lenoir, Marion [Service de Confinement des Dechets et Vitrification - Laboratoire d' Etudes de Base sur les Verres, CEA Valrho, Centre de Marcoule, 30207 Bagnols sur Ceze (France); Physique des Mineraux et des Magmas, UMR 7047 - CNRS, Institut de Physique du Globe de Paris, 7 place Jussieu, 75252 Paris Cedex 05 (France); Grandjean, Agnes [Service de Confinement des Dechets et Vitrification - Laboratoire d' Etudes de Base sur les Verres, CEA Valrho, Centre de Marcoule, 30207 Bagnols sur Ceze (France); Neuville, Daniel R. [Physique des Mineraux et des Magmas, UMR 7047 - CNRS, Institut de Physique du Globe de Paris, 7 place Jussieu, 75252 Paris Cedex 05 (France)

2008-07-01

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{sup -1} was scaled to the sum of the integrated bands between 800 and 1200 cm{sup -1}, bands that are assigned to Q{sup n} 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)

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

International Nuclear Information System (INIS)

McDonell, W.R.

1982-04-01

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

Preparation and characterization of an improved borosilicate glass for the solidification of high level radioactive fission product solutions (HLW). Pt. 2

International Nuclear Information System (INIS)

Kahl, L.; Ruiz-Lopez, M.C.; Saidl, J.; Dippel, T.

1982-04-01

In the 'Institut fuer Nuklare Entsorgungstechnik' the borosilicate glass VG 98/12 has been developed for the solidification of the high level radioactive waste (HLW). This borosilicate glass can be used in a direct heated ceramic melter and forms together with the HLW the borosilicate glass product GP 98/12. This borosilicate glass product has been examined in detail both in liquid and solid state. The elements contained in the HLW can be incorporated without problems. Only in a few exceptions the concentration must be kept below certain limits to exclude the formation of a second phase ('yellow phase') by separation. No spontaneous crystallization and no crystallization over a long time could be observed as long as the temperature of the borosilicate glass product is kept below its transformation area. Simulating accidental conditions in the final storage, samples had been leached at temperatures up to 200 0 C and pressures up to 130 bar with saturated rock salt brine and saturated quinary salt brine. The leaching process seems to be stopped by the formed 'leached layer' on the surface of the borosilicate glass product after a limited leaching time. Detailed investigations have been started to explain this phenomenon. (orig.) [de

Photon emission induced by brittle fracture of borosilicate glasses

Energy Technology Data Exchange (ETDEWEB)

Shiota, Tadashi, E-mail: tshiota@ceram.titech.ac.jp [Department of Metallurgy and Ceramic Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Sato, Yoshitaka [Department of Metallurgy and Ceramic Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Kishi, Tetsuo [Department of Chemistry and Materials Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Yasuda, Kouichi [Department of Metallurgy and Ceramic Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan)

2016-05-15

Photon emission (PE) at wavelength ranges of 430–490 nm (B-PE), 500–600 nm (G-PE) and 610–680 nm (R-PE) caused by brittle fracture was simultaneously measured in the nanosecond-to-microsecond and millisecond time domains for two types of borosilicate glasses: Pyrex-type Tempax glass and BK7 glass. The results were compared to those for silica and soda lime glasses. The time dependence of the PE of Tempax glass was similar to that of silica glass, while the PE intensity was lower. Because Tempax glass contains both silica-rich and borate-rich amorphous phases, the PE must be mainly produced by the fracture of the silica-rich phase. Moreover, the proportion of B-PE of Tempax glass was higher than that of silica glass. This suggests that the measured B-PE might also include very weak PE caused by the fracture of the borate-rich phase. The PE time dependence of BK7 glass was similar to that of soda lime glass, which was different from the case for Tempax glass. The PE intensity of BK7 glass was slightly higher than that of soda lime glass, but much lower than that of Tempax glass. The result indicates that non-bridging oxygen in the glasses affects crack propagation behavior and reduces the PE. - Highlights: • Photon emission (PE) upon brittle fracture of borosilicate glasses was measured. • Pyrex-type Tempax and BK7 glasses showed different PE characteristics. • The rupture of Si–O bonds produces much stronger PE than that of B–O bonds. • Non-bridging oxygen in glass affects crack propagation behavior and reduces the PE.

Utilization of borosilicate glass for transuranic waste immobilization

International Nuclear Information System (INIS)

Ledford, J.A.; Williams, P.M.

1979-01-01

Incinerated transuranic waste and other low-level residues have been successfully vitrified by mixing with boric acid and sodium carbonate and heating to 1050 0 C in a bench-scale continuous melter. The resulting borosilicate glass demonstrates excellent mechanical durability and chemical stability

Investigation of U3O8 immobilization in the GP-91 borosilicate glass by induction melter with a cold crucible (CCIM)

International Nuclear Information System (INIS)

Matyunin, Y.I.; Demin, A.V.; Smelova, T.V.; Yudintsev, S.V.; Lapina, M.I.

1997-01-01

One of the most promising and intensively developed methods for the solidification of high-level wastes is their vitrification with the use of a cold crucible induction melter (CCIM), which offers a number of advantages over ceramic melter. This work is concerned with comparison studies on the behavior of uranium in vitreous borosilicate materials synthesized by the traditional technique (melting in muffle furnaces) and CCIM method. The incorporation of uranium oxide U 3 O 8 into the GP-91 borosilicate glass with the use of CCIM technology is investigated. The limiting solubility of uranium in the GP-91 borosilicate glass is evaluated. The phase composition of precipitated dispersed particles based on uranium is determined. Some physicochemical properties of synthesized materials are explored. Investigations into the behavior of uranium in borosilicate glass prepared in the CCIM show a feasibility to synthesize the X-ray amorphous homogeneous borosilicate glasses incorporating as much as 25 - 28 wt% uranium, which is 4 - 5 times larger than that in glasses obtained by the traditional method. (author)

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.

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

International Nuclear Information System (INIS)

Cunnane, J.C.; Allison, J.

1993-01-01

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

Preliminary assessment of modified borosilicate glasses for chromium and ruthenium immobilization

Energy Technology Data Exchange (ETDEWEB)

Farid, Osama M. [Reactors Department, Nuclear Research Center, Atomic Energy Authority of Egypt, P.O. 13759, Inshas, Cairo (Egypt); Centre of Nuclear Engineering (CNE), Department of Materials, Imperial College London, London, SW7 2BP (United Kingdom); Abdel Rahman, R.O., E-mail: alaarehab@yahoo.com [Hot Laboratory Center, Atomic Energy Authority of Egypt, P.O. 13759, Inshas, Cairo (Egypt)

2017-01-15

The feasibility of using modified alkali borosilicate glasses for ruthenium and chromium immobilization is preliminary assessed by investigating the immobilization system structure under normal conditions. Within this context, reference alkali borosilicate, and simulated Magnox-modified glasses were prepared and studied. The results indicate that ruthenium is immobilized in the vitreous structure as encapsulated RuO{sub 2} crystallites that act as seeds for heterogeneous nucleation of other crystalline phases. The presence of Zn, as modifier, has contributed to chromium immobilization in zincochromite spinel structure, whereas Ca is accommodated in the vitreous structure. Immobilization performance was evaluated by conducting conservative static leach test and studying the leached glass. Leached glass morphology was altered, where near surface reference glass is leached over 400 nm and simulated Magnox-modified sample is altered over 300 nm. Normalized release rates are within normal range for borosilicate material. For simulated Magnox-modified sample, Ca and alkali structural element, i.e. Na and Li, are leached via ion-exchange reaction. The ion-exchanged fraction equals 1.06 × 10{sup −8} mol/m{sup 2} s and chromium has slightly lower normalized release rate value than ruthenium. - Highlights: • The presence of modifiers and waste oxides led to localized de-vitrification. • Ruthenium is encapsulated within the vitreous glass network as RuO{sub 2} crystals. • Chromium is immobilized within the zincochromite spinel structure. • Pitting and cracks induced by leaching did not affect the immobilization performance.

Crystallisation mechanism of a multicomponent lithium alumino-silicate glass

Energy Technology Data Exchange (ETDEWEB)

Wurth, R. [Otto-Schott-Institut, Jena University, Fraunhoferstr. 6, 07743 Jena (Germany); Pascual, M.J., E-mail: mpascual@icv.csic.es [Instituto de Ceramica y Vidrio, CSIC, Kelsen 5, 28049 Madrid (Spain); Mather, G.C.; Pablos-Martin, A.; Munoz, F.; Duran, A. [Instituto de Ceramica y Vidrio, CSIC, Kelsen 5, 28049 Madrid (Spain); Cuello, G.J. [Institut Laue-Langevin, Boite Postale 156, 38042 Grenoble Cedex 9 (France); Ruessel, C. [Otto-Schott-Institut, Jena University, Fraunhoferstr. 6, 07743 Jena (Germany)

2012-06-15

A base glass of composition 3.5 Li{sub 2}O Bullet-Operator 0.15 Na{sub 2}O Bullet-Operator 0.2 K{sub 2}O Bullet-Operator 1.15 MgO Bullet-Operator 0.8 BaO Bullet-Operator 1.5 ZnO Bullet-Operator 20 Al{sub 2}O{sub 3} Bullet-Operator 67.2 SiO{sub 2} Bullet-Operator 2.6 TiO{sub 2} Bullet-Operator 1.7 ZrO{sub 2} Bullet-Operator 1.2 As{sub 2}O{sub 3} (in wt.%), melted and provided by SCHOTT AG (Mainz), was used to study the crystallisation mechanism of lithium alumino-silicate glass employing X-ray diffraction combined with neutron diffraction and non-isothermal differential scanning calorimetry (DSC). A high-quartz solid solution of LiAlSi{sub 2}O{sub 6} with nanoscaled crystals forms at 750 Degree-Sign C. Quantitative Rietveld refinement of samples annealed at 750 Degree-Sign C for 8 h determined a crystallised fraction of around 59 wt.%. The room temperature crystallised phase adopts an ordered, {beta}-eucryptite-like structure (2 Multiplication-Sign 2 Multiplication-Sign 2 cell) with Li ordered in the structural channels. The Avrami parameter (n {approx} 4), calculated from DSC data using different theoretical approaches, indicates that bulk crystallisation occurs and that the number of nuclei increases during annealing. The activation energy of the crystallisation is 531 {+-} 20 kJ mol{sup -1}. - Highlights: Black-Right-Pointing-Pointer Nanoscaled high-quartz crystals from a multicomponent lithium alumino-silicate glass. Black-Right-Pointing-Pointer Combined X-ray and neutron diffraction structural refinement. Black-Right-Pointing-Pointer {beta}-Eucryptite-like structure (2 Multiplication-Sign 2 Multiplication-Sign 2 cell) with Li ordered in the structural channels. Black-Right-Pointing-Pointer 3-Dimensional bulk crystallisation mechanism with an increasing number of nuclei. Black-Right-Pointing-Pointer Usage and validation of an alternative approach to calculate the Avrami parameter.

57Fe Moessbauer effect in borosilicate glasses

International Nuclear Information System (INIS)

Music, S.

1989-01-01

The present study was carried out to elucidate the valence state of iron and its co-ordination in borosilicate glasses, which are being investigated as possible solidification matrices for the immobilization of a simulated nuclear waste. 57 Fe Mossbauer spectroscopy was used as the experimental technique. The chemical compositions of glass samples and the experimental conditions for the preparation of these samples are given. Iron in the form of haematite (α-Fe 2 O 3 ) was used as doping material. Details of the experimental procedure have previously been described. Isomer shifts are calculated relative to α-iron. The results indicate a strong dependence of the valency of the iron and its coordination on the chemical composition of the glass and the Fe 2 O 3 content. The method of preparing the glasses also influences the state of the iron in oxide glasses. (Author)

IR study of Pb–Sr titanate borosilicate glasses

Indian Academy of Sciences (India)

Administrator

IR study of Pb–Sr titanate borosilicate glasses. C R GAUTAM*, DEVENDRA KUMAR. † and OM PARKASH. †. Department of Physics, University of Lucknow, Lucknow 226 007, India. †. Department of Ceramic Engineering, Institute of Technology, Banaras Hindu University, Varanasi 221 005, India. MS received 3 January ...

Sulphate Incorporation in Borosilicate Glasses and Melts: a Kinetic Approach

Energy Technology Data Exchange (ETDEWEB)

Lenoir, M. [CEA, DEN, Laboratoire d' etude et de Developpement de Matrices de Conditionnement, Centre de Marcoule, 30207 Bagnols-sur-Ceze (France); Physique des Mineraux et Magmas, UMR 7047, CNRS- Institut de Physique du Globe de Paris, 7 place Jussieu, 75252 Paris 05 (France); Grandjean, A. [Institut de Chimie Separative de Marcoule, UMR 5257, Laboratoire des Nanomateriaux Autoreparants, Marcoule, 30207 Bagnols-sur-Ceze (France); Dussossoy, J.L. [CEA, DEN, Laboratoire d' etude et de Developpement de Matrices de Conditionnement, Centre de Marcoule, 30207 Bagnols-sur-Ceze (France); Neuville, D.R. [Physique des Mineraux et Magmas, UMR 7047, CNRS- Institut de Physique du Globe de Paris, 7 place Jussieu, 75252 Paris 05 (France)

2008-07-01

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{sup -1} was scaled to the sum of the integrated bands between 800 and 1200 cm{sup -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)

Effects of system size and cooling rate on the structure and properties of sodium borosilicate glasses from molecular dynamics simulations.

Science.gov (United States)

Deng, Lu; Du, Jincheng

2018-01-14

Borosilicate glasses form an important glass forming system in both glass science and technologies. The structure and property changes of borosilicate glasses as a function of thermal history in terms of cooling rate during glass formation and simulation system sizes used in classical molecular dynamics (MD) simulation were investigated with recently developed composition dependent partial charge potentials. Short and medium range structural features such as boron coordination, Si and B Q n distributions, and ring size distributions were analyzed to elucidate the effects of cooling rate and simulation system size on these structure features and selected glass properties such as glass transition temperature, vibration density of states, and mechanical properties. Neutron structure factors, neutron broadened pair distribution functions, and vibrational density of states were calculated and compared with results from experiments as well as ab initio calculations to validate the structure models. The results clearly indicate that both cooling rate and system size play an important role on the structures of these glasses, mainly by affecting the 3 B and 4 B distributions and consequently properties of the glasses. It was also found that different structure features and properties converge at different sizes or cooling rates; thus convergence tests are needed in simulations of the borosilicate glasses depending on the targeted properties. The results also shed light on the complex thermal history dependence on structure and properties in borosilicate glasses and the protocols in MD simulations of these and other glass materials.

Effects of system size and cooling rate on the structure and properties of sodium borosilicate glasses from molecular dynamics simulations

Science.gov (United States)

Deng, Lu; Du, Jincheng

2018-01-01

Borosilicate glasses form an important glass forming system in both glass science and technologies. The structure and property changes of borosilicate glasses as a function of thermal history in terms of cooling rate during glass formation and simulation system sizes used in classical molecular dynamics (MD) simulation were investigated with recently developed composition dependent partial charge potentials. Short and medium range structural features such as boron coordination, Si and B Qn distributions, and ring size distributions were analyzed to elucidate the effects of cooling rate and simulation system size on these structure features and selected glass properties such as glass transition temperature, vibration density of states, and mechanical properties. Neutron structure factors, neutron broadened pair distribution functions, and vibrational density of states were calculated and compared with results from experiments as well as ab initio calculations to validate the structure models. The results clearly indicate that both cooling rate and system size play an important role on the structures of these glasses, mainly by affecting the 3B and 4B distributions and consequently properties of the glasses. It was also found that different structure features and properties converge at different sizes or cooling rates; thus convergence tests are needed in simulations of the borosilicate glasses depending on the targeted properties. The results also shed light on the complex thermal history dependence on structure and properties in borosilicate glasses and the protocols in MD simulations of these and other glass materials.

Alteration of borosilicate glass under water saturated condition

International Nuclear Information System (INIS)

Tsukimura, K.; Matsuhisa, Y.; Kanai, Y.; Hirai, H.

1991-01-01

In the long term of the high-level nuclear waste disposal, the dissolving rates of radionuclides from the waste will be controlled by crystalline phases secondarily formed in the borosilicate glass by reaction with ground water. We have determined the crystalline phases formed from borosilicate glass in a hydrothermal experiment. Borosilicate glass powder (50 mg, Si 40 B 20 Al 4 Li 12 Na 14 K 3 Ca 2 Fe 5 O 140 ) and 200 ml of water were reacted at 300degC and 300 bars for 2 weeks with a cold-seal type hydrothermal high pressure apparatus. After the reaction the liquid phase was analyzed with atomic absorption spectroscopy and the solid phases with x-ray powder diffraction and analytical electron microscopy. The liquid phase contains 58 % of Na, 14 % of Li and 11 % of K but less than 1 % of Ca and Fe. The solid phases were found to be zeolite and smectite. The zeolite is isostructural with analcime Na 2 Al 2 (SiO 3 ) 4 · 2H 2 O or wairakite CaAl 2 (SiO 3 ) 4 · 2H 2 O and contains Ca and Si as major constituents but does not contain Al. Although no direct analytical evidence is available, logical induction of the experimental results indicates that the chemical composition of the zeolite is CaB 2 (SiO 3 ) 4 . The remaining x-ray powder diffraction peaks are same as those of smectite Na 06.7 (Al 3.33 Mg 0.67 )Si 8 O 20 (OH) 4 . However, since our starting material was free of Mg, and Na was not detected by AEM, the smectite may contain Fe instead of Mg, and Li instead of Na. (author)

Systems approach to nuclear waste glass development

International Nuclear Information System (INIS)

Jantzen, C.M.

1986-01-01

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

Method of manufacturing borosilicate glass solidification products

International Nuclear Information System (INIS)

Tanaka, Tsuneya.

1986-01-01

Purpose: To obtain glass solidification products efficiently in a dry process from medium and high level radioactive liquid wastes discharged from PWR type reactors. Method: Boric acid-containing radioactive liquid wastes generated from primary coolants of PWR type reactors are evaporated to condensate as the pre-treatment. The concentrated liquid wastes are supplied to a drum type rotary kiln. While on the other hand, usual glass frits are introduced into the kiln. The liquid wastes are dried in the rotary kiln, as well as B 2 O 3 and the glass frits in the liquid wastes are combined into glass particles. In this case, since the kiln is rotated, no glass particles are deposited on the wall of the kiln. Then, the glass particles are introduced for melting into a high frequency melting furnace made of metal. The melting temperature is set to 1100 - 1150 deg C. The molten borosilicate glass is recovered from the bottom of the melting furance, contained in a canister and cooled for several hours, and then a cover is welded to the canister. (Ikeda, J.)

Surface chemistry and durability of borosilicate glass

International Nuclear Information System (INIS)

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

1994-01-01

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

There Is Still Room for Improvement: Presentation of a Neutral Borosilicate Glass with Improved Chemical Stability for Parenteral Packaging.

Science.gov (United States)

Boltres, Bettine; Tratzky, Stephan; Kass, Christof; Eichholz, Rainer; Naß, Peter

2016-01-01

For pharmaceutical parenteral packaging the glass compositions have always been either Type I borosilicate or Type III soda-lime glass. As both the compositions and certain chemical and physical properties are mandated by international standards, there has not been room for any changes. However, by applying only minor adjustments, a borosilicate glass was developed that showed improved chemical stability. The chemical composition is still in the range of currently used borosilicate glasses, which makes it a Type I glass according to all current pharmacopeia. A study was performed on glass vials comparing the new glass with the standard FIOLAX(®) and two other publicly available glasses. In an extraction study with water at 121 °C the new glass showed the highest chemical stability with the lowest amount of extractables. In an accelerated ageing study, which was done with water, phosphate, and carbonate buffer at 40 °C for 12 months, the new glass also proved to have the lowest amount of leachables. In this article the new glass and the results from the studies are presented, showing the reader how much of an effect can be attained with only minor adjustments if the scientific fundamentals are clear. The pharmaceutical market has been quite constant and risk-oriented due to the high impact on the safety of the patient. As any change necessitates a complicated change process, this has, in consequence, lead the industry to resist changing the parenteral primary packaging material for decades. The main glasses have either been Type I borosilicate or Type III soda-lime glass. On the other hand, a combination of improved inspection systems and the development of more sensitive biologically based drugs has elevated the standards for parental packaging materials. For example, the measurement of extractables and leachables from the packaging material steadily came into focus. In this article, a new glass is presented that still belongs to the group of Type I borosilicate

Characterization of borosilicate glasses containing simulated high-level radioactive wastes from PNC

International Nuclear Information System (INIS)

Terai, R.; Eguchi, K.; Yamanaka, H.

1979-01-01

The characterization of borosilicate glasses containing simulated HLW from PNC has been carried out. Phase separation of molybdates, volatilization, viscosity, electrical resistivity, thermal conductivity, elastic modulus, chemical durability, and devitrification of these glasses have been measured, and the suitability of the glasses for the vitrified solidification processes is discussed from the viewpoint of safety

Effects of β-irradiation in multicomponent glasses simulating the matrix of the French nuclear waste glass (R7T7)

International Nuclear Information System (INIS)

Boizot, B.; Ghaleb, D.; Petite, G.

2001-01-01

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 11 B 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)

Advances in understanding the structure of borosilicate glasses: A Raman spectroscopy study

Energy Technology Data Exchange (ETDEWEB)

Manara, D.; Grandjean, A. [CEA Marcoule, Serv Confinement Deches and Vitrificat, DTCD, DEN - 30 (France); Neuville, D.R. [Institut Physique Globe, Physique des Mineraux et Magmas, CNRS, F-75252 Paris 05 (France)

2009-05-15

This study is focused on the behavior of ternary SiO{sub 2}-Na{sub 2}O-B{sub 2}O{sub 3} borosilicate glasses at temperatures between 298 and 1800 K. Unpolarized Raman spectra were measured up to high temperature. SiO{sub 2}-Na{sub 2}O-B{sub 2}O{sub 3} glass samples were prepared with different values of the ratio R [Na{sub 2}O]/[B{sub 2}O{sub 3}], while the ratio K = [SiO{sub 2}]/[B{sub 2}O{sub 3}] was kept constant and equal 2.12. Spectra were measured at room temperature in samples with 0.43 {<=} R {<=} 1.68, and the effect of the modifier content was clearly observed in these glasses, only in partial agreement with previous literature results. In particular, the formation in the glass of sodium-danburite units Na{sub 2}O-B{sub 2}O{sub 3}-2SiO{sub 2} was postulated. This feature led to a new assessment of R{sup *}, the critical value of R above which every new alkali atom added to the system breaks a Fo-O-Fo (Fo=glass former) bridge causing depolymerization of the glass. A revised formula is proposed to obtain the value of R{sup *} as a function of K. Raman spectra measured at high temperature yielded important information about the temperature-dependent evolution of the borosilicate system. In particular, borate and borosilicate units including tetra-coordinated boron seem to be unstable at high temperature, where the formation of metaborate chains or rings is fostered. Above 1500 degrees C, evaporation of borate compounds is clearly observed, stemming from the small sample size. (authors)

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...

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

International Nuclear Information System (INIS)

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

1987-12-01

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

Stress corrosion in a borosilicate glass nuclear wasteform

International Nuclear Information System (INIS)

Ringwood, A.E.; Willis, P.

1984-01-01

The authors discuss a typical borosilicate glass wasteform which, when exposed to water vapour and water for limited periods, exhibits evidence of stress corrosion cracking arising from the interaction of polar OH groups with stressed glass surfaces. Glass wasteforms may experience similar stress corrosion cracking when buried in a geological repository and exposed to groundwaters over an extended period. This would increase the effective surface areas available for leaching by groundwater and could decrease the lifetime of the wasteform. Conventional leach-testing methods are insensitive to the longer-term effects of stress corrosion cracking. It is suggested that specific fracture-mechanics tests designed to evaluate susceptibility to stress corrosion cracking should be used when evaluating the wasteforms for high-level nuclear wastes. (author)

Commercial Ion Exchange Resin Vitrification in Borosilicate Glass

International Nuclear Information System (INIS)

Cicero-Herman, C.A.; Workman, P.; Poole, K.; Erich, D.; Harden, J.

1998-05-01

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

Alpha self irradiation effects in nuclear borosilicate glass

International Nuclear Information System (INIS)

Peuget, S.; Roudil, D.; Deschanels, X.; Jegou, C.; Broudic, V.; Bart, J.M.

2004-01-01

The properties of actinide glasses are studied in the context of high-level waste management programs. Reprocessing high burnup fuels in particular will increase the minor actinide content in the glass package, resulting in higher cumulative alpha decay doses in the glass, and raising the question of the glass matrix behavior and especially its containment properties. The effect of alpha self-irradiation on the glass behavior is evaluated by doping the glass with a short-lived actinide ( 244 Cm) to reach in several years the alpha dose received by the future glass packages over several thousand years. 'R7T7' borosilicate glasses were doped with 3 different curium contents (0.04, 0.4 and 1.2 wt% 244 CmO 2 ). The density and mechanical properties of the curium-doped glasses were characterized up to 2. 10 18 α/g, revealing only a slight evolution of the macroscopic behavior of R7T7 glass in this range. The leaching behavior of curium-doped glass was also studied by Soxhlet tests. The results do not show any significant evolution of the initial alteration rate with the alpha dose. (authors)

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

International Nuclear Information System (INIS)

Ledieu, A.

2004-10-01

This work is concerned with the corrosion of borosilicate glasses with variable oxide contents. The originality of this study is the complementary use of experiments and numerical simulations. This study is expected to contribute to a better understanding of the corrosion of nuclear waste confinement glasses. First, the corrosion of glasses containing only silicon, boron and sodium oxides has been studied. The kinetics of leaching show that the rate of leaching and the final degree of corrosion sharply depend on the boron content through a percolation mechanism. For some glass contents and some conditions of leaching, the layer which appears at the glass surface stops the release of soluble species (boron and sodium). This altered layer (also called the gel layer) has been characterized with nuclear magnetic resonance (NMR) and small angle X-ray scattering (SAXS) techniques. Second, additional elements have been included in the glass composition. It appears that calcium, zirconium or aluminum oxides strongly modify the final degree of corrosion so that the percolation properties of the boron sub-network is no more a sufficient explanation to account for the behavior of these glasses. Meanwhile, we have developed a theoretical model, based on the dissolution and the reprecipitation of the silicon. Kinetic Monte Carlo simulations have been used in order to test several concepts such as the boron percolation, the local reactivity of weakly soluble elements and the restructuring of the gel layer. This model has been fully validated by comparison with the results on the three oxide glasses. Then, it has been used as a comprehensive tool to investigate the paradoxical behavior of the aluminum and zirconium glasses: although these elements slow down the corrosion kinetics, they lead to a deeper final degree of corrosion. The main contribution of this work is that the final degree of corrosion of borosilicate glasses results from the competition of two opposite mechanisms

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

International Nuclear Information System (INIS)

Ledieu, A.

2004-10-01

This work is concerned with the corrosion of borosilicate glasses with variable oxide contents. The originality of this study is the complementary use of experiments and numerical simulations. This study is expected to contribute to a better understanding of the corrosion of nuclear waste confinement glasses. First, the corrosion of glasses containing only silicon, boron and sodium oxides has been studied. The kinetics of leaching show that the rate of leaching and the final degree of corrosion sharply depend on the boron content through a percolation mechanism. For some glass contents and some conditions of leaching, the layer which appears at the glass surface stops the release of soluble species (boron and sodium). This altered layer (also called the gel layer) has been characterized with nuclear magnetic resonance (NMR) and small angle X-ray scattering (SAXS) techniques. Second, additional elements have been included in the glass composition. It appears that calcium, zirconium or aluminum oxides strongly modify the final degree of corrosion so that the percolation properties of the boron sub-network is no more a sufficient explanation to account for the behavior of these glasses. Meanwhile, we have developed a theoretical model, based on the dissolution and the reprecipitation of the silicon. Kinetic Monte Carlo simulations have been used in order to test several concepts such as the boron percolation, the local reactivity of weakly soluble elements and the restructuring of the gel layer. This model has been fully validated by comparison with the results on the three oxide glasses. Then, it has been used as a comprehensive tool to investigate the paradoxical behavior of the aluminum and zirconium glasses: although these elements slow down the corrosion kinetics, they lead to a deeper final degree of corrosion. The main contribution of this work is that the final degree of corrosion of borosilicate glasses results from the competition of two opposite mechanisms

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

Science.gov (United States)

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

2018-04-01

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

Electron irradiation induced nanocrystal formation in Cu-borosilicate glass

Energy Technology Data Exchange (ETDEWEB)

Sabri, Mohammed Mohammed; Möbus, Günter, E-mail: g.moebus@sheffield.ac.uk [University of Sheffield, Department of Materials Science and Engineering (United Kingdom)

2016-03-15

Nanoscale writing of Cu nanoparticles in glasses is introduced using focused electron irradiation by transmission electron microscopy. Two types of copper borosilicate glasses, one with high and another with low Cu loading, have been tested at energies of 200–300 keV, and formation of Cu nanoparticles in a variety of shapes and sizes using different irradiation conditions is achieved. Electron energy loss spectroscopy analysis, combined with high-resolution transmission electron microscopy imaging, confirmed the irradiation-induced precipitated nanoparticles as metallic, while furnace annealing of the glass triggered dendrite-shaped particles of copper oxide. Unusual patterns of nanoparticle rings and chains under focused electron beam irradiation are also presented. Conclusively, electron beam patterning of Cu-loaded glasses is a promising alternative route to well-established femtosecond laser photoreduction of Cu ions in glass.

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

International Nuclear Information System (INIS)

Yadav, Avadhesh Kumar; Gautam, C.R.

2013-01-01

Various perovskite (Ba,Sr)TiO 3 borosilicate glasses were prepared by rapid melt-quench technique in the glass system ((Ba 1-x Sr x ).TiO 3 )-(2SiO 2 .B 2 O 3 )-(K 2 O)-(La 2 O 3 ). 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. La 2 O 3 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)

The structure of leached sodium borosilicate glass

International Nuclear Information System (INIS)

Bunker, B.C.; Tallant, D.R.; Headley, T.J.; Turner, G.L.; Kirkpatrick, R.J.

1988-01-01

Raman spectroscopy, solid state 29 Si, 11 B, 17 O, and 23 Na nuclear magnetic resonance spectroscopy, and transmission electron microscopy have been used to investigate how the structures of sodium borosilicate glasses change during leaching in water at pH 1, 9, and 12. Results show that the random network structure present prior to leaching is transformed into a network of small condensed ring structures and/or colloidal silica particles. The restructuring of leached glass can be rationalised on the basis of simple hydrolysis (depolymerisation) and condensation (repolymerisation) reactions involving Si-O-Si and Si-O-B bonds. The structural changes that occur during leaching influence the properties of the leached layer, including leaching kinetics, crazing and spalling, and slow crack growth. (author)

Modelling the evaporation of boron species. Part 1: Alkali-free borosilicate glass melts

NARCIS (Netherlands)

Limpt, J.A.C. van; Beerkens, R.G.C.; Cook, S.; O'Connor, R.; Simon, J.

2011-01-01

A laboratory test facility has been used to measure the boron evaporation rates from borosilicate glass melts. The impact of furnace atmosphere composition and glass melt composition on the temperature dependent boron evaporation rates has been investigated experimentally. In Part 1 of this paper

Influence of Cu doping in borosilicate bioactive glass and the properties of its derived scaffolds.

Science.gov (United States)

Wang, Hui; Zhao, Shichang; Xiao, Wei; Xue, Jingzhe; Shen, Youqu; Zhou, Jie; Huang, Wenhai; Rahaman, Mohamed N; Zhang, Changqing; Wang, Deping

2016-01-01

Copper doped borosilicate glasses (BG-Cu) were studied by means of FT-IR, Raman, UV-vis and NMR spectroscopies to investigate the changes that appeared in the structure of borosilicate glass matrix by doping copper ions. Micro-fil and immunohistochemistry analysis were applied to study the angiogenesis of its derived scaffolds in vivo. Results indicated that the Cu ions significantly increased the B-O bond of BO4 groups at 980 cm(-1), while they decrease that of BO2O(-) groups at 1440-1470 cm(-1) as shown by Raman spectra. A negative shift was observed from (11)B and (29)Si NMR spectra. The (11)B NMR spectra exhibited a clear transformation from BO3 into BO4 groups, caused by the agglutination effect of the Cu ions and the charge balance of the agglomerate in the glass network, leading to a more stable glass network and lower ions release rate in the degradation process. Furthermore, the BG-Cu scaffolds significantly enhanced blood vessel formation in rat calvarial defects at 8 weeks post-implantation. Generally, it suggested that the introduction of Cu into borosilicate glass endowed glass and its derived scaffolds with good properties, and the cooperation of Cu with bioactive glass may pave a new way for tissue engineering. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrical conductivity and viscosity of borosilicate glasses and melts

DEFF Research Database (Denmark)

Ehrt, Doris; Keding, Ralf

2009-01-01

, 0 to 62·5 mol% B2O3, and 25 to 85 mol% SiO2. The glass samples were characterised by different methods. Refractive indices, density and thermal expansion were measured. Phase separation effects were investigated by electron microscopy. The electrical conductivity of glasses and melts were determined......Simple sodium borosilicate and silicate glasses were melted on a very large scale (35 l Pt crucible) to prepare model glasses of optical quality in order to investigate various properties depending on their structure. The composition of the glass samples varied in a wide range: 3 to 33·3 mol% Na2O...... 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...

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

International Nuclear Information System (INIS)

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

2014-01-01

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

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

International Nuclear Information System (INIS)

Techer, I.

1999-01-01

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 -1 . As the reaction progresses, the alteration rate drops by over four orders of magnitude from the initial rate r 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)

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

International Nuclear Information System (INIS)

Cunnane, J.C.

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

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.

Effect of heat treatment duration on phase separation of sodium borosilicate glass, containing copper

International Nuclear Information System (INIS)

Shejnina, T.G.; Gutner, S.Kh.; Anan'in, N.I.

1989-01-01

The effect of heat treatment duration on phase separation of sodium borosilicate (SBS) glass, containing copper is studied. It is stated that phase separation close to equilibrium one is attained under 12 hours of heat treatment of SBS glass containing copper

Thermodynamic properties of alkali borosilicate gasses and metaborates

International Nuclear Information System (INIS)

Asano, Mitsuru

1992-01-01

Borosilicate glasses are the proposed solidifying material for storing high level radioactive wastes in deep underground strata. Those have low melting point, and can contain relatively large amount of high level radioactive wastes. When borosilicate glasses are used for this purpose, they must be sufficiently stable and highly reliable in the vitrification process, engineered storage and the disposal in deep underground strata. The main vaporizing components from borosilicate glasses are alkali elements and boron. In this report, as for the vaporizing behavior of alkali borosilicate glasses, the research on thermodynamic standpoint carried out by the authors is explained, and the thermodynamic properties of alkali metaborates of monomer and dimer which are the main evaporation gases are reported. The evaporation and the activity of alkali borosilicate glasses, the thermodynamic properties of alkali borosilicate glasses, gaseous alkali metaborates and alkali metaborate system solid solution and so on are described. (K.I.)

Conversion of radwaste-loaded zeolites into a borosilicate glass to improve their properties for final disposal (preliminary results)

International Nuclear Information System (INIS)

Kazemian, H.; Ghannadi Maraghe, M.; Mallah, M.H.; Firooz Zare, M.; Kooshkestani, R.; Naghavi, S.Sh.

2002-01-01

Research was undertaken to fix radioisotopes from simulated nuclear waste streams into durable and stable borosilicate glass matrices based on the conversion of different type of zeolites. It was found that the selectivity of Iranian clinoptilolite and the relevant synthetic zeolite toward cesium and strontium were quite good whereas the leach resistance of the loaded zeolite was relatively poor. To improve the leach resistance of the used zeolites, conversion of the spent exchangers into borosilicate glass was investigated. Results obtained in the non active bench scale tests phase were promising. It is concluded that spent zeolites loaded with radioactive materials can be converted into a durable, high leach resistant borosilicate glass, a proper matrix for final disposal of nuclear waste. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2018-02-10

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

X-ray absorption and Raman spectroscopy studies of molybdenum environments in borosilicate waste glasses

Science.gov (United States)

McKeown, David A.; Gan, Hao; Pegg, Ian L.

2017-05-01

Mo-containing high-level nuclear waste borosilicate glasses were investigated as part of an effort to improve Mo loading while avoiding yellow phase crystallization. Previous work showed that additions of vanadium decrease yellow phase formation and increases Mo solubility. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to characterize Mo environments in HLW borosilicate glasses and to investigate possible structural relationships between Mo and V. Mo XAS spectra for the glasses indicate isolated tetrahedral Mo6+O4 with Mo-O distances near 1.75 Å. V XANES indicate tetrahedral V5+O4 as the dominant species. Raman spectra show composition dependent trends, where Mo-O symmetrical stretch mode frequencies (ν1) are sensitive to the mix of alkali and alkaline earth cations, decreasing by up to 10 cm-1 for glasses that change from Li+ to Na+ as the dominant network-modifying species. This indicates that MoO4 tetrahedra are isolated from the borosilicate network and are surrounded, at least partly, by Na+ and Li+. Secondary ν1 frequency effects, with changes up to 7 cm-1, were also observed with increasing V2O5 and MoO3 content. These secondary trends may indicate MoO4-MoO4 and MoO4-VO4 clustering, suggesting that V additions may stabilize Mo in the matrix with respect to yellow phase formation.

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

International Nuclear Information System (INIS)

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

1996-01-01

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

Corrosion of inconel in high-temperature borosilicate glass melts containing simulant nuclear waste

Science.gov (United States)

Mao, Xianhe; Yuan, Xiaoning; Brigden, Clive T.; Tao, Jun; Hyatt, Neil C.; Miekina, Michal

2017-10-01

The corrosion behaviors of Inconel 601 in the borosilicate glass (MW glass) containing 25 wt.% of simulant Magnox waste, and in ZnO, Mn2O3 and Fe2O3 modified Mg/Ca borosilicate glasses (MZMF and CZMF glasses) containing 15 wt.% of simulant POCO waste, were evaluated by dimensional changes, the formation of internal defects and changes in alloy composition near corrosion surfaces. In all three kinds of glass melts, Cr at the inconel surface forms a protective Cr2O3 scale between the metal surface and the glass, and alumina precipitates penetrate from the metal surface or formed in-situ. The corrosion depths of inconel 601 in MW waste glass melt are greater than those in the other two glass melts. In MW glass, the Cr2O3 layer between inconel and glass is fragmented because of the reaction between MgO and Cr2O3, which forms the crystal phase MgCr2O4. In MZMF and CZMF waste glasses the layers are continuous and a thin (Zn, Fe, Ni, B)-containing layer forms on the surface of the chromium oxide layer and prevents Cr2O3 from reacting with MgO or other constituents. MgCr2O4 was observed in the XRD analysis of the bulk MW waste glass after the corrosion test, and ZrSiO4 in the MZMF waste glass, and ZrSiO4 and CaMoO4 in the CZMF waste glass.

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

International Nuclear Information System (INIS)

Lassalle-Herraud, Olivier; Matecki, Marc; Glorieux, Benoit; Sadiki, Najim; Montoullout, Valerie; Dussossoy, Jean-Luc

2006-01-01

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.)

Influence of Cu doping in borosilicate bioactive glass and the properties of its derived scaffolds

Energy Technology Data Exchange (ETDEWEB)

Wang, Hui [School of Materials Science and Engineering, Tongji University, Shanghai 2001804 (China); Zhao, Shichang [Department of Orthopedic Surgery, Shanghai Sixth People' s Hospital, Shanghai Jiao Tong University, Shanghai 200233 (China); Xiao, Wei [Department of Materials Science and Engineering, and Center for Biomedical Science and Engineering, Missouri University of Science and Technology, Rolla, MO 65409-0340 (United States); Xue, Jingzhe [Department of Chemistry, Tongji University, Shanghai 200092 (China); Shen, Youqu [Department of Materials Science and Engineering, and Center for Biomedical Science and Engineering, Missouri University of Science and Technology, Rolla, MO 65409-0340 (United States); Zhou, Jie; Huang, Wenhai [School of Materials Science and Engineering, Tongji University, Shanghai 2001804 (China); Rahaman, Mohamed N. [Department of Materials Science and Engineering, and Center for Biomedical Science and Engineering, Missouri University of Science and Technology, Rolla, MO 65409-0340 (United States); Zhang, Changqing, E-mail: shzhangchangqing@163.com [Department of Orthopedic Surgery, Shanghai Sixth People' s Hospital, Shanghai Jiao Tong University, Shanghai 200233 (China); Wang, Deping, E-mail: wdpshk@tongji.edu.cn [School of Materials Science and Engineering, Tongji University, Shanghai 2001804 (China)

2016-01-01

Copper doped borosilicate glasses (BG–Cu) were studied by means of FT-IR, Raman, UV–vis and NMR spectroscopies to investigate the changes that appeared in the structure of borosilicate glass matrix by doping copper ions. Micro-fil and immunohistochemistry analysis were applied to study the angiogenesis of its derived scaffolds in vivo. Results indicated that the Cu ions significantly increased the B–O bond of BO{sub 4} groups at 980 cm{sup −1}, while they decrease that of BO{sub 2}O{sup −} groups at 1440–1470 cm{sup −1} as shown by Raman spectra. A negative shift was observed from {sup 11}B and {sup 29}Si NMR spectra. The {sup 11}B NMR spectra exhibited a clear transformation from BO{sub 3} into BO{sub 4} groups, caused by the agglutination effect of the Cu ions and the charge balance of the agglomerate in the glass network, leading to a more stable glass network and lower ions release rate in the degradation process. Furthermore, the BG–Cu scaffolds significantly enhanced blood vessel formation in rat calvarial defects at 8 weeks post-implantation. Generally, it suggested that the introduction of Cu into borosilicate glass endowed glass and its derived scaffolds with good properties, and the cooperation of Cu with bioactive glass may pave a new way for tissue engineering. - Highlights: • Agglutination effect of Cu{sup 2+} and charge balance of agglomerate lead to more stable glass. • Lower degradability and lower ions release were found in BG-Cu scaffolds. • Excellent angiogenesis and sustain Cu{sup 2+} release were endowed by doping Cu.

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.

Mineralogical textural and compositional data on the alteration of basaltic glass from Kilauea, Hawaii to 300 degrees C: Insights to the corrosion of a borosilicate glass waste-form

International Nuclear Information System (INIS)

Smith, D.K.

1990-01-01

Mineralogical, textural and compositional data accompanying greenschist facies metamorphism (to 300 degrees C) of basalts of the East Rift Zone (ERZ), Kilauea, Hawaii may be evaluated relative to published and experimental results for the surface corrosion of borosilicate glass. The ERZ alteration sequence is dominated by intermittent palagonite, interlayered smectite-chlorite, chlorite, and actinolite-epidote-anhydrite. Alteration is best developed in fractures and vesicles where surface reaction layers root on the glass matrix forming rinds in excess of 100 microns thick. Fractures control fluid circulation and the alteration sequence. Proximal to the glass surface, palagonite, Fe-Ti oxides and clays replace fresh glass as the surface reaction layer migrates inwards; away from the surface, amphibole, anhydrite, quartz and calcite crystallize from hydrothermal fluids in contact with the glass. The texture and composition of basaltic glass surfaces are similar to those of a SRL-165 glass leached statically for sixty days at 150 degrees C. While the ERZ reservoir is a complex open system, conservative comparisons between the alteration of ERZ and synthetic borosilicate glass are warranted. 31 refs., 2 figs

Determination of occluded helium and oxygen in irradiated borosilicate glass samples

International Nuclear Information System (INIS)

Ramanjaneyulu, P.S.; Kulkarni, A.S.; Shrivastava, K.C.; Yadav, C.S.; Saxena, M.K.; Tomar, B.S.; Ramakumar, K.L.; Shah, J.G.

2015-01-01

Occluded gases in irradiated borosilicate glass were determined at 573, 873 and 1273 K for understanding the radiation damage in glass matrix. Hot vacuum extraction coupled with a quadrupole mass spectrometer technique was employed for the measurements. Relative sensitivity factors of various gases in QMS system were also determined and used for gas composition calculations. At 573 K only helium was found to get released whereas at 873 and 1273 K both helium and oxygen were released with major fraction of oxygen. (author)

Studies on the accelerated chemical durability test and its impact on structural changes in borosilicate glass matrix

International Nuclear Information System (INIS)

Thorat, Vidya S.; Kadam, P.S.; Mishra, R.K.; Kumar, Amar; Kaushik, C.P.; Sudarsan, V.; Tyagi, A.K.

2015-01-01

Sodium borosilicate glass used for the immobilisation of high level nuclear waste with tentative compositions (SiO 2 ) 0.477 (B 2 O 3 ) 0.239 (Na 2 O) 0.170 (TiO 2 ) 0.02 )3 (CaO) 0.068 (Al 2 O 3 ) 0.023 was evaluated for its long term stability in the repository conditions where it may be exposed to high temperature and pressure. 29 Si MAS NMR studies have confirmed that, upon leaching, sodium borosilicate glass undergoes congruent crystallization leading to the formation of an aluminosilicate phase, Na 6 Al 6 Si 10 O 32 . Further the residual glass structure in the composite sample is identical with that of the un-leached glass. Boron structural units are unaffected in the glass compositions upon leaching

X-ray absorption and Raman spectroscopy studies of molybdenum environments in borosilicate waste glasses

Energy Technology Data Exchange (ETDEWEB)

McKeown, David A., E-mail: davidm@vsl.cua.edu; Gan, Hao; Pegg, Ian L.

2017-05-15

Mo-containing high-level nuclear waste borosilicate glasses were investigated as part of an effort to improve Mo loading while avoiding yellow phase crystallization. Previous work showed that additions of vanadium decrease yellow phase formation and increases Mo solubility. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to characterize Mo environments in HLW borosilicate glasses and to investigate possible structural relationships between Mo and V. Mo XAS spectra for the glasses indicate isolated tetrahedral Mo{sup 6+}O{sub 4} with Mo-O distances near 1.75 Å. V XANES indicate tetrahedral V{sup 5+}O{sub 4} as the dominant species. Raman spectra show composition dependent trends, where Mo-O symmetrical stretch mode frequencies (ν{sub 1}) are sensitive to the mix of alkali and alkaline earth cations, decreasing by up to 10 cm{sup −1} for glasses that change from Li{sup +} to Na{sup +} as the dominant network-modifying species. This indicates that MoO{sub 4} tetrahedra are isolated from the borosilicate network and are surrounded, at least partly, by Na{sup +} and Li{sup +}. Secondary ν{sub 1} frequency effects, with changes up to 7 cm{sup −1}, were also observed with increasing V{sub 2}O{sub 5} and MoO{sub 3} content. These secondary trends may indicate MoO{sub 4}-MoO{sub 4} and MoO{sub 4}-VO{sub 4} clustering, suggesting that V additions may stabilize Mo in the matrix with respect to yellow phase formation. - Highlights: •Raman and XAS data indicate isolated MoO{sub 4} tetrahedra from the borosilicate network. •Mo-O stretch frequency is sensitive to network-modifying Li and Na concentrations. •Mo-O stretch frequency shifts were also seen with increasing V{sub 2}O{sub 5} and MoO{sub 3} content. •The Raman trends may indicate MoO{sub 4}-MoO{sub 4} and MoO{sub 4}-VO{sub 4} clustering in the glass. •V may stabilize Mo in the glass matrix avoiding yellow phase formation.

Evaluation of long-term leaching of borosilicate glass in pure water

International Nuclear Information System (INIS)

Lanza, F.; Parnisari, E.

1979-01-01

In order to confirm the validity of the model of the dissolving sphere, a series of tests of leaching of borosilicate glasses has been performed. The leaching rate is followed by measurements of weight loss and analysis of the surface composition. An accumulation at the surface of the less soluble cations is observed

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

International Nuclear Information System (INIS)

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

1995-01-01

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

Optical and structural investigation on sodium borosilicate glasses doped with Cr2O3

Science.gov (United States)

Ebrahimi, E.; Rezvani, M.

2018-02-01

In this work, Sodium borosilicate glasses with chemical composition of 60% SiO2-20% B2O3-20%Na2O doped with different contents of Cr2O3 were prepared by melting-quenching method. Physical, structural and optical properties of glasses were investigated by studying density and molar volume, Fourier Transform Infrared (FT-IR) Spectra and UV-visible absorption spectroscopy. The results showed an increase in density of glasses with the increase of Cr2O3 that can be due to addition of oxide with high molar mass. The optical absorption spectra of un-doped glass reveals UV absorption due to trace iron impurities with no visible band however Cr2O3 doped glasses shows absorption in visible range that are characteristic. Increasing of Cr3 + ions in the glassy microstructure of samples provides a semiconducting character to Sodium borosilicate glass by reducing the direct and indirect optical band gaps of glass samples from 3.79 to 2.59 (ev) and 3.36 to 2.09 (ev), respectively. These changes could be attributed to the role of Cr3 + ions as the network former which asserts improvement of semiconducting behavior in presence of Cr2O3.

X-ray irradiation induced reduction and nanoclustering of lead in borosilicate glass

NARCIS (Netherlands)

Stanley, H.B.; Banerjee, D.; Breemen, van L.C.A.; Ciston, J.; Liebscher, C.H.; Martis, V.; Merino, D.H.; Longo, A.; Pattison, P.; Peters, G.W.M.; Portale, G.; Sen, Sabyasachi; Bras, W.

2014-01-01

We have studied the formation of nanoparticles in lead sulfide (PbS)-doped borosilicate glass subjected to a two-step nucleation and growth heat treatment using in situ small-angle X-ray scattering (SAXS). The microstructure produced was subsequently characterized using X-ray powder diffraction

New insight into nanoparticle precipitation by electron beams in borosilicate glasses

Science.gov (United States)

Sabri, M. M.; Möbus, G.

2017-06-01

Nanoprecipitation in different oxide glasses by means of electron irradiation in transmission electron microscopy (TEM) has been compared in this study. Upon irradiation, groups or patterns of nanoparticles with various morphologies and sizes were formed in borosilicate glasses, loaded with zinc, copper, and silver. The study successfully includes loading ranges for the target metal from doping level (1%) over medium level (20%) to majority phase (60%). It is found that particle patterning resolution is affected by parallel processes of amorphous phase separation, glass ablation, and delocalised precipitation. In addition, via an in-situ study, it is confirmed that by heating alone without irradiation, no precipitate nanoparticles form.

New insight into nanoparticle precipitation by electron beams in borosilicate glasses

Energy Technology Data Exchange (ETDEWEB)

Sabri, M.M.; Moebus, G. [University of Sheffield, Department of Materials Science and Engineering (United Kingdom)

2017-06-15

Nanoprecipitation in different oxide glasses by means of electron irradiation in transmission electron microscopy (TEM) has been compared in this study. Upon irradiation, groups or patterns of nanoparticles with various morphologies and sizes were formed in borosilicate glasses, loaded with zinc, copper, and silver. The study successfully includes loading ranges for the target metal from doping level (1%) over medium level (20%) to majority phase (60%). It is found that particle patterning resolution is affected by parallel processes of amorphous phase separation, glass ablation, and delocalised precipitation. In addition, via an in-situ study, it is confirmed that by heating alone without irradiation, no precipitate nanoparticles form. (orig.)

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.

Antagonist effects of calcium on borosilicate glass alteration

International Nuclear Information System (INIS)

Mercado-Depierre, S.; Angeli, F.; Frizon, F.; Gin, S.

2013-01-01

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

Structural and luminescence properties of samarium doped lead alumino borate glasses

Science.gov (United States)

Mohan, Shaweta; Kaur, Simranpreet; Singh, D. P.; Kaur, Puneet

2017-11-01

The study reports the effect of samarium concentration on the physical, structural and spectroscopic characteristics of samarium doped lead alumino borate glasses having composition 20PbO-(10-x)Al2O3-70B2O3-xSm2O3; x = 0.1, 0.5, 1.0 and 2.0 mol %. The glasses were fabricated by conventional melt-quenching technique and then characterized by XRD, FTIR, optical absorption and fluorescence spectra. X-ray diffraction studies confirmed the amorphous nature of the prepared glasses. FTIR spectra indicate the presence of BO3, BO4, AlO6 and a few other structural groups. Various physical properties such as density, molar volume, refractive index, rare earth ion concentration, boron-boron distance and polarizability etc. were determined using conventional methods and standard formulae. The Judd-Ofelt theory was applied on the optical absorption spectra of the glasses to evaluate the three phenomenological intensity parameters Ω2, Ω4 and Ω6. The value of Ω2 was found to be highest for glass with 1 mol% Sm2O3 and attributed to the asymmetry of the ligand field at the rare earth ion site and the rare earth oxygen (Sm-O) covalency. The calculated intensity parameters and fluorescence spectra were further used to predict the radiative transition probability (A), radiative lifetime (τR), branching ratio (βR), peak wavelength (λp), effective line widths (Δλeff) and stimulated emission cross-section (σ) for the characteristic 4G5/2 → 6H5/2, 6H7/2 and 6H9/2 transitions of the Sm3+ ion. Concentration quenching was observed for 2 mol% concentration of Sm2O3 and ascribed to energy transfer through various cross-relaxation channels between Sm3+ ions. Reasonably high values of branching ratios and stimulated emission cross-section for the prepared glasses points towards their utility in the development of visible lasers emitting in the reddish-orange spectral region. However, the glass with 1 mol% Sm2O3 was found to show better radiative properties.

Effects of alpha radiation on hardness and toughness of the borosilicate glass applied to radioactive wastes immobilization

International Nuclear Information System (INIS)

Prado, Miguel Oscar; Bernasconi, Norma B. Messi de; Bevilacqua, Arturo Miguel; Arribere, Maria Angelica; Heredia, Arturo D.; Sanfilippo, Miguel

1999-01-01

Borosilicate german glass SG7 samples, obtained by frit sintering, were irradiated with different fluences of thermal neutrons in the nucleus of a nuclear reactor. The nuclear reaction 10 B(n,α) 7 Li, where the 10 B isotope is one of the natural glass components, was used to generate alpha particles throughout the glass volume. The maximum alpha disintegration per unit volume achieved was equivalent to that accumulated in a borosilicate glass with nuclear wastes after 3.8 million years. Through Vickers indentations values for microhardness, stress for 50% fracture probability (Weibull statistics) and estimation of the toughness were obtained as a function of alpha radiation dose. Two counterbalanced effects were found: that due to the disorder created by the alpha particles in the glass and that due to the annealing during irradiation (temperature below 240 deg C). Considering the alpha radiation effect, glasses tend decrease Vickers hardness, and to increase thr 50% fracture probability stress with the dose increase. (author)

Influence of Mo on the structure of borosilicate glass for the immobilization of high level waste

International Nuclear Information System (INIS)

Petrov, I.; Dimitriev, Y.; Kashchieva, E.

2015-01-01

It has been shown that the classic multi-borosilicate glass with concentration of MoO 3 has a low melting in the range of 1300 to 1400 ° C, but for achieving of complete homogenization and vitrification it is required temperature above 1400 ° C. Under this temperature in all tested samples areas of crystallization were observed, due to incomplete vitrification processes. It is understood that in all multicomponent borosilicate glass featuring MoO 3 , occur micro vitrification processes, and at a concentration of MoO 3 above 20% - macro segregation; It has been shown that the introduction of Nd in compound borosilicate glass featuring MoO 3 is observed crystallization of the phase Na 0.5 Nd 0.5 Mo, and it has been also found that the phase Na 0.5 Nd 0.5 Mo 4 can be synthesized either by solid phase reaction or supercooled melt. The results of surveys show that It is possible to prevent the occurrence of liquid phase separation in the studied multicomponent glass. From a structural point of view, the cause of liquid phase separation is the result of structural incompatibility of molybdenum units with structural units borosilicate network since not been established links Mo-O-B-O and Mo-Si. From a thermodynamic point of view in the lamination multi windows may be due to overlapping areas of delamination in component binary and triple systems. From the kinetic point of view of course the liquid phase by settling, and crystallization may be due to imbalances conditions the cooling process, in the course of which flow various processes of imbalances metastable settling, followed by crystallization of molybdate phases

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

International Nuclear Information System (INIS)

Chen, X.; Birtcher, R. C.; Donnelly, S. E.

2000-01-01

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

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

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

Determination of boron in borosilicate glasses by neutron capture prompt gamma-ray activation analysis

Energy Technology Data Exchange (ETDEWEB)

Riley, Jr, J E; Lindstrom, R M

1987-01-01

Major levels of boron in borosilicate glasses were determined nondestructively by neutron activation analysis. The effects of neutron self-shielding by boron (1 to 8% by weight) are examined. Results of the analysis of a series of glasses with increasing boron composition are 1.150 +- .005% and 7.766 +- .035% for the low and high members of the series. Once analyzed, the glasses are useful as secondary standards for alpha track counting, and also ion and electron microprobe analyses of glasses. 12 refs.; 3 tables.

Gas gain stability of MSGCs on borosilicate glass

International Nuclear Information System (INIS)

Berg, F.D. van den; Daum, C.; Eijk, B. van; Hartjes, F.G.; Udo, F.; Zhukov, V.

1996-01-01

The gas gain stability in Micro Strip Gas Counters fabricated on borosilicate glass has been investigated for operation at high radiation fluxes up to 10 5 Hz/mm 2 in a X-ray set-up. We discuss effects of short and long term irradiation on the gain for different voltage settings and strip metalisations. The application of a high drift field and a back plane on positive potential provides good high rate operation up to 10 4 Hz/mm 2 . Ageing is observed to be strongly dependent on the stirp metalisation; gold and nickel perform better than aluminium and copper. (orig.)

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

Science.gov (United States)

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

2012-11-20

The immobilization of technetium-99 ((99)Tc) in a suitable host matrix has proven to be a challenging task for researchers in the nuclear waste community around the world. In this context, the present work reports on the solubility and retention of rhenium, a nonradioactive surrogate for (99)Tc, in a sodium borosilicate glass. Glasses containing target Re concentrations from 0 to 10,000 ppm [by mass, added as KReO(4) (Re(7+))] were synthesized in vacuum-sealed quartz ampules to minimize the loss of Re from volatilization during melting at 1000 °C. The rhenium was found as Re(7+) in all of the glasses as observed by X-ray absorption near-edge structure. The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) using inductively coupled plasma optical emission spectroscopy. At higher rhenium concentrations, additional rhenium was retained in the glasses as crystalline inclusions of alkali perrhenates detected with X-ray diffraction. Since (99)Tc concentrations in a glass waste form are predicted to be wastes, assuming Tc as Tc(7+) and similarities between Re(7+) and Tc(7+) behavior in this glass system.

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

Energy Technology Data Exchange (ETDEWEB)

Deschanels, X.; Cachia, J.N.; Lopez, C.; Peuget, S. [CEA Marcoule, BP 17171, 30207 Bagnols sur Ceze (France)

2008-07-01

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.

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

International Nuclear Information System (INIS)

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

2003-01-01

The following results are a part of an independent thesis study conducted at Diagnostic Instrumentation and Analysis Laboratory-Mississippi State University. A series of small-scale borosilicate glass melts from high-level waste simulant were produced with waste loadings ranging from 20% to 55% (by mass). Crushed glass was allowed to react in an aqueous environment under static conditions for 7 days. The data obtained from the chemical analysis of the leachate solutions were used to test the durability of the resulting glasses. Studies were performed to determine the qualitative effects of increasing the B2O3 content on the overall waste glass leaching behavior. Structural changes in a glass arising due to B2O3 were detected indirectly by its chemical durability, which is a strong function of composition and structure. Modeling was performed to predict glass durability quantitatively in an aqueous environment as a direct function of oxide composition

Gamma rays shielding and sensing application of some rare earth doped lead-alumino-phosphate glasses

Science.gov (United States)

Kaur, Preet; Singh, Devinder; Singh, Tejbir

2018-03-01

Seven rare earth (Sm3+, Eu3+ and Nd3+) doped lead alumino phosphate glasses were prepared. The protective and sensing measures from gamma rays were analysed in terms of parameters viz. density (ρ), refractive index, energy band gap (Eg), mean free path (mfp), effective atomic number (Zeff) and buildup factors (energy absorption EABF as well as exposure buildup factor EBF). The energy dependent parameters (mfp, Zeff, EABF and EBF) were investigated in the energy region from 15 keV to 15 MeV. EABF and EBF values were observed to be maximum in the intermediate energy region. Besides, the EABF and EBF values for the prepared samples are shown to have strong dependence on chemical composition of the glass at lower energy, whereas, it is almost independent of chemical composition in higher energy region. The prepared glass samples are found to have potential applications in radiation shielding as well as radiation sensing, which further find numerous applications in the field of medicine and industry.

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

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

Effect of MoO3 addition on phase separation in borosilicate glasses

International Nuclear Information System (INIS)

Wakabayashi, Hajimu; Yamanaka, Hiroshi; Terai, Ryohei; Fukumoto, Shinji.

1987-01-01

The effect of MoO 3 addition on the phase separation of sodium borosilicate glasses has been studied by electron microscopic observation and electrical conductivity measurement. With increasing MoO 3 addition, the immiscibility temperatures rose, the growth rate of phase separation increased, and the immiscibility region in the Na 2 O-B 2 O 3 -SiO 2 system extended. When MoO 3 more than 5 mol% was added to the glasses, two stages of phase separation appeared ; one is metastable immiscibility, which takes place below the liquidus temperature, and the other is stable immiscibility, occurring above the liquidus temperature. The present experiment confirmed that the conductivity measurement of molten glasses is usefull to detect phase separation in the glasses, giving some suggestions for preventing the separation of molybdates in nuclear waste glasses and also for controlling the micro-pore sizes of porous glasses. (author)

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

International Nuclear Information System (INIS)

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

Preparation and characterization of an improved borosilicate glass matrix for the incorporation of high level radioactive waste (HAW). Pt. 1

International Nuclear Information System (INIS)

Guber, W.; Hussain, M.; Kahl, L.; Ondracek, G.; Saidl, J.; Dippel, T.

1979-08-01

On the basis of laboratory and technical experience with the preparation and the characterization of borosilicate glasses as solidification matrix for high level radioactive waste solution (HAW), a borosilicate glass composition with optimum properties has been developed. Keeping in view the technical and final storage requirements, a number of glass compositions with varying proportions of influential components as Al, Mg, Na were prepared and thoroughly investigated for certain parameters as specific gravity, thermal conductivity, impact resistance, thermal expansion, viscosity, characteristic temperature points, specific heat, evaporation losses from the melt, electrical conductivity, leach resistance, tendency toward recrystallization and second phase formation. All the compositions (some with different amounts of Gd 2 O 3 , an expected neutron poision) contained 15 wt. % simulated HAW oxides. Samples for investigation were fabricated very close to the actual process conditions of vitrification. Two glass products GP12 and GP26 (3.7% Gd 2 O 3 ) have been selected out of 25 glasses as the optimised products for further thorough investigations. Leach resistance, viscosity at 1420 K, tendency towards recrystallization and second phase formation were the most important deciding factors. (orig.) [de

Effect of ThO2 concentration on thermo-physical properties of barium borosilicate glass

International Nuclear Information System (INIS)

Mishra, R.K.; Munshi, A.K.; Kaushik, C.P.; Raj, Kanwar; Shobha, M.; Srikhande, V.K.; Kothiyal, G.P.; Tyagi, A.K.

2006-01-01

An advanced heavy water reactor is being developed at Bhabha Atomic Research Centre (BARC) India with an aim of utilizing thorium for power generation. The high level radioactive liquid waste (HLW) generated from reprocessing of Th-based spent fuel is expected to contain Th as one of the main constituents other than fission products, corrosion products, actinides and added chemicals. Barium borosilicate (BBS) glass is being used for vitrification of the HLW generated at the reprocessing plant at BARC, Trombay, Mumbai

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

International Nuclear Information System (INIS)

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

1990-01-01

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

Investigation of local environment around rare earths (La and Eu) by fluorescence line narrowing during borosilicate glass alteration

Energy Technology Data Exchange (ETDEWEB)

Molières, Estelle [CEA – DEN-DTCD-LCV-SECM Laboratoire d' études du Comportement à Long Terme, 30207 Bagnols-sur-Cèze (France); Panczer, Gérard; Guyot, Yannick [Institut Lumière Matière, UMR5306 Université Lyon 1-CNRS, Université de Lyon, 69622 Villeurbanne cedex (France); Jollivet, Patrick [CEA – DEN-DTCD-LCV-SECM Laboratoire d' études du Comportement à Long Terme, 30207 Bagnols-sur-Cèze (France); Majérus, Odile; Aschehoug, Patrick; Barboux, Philippe [Laboratoire de Chimie de la Matière Condensée de Paris, UMR-CNRS 7574, École Nationale Supérieure de Chimie de Paris (ENSCP Chimie-ParisTech), 11 rue Pierre et Marie Curie, 75231 Paris (France); Gin, Stéphane [CEA – DEN-DTCD-LCV-SECM Laboratoire d' études du Comportement à Long Terme, 30207 Bagnols-sur-Cèze (France); Angeli, Frédéric, E-mail: frederic.angeli@cea.fr [CEA – DEN-DTCD-LCV-SECM Laboratoire d' études du Comportement à Long Terme, 30207 Bagnols-sur-Cèze (France)

2014-01-15

The local environment of europium in soda-lime borosilicate glasses with a range of La{sub 2}O{sub 3} content was probed by continuous luminescence and Fluorescence Line Narrowing (FLN) to investigate the local environment of rare earth elements in pristine and leached glass. After aqueous leaching at 90 °C at pH 7 and 9.5, rare earths were fully retained and homogeneously distributed in the amorphous alteration layer (commonly called gel). Two separate silicate environments were observed in pristine and leached glasses regardless of the lanthanum content and the leaching conditions. A borate environment surrounding europium was not observed in pristine and leached glasses. During glass alteration, OH groups were located around the europium environment, which became more organized (higher symmetry) in the first coordination shell. -- Highlights: • No borate environment surrounding europium was detected in pristine borosilicate glasses. • Up to 12 mol% of REE2O3 in glass, local environment of europium does not significantly change. • Europium environment becomes more ordered and symmetric in gels than in pristine glasses. • Two distinct silicate sites were observed, as well in pristine glass as in gels (leached glasses). • In altered glasses, OH groups were located around europium.

Investigation of local environment around rare earths (La and Eu) by fluorescence line narrowing during borosilicate glass alteration

International Nuclear Information System (INIS)

Molières, Estelle; Panczer, Gérard; Guyot, Yannick; Jollivet, Patrick; Majérus, Odile; Aschehoug, Patrick; Barboux, Philippe; Gin, Stéphane; Angeli, Frédéric

2014-01-01

The local environment of europium in soda-lime borosilicate glasses with a range of La 2 O 3 content was probed by continuous luminescence and Fluorescence Line Narrowing (FLN) to investigate the local environment of rare earth elements in pristine and leached glass. After aqueous leaching at 90 °C at pH 7 and 9.5, rare earths were fully retained and homogeneously distributed in the amorphous alteration layer (commonly called gel). Two separate silicate environments were observed in pristine and leached glasses regardless of the lanthanum content and the leaching conditions. A borate environment surrounding europium was not observed in pristine and leached glasses. During glass alteration, OH groups were located around the europium environment, which became more organized (higher symmetry) in the first coordination shell. -- Highlights: • No borate environment surrounding europium was detected in pristine borosilicate glasses. • Up to 12 mol% of REE2O3 in glass, local environment of europium does not significantly change. • Europium environment becomes more ordered and symmetric in gels than in pristine glasses. • Two distinct silicate sites were observed, as well in pristine glass as in gels (leached glasses). • In altered glasses, OH groups were located around europium

Determination of the free enthalpies of formation of borosilicate glasses

International Nuclear Information System (INIS)

Linard, Y.

2000-01-01

This work contributes to the study of the thermochemical properties of nuclear waste glasses. Results are used to discuss mechanisms and parameters integrated in alteration models of conditioning materials. Glass is a disordered material defined thermodynamically as a non-equilibrium state. Taking into account one order parameter to characterise its configurational state, the metastable equilibrium for the glass was considered and the main thermochemical properties were determined. Calorimetric techniques were used to measure heat capacities and formation enthalpies of borosilicate glasses (from 3 to 8 constitutive oxides). Formation Entropies were measured too, using the entropy theory of relaxation processes proposed by Adam and Gibbs (1965). The configurational entropy contribution were determined from viscosity measurements. This set of data has allowed the calculation of Gibb's free energies of dissolution of glasses in pure water. By comparison with leaching experiments, it has been demonstrated that the decreasing of the dissolution rate at high reaction progress cannot be associated to the approach of an equilibrium between the sound glass and the aqueous solution. The composition changes of the reaction area at the glass surface need to be considered too. To achieve a complete description of the thermodynamic stability, the equilibrium between hydrated de-alkalinized glass and/or the gel layer with the aqueous solution should also be evaluated. (author)

Wetspun poly-L-(lactic acid)-borosilicate bioactive glass scaffolds for guided bone regeneration

Energy Technology Data Exchange (ETDEWEB)

Fernandes, João S., E-mail: joao.fernandes@dep.uminho.pt [3B' s Research Group - Biomaterials, Biodegradables and Biomimetics, University of Minho, Headquarters of the European Institute of Excellence on Tissue Engineering and Regenerative Medicine, AvePark-Parque de Ciência e Tecnologia, Zona Industrial da Gandra, 4805-017 Barco GMR (Portugal); ICVS/3B' s - PT Government Associate Laboratory, Braga/Guimarães (Portugal); Reis, Rui L. [3B' s Research Group - Biomaterials, Biodegradables and Biomimetics, University of Minho, Headquarters of the European Institute of Excellence on Tissue Engineering and Regenerative Medicine, AvePark-Parque de Ciência e Tecnologia, Zona Industrial da Gandra, 4805-017 Barco GMR (Portugal); ICVS/3B' s - PT Government Associate Laboratory, Braga/Guimarães (Portugal); Pires, Ricardo A., E-mail: rpires@dep.uminho.pt [3B' s Research Group - Biomaterials, Biodegradables and Biomimetics, University of Minho, Headquarters of the European Institute of Excellence on Tissue Engineering and Regenerative Medicine, AvePark-Parque de Ciência e Tecnologia, Zona Industrial da Gandra, 4805-017 Barco GMR (Portugal); ICVS/3B' s - PT Government Associate Laboratory, Braga/Guimarães (Portugal)

2017-02-01

We developed a porous poly-L-lactic acid (PLLA) scaffold compounded with borosilicate bioactive glasses (BBGs) endowing it with bioactive properties. Porous PLLA-BBG fibre mesh scaffolds were successfully prepared by the combination of wet spinning and fibre bonding techniques. Micro-computed tomography (μCT) confirmed that the PLLA-BBG scaffolds containing ≈ 25% of BBGs (w/w) exhibited randomly interconnected porous (58 to 62% of interconnectivity and 53 to 67% of porosity) with mean pore diameters higher that 100 μm. Bioactivity and degradation studies were performed by immersing the scaffolds in simulated body fluid (SBF) and ultrapure water, respectively. The PLLA-BBG scaffolds presented a faster degradation rate with a constant release of inorganic species, which are capable to produce calcium phosphate structures at the surface of the material after 7 days of immersion in SBF (Ca/P ratio of ~ 1.7). Cellular in vitro studies with human osteosarcoma cell line (Saos-2) and human adipose-derived stem cells (hASCs) showed that PLLA-BBGs are not cytotoxic to cells, while demonstrating their capacity to promote cell adhesion and proliferation. Overall, we showed that the proposed scaffolds present a tailored kinetics on the release of inorganic species and controlled biological response under conditions that mimic the bone physiological environment. - Highlights: • We prepared borosilicate glasses and their PLLA composites in the form of fibres. • These glasses imparted bioactivity and controlled degradability to the fibres. • The prepared fibres did not elicit cytotoxicity. • hASCs attached and proliferated in the surface and inner sections of the scaffolds. • The composites present appropriate properties to be used in bone tissue engineering.

Wetspun poly-L-(lactic acid)-borosilicate bioactive glass scaffolds for guided bone regeneration

International Nuclear Information System (INIS)

Fernandes, João S.; Reis, Rui L.; Pires, Ricardo A.

2017-01-01

We developed a porous poly-L-lactic acid (PLLA) scaffold compounded with borosilicate bioactive glasses (BBGs) endowing it with bioactive properties. Porous PLLA-BBG fibre mesh scaffolds were successfully prepared by the combination of wet spinning and fibre bonding techniques. Micro-computed tomography (μCT) confirmed that the PLLA-BBG scaffolds containing ≈ 25% of BBGs (w/w) exhibited randomly interconnected porous (58 to 62% of interconnectivity and 53 to 67% of porosity) with mean pore diameters higher that 100 μm. Bioactivity and degradation studies were performed by immersing the scaffolds in simulated body fluid (SBF) and ultrapure water, respectively. The PLLA-BBG scaffolds presented a faster degradation rate with a constant release of inorganic species, which are capable to produce calcium phosphate structures at the surface of the material after 7 days of immersion in SBF (Ca/P ratio of ~ 1.7). Cellular in vitro studies with human osteosarcoma cell line (Saos-2) and human adipose-derived stem cells (hASCs) showed that PLLA-BBGs are not cytotoxic to cells, while demonstrating their capacity to promote cell adhesion and proliferation. Overall, we showed that the proposed scaffolds present a tailored kinetics on the release of inorganic species and controlled biological response under conditions that mimic the bone physiological environment. - Highlights: • We prepared borosilicate glasses and their PLLA composites in the form of fibres. • These glasses imparted bioactivity and controlled degradability to the fibres. • The prepared fibres did not elicit cytotoxicity. • hASCs attached and proliferated in the surface and inner sections of the scaffolds. • The composites present appropriate properties to be used in bone tissue engineering.

Glass packages in interim storage

International Nuclear Information System (INIS)

Jacquet-Francillon, N.

1994-10-01

This report summarize the current state of knowledge concerning the behavior of type C waste packages consisting of vitrified high-level solutions produced by reprocessing spent fuel. The composition and the physical and chemical properties of the feed solutions are reviewed, and the vitrification process is described. Sodium alumino-borosilicate glass compositions are generally employed - the glass used at la Hague for LWR fuel solutions, for example, contains 45 % SiO 2 . The major physical, chemical, mechanical and thermal properties of the glass are reviewed. In order to allow their thermal power to diminish, the 3630 glass packages produced (as of January 1993) in the vitrification facilities at Marcoule and La Hague are placed in interim storage for several decades. The actual interim storage period has not been defined, as it is closely related to the concept and organization selected for the final destination of the packages: a geological repository. The glass behavior under irradiation is described. Considerable basic and applied research has been conducted to assess the aqueous leaching behavior of nuclear containment glass. The effects of various repository parameters (temperature, flow rate, nature of the environmental materials) have been investigated. The experimental findings have been used to specify a model describing the kinetics of aqueous corrosion of the glass. More generally all the ''source term'' models developed in France by the CEA or by ANDRA are summarized. (author). 152 refs., 33 figs

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

International Nuclear Information System (INIS)

Cunnane, J.C.

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

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.

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

International Nuclear Information System (INIS)

Kaushik, C.P.; Mishra, R.K.; Thorat, Vidya; Ramchandran, M.; Amar Kumar; Ozarde, P.D.; Raj, Kanwar; Das, D.

2004-07-01

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 (SiO 2 :B 2 O 3 :Na 2 O : MnO : TiO 2 ) 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)

Physical and optical properties of lithium borosilicate glasses doped with Dy3+ ions

Science.gov (United States)

Ramteke, D. D.; Gedam, R. S.; Swart, H. C.

2018-04-01

The borosilicate glasses with Dy3+ ions were prepared by the melt quench technique with varying concentration of Dy2O3. The glasses were characterized by the density calculation, absorbance and photoluminescence (PL) spectroscopy measurements. Density and molar volume of the glasses increases with increase in Dy3+ ions in the glass matrix. This behavior is correlated with the higher molecular weight and larger ionic radius of Dy3+ ion compared to the other constituents of glass matrix. Emission of Dy3+ doped glasses showed three bands at 482, 573 and at 665 nm which correspond to 6H15/2 (blue), 6H13/2 (yellow) and 6H11/2 (red) transitions. The emission spectra of glasses with different concentration of Dy3+ ions shows that, glasses with 0.5 mol% of Dy2O3 shows highest emission and decreases with further doping. CIE 1931 chromaticity diagram showed that the emission of these glasses was in the white region. Photographs of these glasses under 349 nm Light emitting diode excitation also confirmed the white light emission from these glasses.

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.

Deformation mechanisms during nanoindentation of sodium borosilicate glasses of nuclear interest

Energy Technology Data Exchange (ETDEWEB)

Kilymis, D. A.; Delaye, J.-M., E-mail: jean-marc.delaye@cea.fr [CEA Marcoule, DEN/DTCD, Service d’Etude et Comportement des Matériaux de Conditionnement, BP17171 30207 Bagnols-sur-Cèze Cedex (France)

2014-07-07

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

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

Science.gov (United States)

Kilymis, D A; Delaye, J-M

2014-07-07

In this paper we analyze results of Molecular Dynamics simulations of Vickers nanoindentation, performed for sodium borosilicate glasses of interest in the nuclear industry. Three glasses have been studied in their pristine form, as well as a disordered one that is analogous to the real irradiated glass. We focused in the behavior of the glass during the nanoindentation in order to reveal the mechanisms of deformation and how they are affected by microstructural characteristics. Results have shown a strong dependence on the SiO2 content of the glass, which promotes densification due to the open structure of SiO4 tetrahedra and also due to the strength of Si-O bonds. Densification for the glasses is primarily expressed by the relative decrease of the Si-O-Si and Si-O-B angles, indicating rotation of the structural units and decrease of free volume. The increase of alkali content on the other hand results to higher plasticity of the matrix and increased shear flow. The most important effect on the deformation mechanism of the disordered glasses is that of the highly depolymerized network that will also induce shear flow and, in combination with the increased free volume, will result in the decreased hardness of these glasses, as has been previously observed.

Influence of Some Nuclear Waste on The Durability and Mechanical Properties of Borosilicate glass

International Nuclear Information System (INIS)

El-Alaily, N.A.

2003-01-01

Various glass systems have been shown to be suitable for producing waste glass forms that are thermally and mechanically stable and exhibit good chemical durability. In this study borosilicate glass containing sodium oxide and aluminum oxide was prepared as a host for high level nuclear waste. The glass durability when the samples were immersed either in distilled water or ground water at 70 degree was studied. The density, porosity and mechanical properties were also investigated. The effects of exposing the samples immersed in groundwater to gamma rays in the glass durability and all other mentioned properties were also studied. The results showed that immersing the glass in ground water causing a decrease in the glass durability. The exposure of the glass immersed in ground water to the gamma rays increases the durability of the glass. The mechanical properties of the prepared glass were good. Although these properties decrease for the corroded glass but they were still good

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)

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

International Nuclear Information System (INIS)

Khalil, T.K.; Bossert, J.; Aly, H.F.; Bossert, J.

1999-01-01

Composite concept in materials science can be conveniently applied in the waste treatment technology to construct specific t ailor made c omposite 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

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

International Nuclear Information System (INIS)

Maheshwari, Aditya; Om Prakash; Kumar, Devendra; Rai, S.B.

2011-01-01

Upconversion behaviour has been studied in various matrices and fine powders of SrTiO 3 by previous workers. In present work, Er 3+ /Yb 3+ were doped in appropriate ratio in SrO.TiO 2 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 Er 3+ /Yb 3+ :SrO.TiO 2 borosilicate glasses with same amount of Er 2 O 3 and Yb 2 O 3 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, Sr 3 Ti 2 O 7 , Ti 10 O 19 and SrTiO 3 , TiO 2 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

Tc and Re Behavior in Borosilicate Waste Glass Vapor Hydration Tests

International Nuclear Information System (INIS)

McKeown, David A.; Buechele, Andrew C.; Pegg, Ian L.; Lukens, Wayne W.; Shuh, David K.

2007-01-01

Technetium (Tc), found in some nuclear wastes, is of particular concern with regard to long-term storage, because of its long-lived radioactivity and high mobility in the environment. Tc and rhenium (Re), commonly used as a non-radioactive surrogate for Tc, were studied to assess their behavior in borosilicate glass under hydrothermal conditions in the Vapor Hydration Test (VHT). X-ray absorption spectroscopy (XAS) and scanning electron microscopy (SEM) measurements were made on the original Tc- and Re-containing glasses and their corresponding VHT samples, and show different behavior for Tc and Re under VHT conditions. XAS indicates that, despite starting with different Tc(IV) and Tc(VII) distributions in each glass, the VHT samples have 100% Tc(IV)O 6 environments. SEM shows complete alteration of the original glass, Tc enrichment near the sample surface, and Tc depletion in the center. Perrhenate (Re(VII)O 4 - ) is dominant in both Re-containing samples before and after the VHT, where Re is depleted near the VHT sample surface and more concentrated toward the center. (authors)

A review of phase separation in borosilicate glasses, with reference to nuclear fuel waste immobilization

International Nuclear Information System (INIS)

Taylor, P.

1990-08-01

This report reviews information on miscibility limits in borosilicate glass-forming systems. It includes both a literature survey and an account of experimental work performed within the Canadian Nuclear Fuel Waste Management Program. Emphasis is placed on the measurement and depiction of miscibility limits in multicomponent (mainly quaternary) systems, and the effects of individual components on the occurrence of phase separation. The behaviour of the multicomponent system is related to that of simpler (binary and ternary) glass systems. The possible occurrence of phase separation, as well as its avoidance, during processing of nuclear waste glasses is discussed

3 and 4 oxidation state element solubilities in borosilicate glasses. Implement to actinides in nuclear glasses

International Nuclear Information System (INIS)

Cachia, J.N.

2005-12-01

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 3 N 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)

Photoelastic examination of borosilicate glass discs used in the insulating legs for the NSF tandem

International Nuclear Information System (INIS)

Acton, W.J.; Cundy, D.

1981-04-01

The results are presented of a photoelastic stress analysis carried out to establish the effect of re-annealing borosilicate glass discs used in the insulating legs of the 30 MV tandem van de Graaff accelerator of the NSF. The results show that re-annealing of the glass discs has no measurable effect on reducing the high stress at inclusions and re-emphasise the need to exercise great care in selecting suitable discs for use in the insulating legs. (U.K.)

Development of Li+ alumino-silicate ion source

International Nuclear Information System (INIS)

Roy, P.K.; Seidl, P.A.; Waldron, W.; Greenway, W.; Lidia, S.; Anders, A.; Kwan, J.

2009-01-01

To uniformly heat targets to electron-volt temperatures for the study of warm dense matter, one strategy is to deposit most of the ion energy at the peak of energy loss (dE/dx) with a low (E < 5 MeV) kinetic energy beam and a thin target. Lower mass ions have a peak dE/dx at a lower kinetic energy. To this end, a small lithium (Li+) alumino-silicate source has been fabricated, and its emission limit has been measured. These surface ionization sources are heated to 1000-1150 C where they preferentially emit singly ionized alkali ions. Alumino-silicates sources of K+ and Cs+ have been used extensively in beam experiments, but there are additional challenges for the preparation of high-quality Li+ sources: There are tighter tolerances in preparing and sintering the alumino-silicate to the substrate to produce an emitter that gives uniform ion emission, sufficient current density and low beam emittance. We report on recent measurements ofhigh ( up to 35 mA/cm2) current density from a Li+ source. Ion species identification of possible contaminants is being verified with a Wien (E x B) filter, and via time-of-flight.

Raman and X-ray absorption spectroscopic studies of hydrothermally altered alkali-borosilicate nuclear waste glass

Energy Technology Data Exchange (ETDEWEB)

McKeown, David A., E-mail: davidm@vsl.cua.ed [Vitreous State Laboratory, Catholic University of America, 620 Michigan Ave., N.E., Washington, DC 20064 (United States); Buechele, Andrew C.; Viragh, Carol; Pegg, Ian L. [Vitreous State Laboratory, Catholic University of America, 620 Michigan Ave., N.E., Washington, DC 20064 (United States)

2010-04-01

Raman spectroscopy and X-ray absorption spectroscopy (XAS) are used to characterize structural changes that took place in hydrothermally altered (Na,K)-alumina-borosilicate glasses with different Na/K ratios, formulated as part of a durability study to investigate the behavior of glasses for nuclear waste storage. The hydrothermal experiments, or vapor hydration tests (VHT), were performed on each glass for 3 and 20 days at 200 deg. C to accelerate and approximate long-term alteration processes that may occur in a nuclear waste repository. Results found for both glasses and their VHT altered counterparts show little, if any, structural influence from the different starting Na/K ratios. X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, and Raman spectroscopy indicate that the altered samples are mostly amorphous with small amounts of analcime-like and leucite-like crystals within 200 mum of the sample surface and contain up to 9.7 wt.% water or OH. The Raman data are nearly identical for the amorphous portions of all altered VHT samples investigated, and indicate that two glass structural changes took place during alteration: one, partial depolymerization of the alumina-borosilicate network, and two, introduction of water or OH. Al and Si XAS data indicate tetrahedral AlO{sub 4} and SiO{sub 4} environments in the original glasses as well as in the altered samples. Small energy shifts of the Si K-edge also show that the altered VHT samples have less polymerized networks than the original glass. Na XAS data indicate expanded Na environments in the VHT samples with longer Na-O distances and more nearest-neighbor oxygen atoms, compared with the original glasses, which may be due to hydrous species introduced into the expanding Na-sites.

Silicate glasses

International Nuclear Information System (INIS)

Lutze, W.

1988-01-01

Vitrification of liquid high-level radioactive wastes has received the greatest attention, world-wide, compared to any other HLW solidification process. The waste form is a borosilicate-based glass. The production of phosphate-based glass has been abandoned in the western world. Only in the Soviet Union are phosphate-based glasses still being developed. Vitrification techniques, equipment and processes and their remote operation have been developed and studied for almost thirty years and have reached a high degree of technical maturity. Industrial demonstration of the vitrification process has been in progress since 1978. This chapter is a survey of world-wide research and development efforts in nuclear waste glasses and its production technology. The principal glasses considered are silicate glasses which contain boron, i.e., borosilicate glasses

Diffusion of cesium in sodium-borosilicate glasses for nuclear waste immobilisation. Diffusie van cesium in natrium borosilicaat glazen voor het immobiliseren van radioaktief afval

Energy Technology Data Exchange (ETDEWEB)

Janssen, F.J.J.G.; Sengers, E.G.F. (Keuring van Electrotechnische Materialen NV, Arnhem (Netherlands)); Waal, H. de (TPD-TNO-Glass technology, Eindhoven (Netherlands))

1989-09-26

Diffusion of cesium in borosilicate glass for high-level radioactive waste is discussed. For this purpose model glasses with non-radioactive elements are being made, in accordance with the specifications of the reprocessing plants, from which concentration couples are composed. A concentration couple consists of two cylinders of borosilicate glass which contain different amounts of cesium. After heat treatment the couples are studied by means of the scanning electron microscopy and X-ray microanalysis. The model study will provide a basis for predictions of the containment achieved over a longer period of time. (author). 11 refs.; 2 figs.; 2 tabs.

Optical band gap and spectroscopic study of lithium alumino silicate glass containing Y3+ ions.

Science.gov (United States)

Shakeri, M S; Rezvani, M

2011-09-01

The effect of different amounts of Y2O3 dopant on lithium alumino silicate (LAS) glass has been studied in this work. Glasses having 14.8Li2O-20Al2O3-65.2SiO2 (wt%) composition accompanied with Y2O3 dopant were prepared by normal melting process. In order to calculate the absorption coefficient of samples, transmittance and reflectance spectra of polished samples were measured in the room temperature. Optical properties i.e. Fermi energy level, direct and indirect optical band gaps and Urbach energy were calculated using functionality of extinction coefficient from Fermi-Dirac distribution function, Tauc's plot and the exponential part of absorption coefficient diagram, respectively. It has been clarified that variation in mentioned optical parameters is associated with the changes in physical properties of samples i.e. density or molar mass. On the other hand, increasing of Y3+ ions in the glassy microstructure of samples provides a semiconducting character to LAS glass by reducing the direct and indirect optical band gaps of glass samples from 1.97 to 1.67 and 3.46 to 2.1 (eV), respectively. These changes could be attributed to the role of Y3+ ions as the network former in the track of SiO4 tetrahedrals. Copyright © 2011 Elsevier B.V. All rights reserved.

Preliminary assessment of the controlled release of radionuclides from waste packages containing borosilicate waste glass

International Nuclear Information System (INIS)

Strachan, D.M.; McGrail, B.P.; Apted, M.J.; Engle, D.W.; Eslinger, P.W.

1990-06-01

The purpose of this report is to provide a preliminary assessment of the release-rate for an engineered barriers subsystem (EBS) containing waste packages of defense high-level waste borosilicate glass at geochemical and hydrological conditions similar to the those at Yucca Mountain. The relationship between the proposed Waste Acceptance Preliminary Specifications (WAPS) test of glass- dissolution rate and compliance with the NRC's release-rate criterion is also evaluated. Calculations are reported for three hierarchical levels: EBS analysis, waste-package analysis, and waste-glass analysis. The following conclusions identify those factors that most acutely affect the magnitude of, or uncertainty in, release-rate performance

Entrapment of 137Cs vapour generated during vitrification and casting of cesium borosilicate glass by inorganic materials

International Nuclear Information System (INIS)

Ram, Ramu; Gandhi, Shyamala; Dash, A.; Varma, R.N.

2003-01-01

Efficiency of different inorganic materials like zirconium antimonate (ZrA), ammonium molybdophosphate (AMP), synthetic zeolites, activated charcoal, glass wool etc, towards the entrapment of 137 Cs vapour escaping during vitrification and casting of cesium borosilicate glass required for the preparation of 137 Cs sources for medical and industrial applications have been determined. The recovery of entrapped cesium using dilute acids for subsequent recycling has also been explored. (author)

Li+ alumino-silicate ion source development for the Neutralized Drift Compression Experiment (NDCX)

Energy Technology Data Exchange (ETDEWEB)

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

2010-10-01

We report results on lithium alumino-silicate ion source development in preparation for warmdense-matter heating experiments on the new Neutralized Drift Compression Experiment (NDCXII). The practical limit to the current density for a lithium alumino-silicate source is determined by the maximum operating temperature that the ion source can withstand before running into problems of heat transfer, melting of the alumino-silicate material, and emission lifetime. Using small prototype emitters, at a temperature of ~;;1275 oC, a space-charge-limited Li+ beam current density of J ~;;1 mA/cm2 was obtained. The lifetime of the ion source was ~;;50 hours while pulsing at a rate of 0.033 Hz with a pulse duration of 5-6 mu s.

Li+ alumino-silicate ion source development for the Neutralized Drift Compression Experiment (NDCX)

International Nuclear Information System (INIS)

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

2010-01-01

We report results on lithium alumino-silicate ion source development in preparation for warm-dense-matter heating experiments on the new Neutralized Drift Compression Experiment (NDCX-II). The practical limit to the current density for a lithium alumino-silicate source is determined by the maximum operating temperature that the ion source can withstand before running into problems of heat transfer, melting of the alumino-silicate material, and emission lifetime. Using small prototype emitters, at a temperature of ∼1275 C, a space-charge-limited Li + beam current density of J ∼1 mA/cm 2 was obtained. The lifetime of the ion source was ∼50 hours while pulsing at a rate of 0.033 Hz with a pulse duration of 5-6 (micro) s.

Composition-Structure-Property Relations of Compressed Borosilicate Glasses

Science.gov (United States)

Svenson, Mouritz N.; Bechgaard, Tobias K.; Fuglsang, Søren D.; Pedersen, Rune H.; Tjell, Anders Ø.; Østergaard, Martin B.; Youngman, Randall E.; Mauro, John C.; Rzoska, Sylwester J.; Bockowski, Michal; Smedskjaer, Morten M.

2014-08-01

Hot isostatic compression is an interesting method for modifying the structure and properties of bulk inorganic glasses. However, the structural and topological origins of the pressure-induced changes in macroscopic properties are not yet well understood. In this study, we report on the pressure and composition dependences of density and micromechanical properties (hardness, crack resistance, and brittleness) of five soda-lime borosilicate glasses with constant modifier content, covering the extremes from Na-Ca borate to Na-Ca silicate end members. Compression experiments are performed at pressures ≤1.0 GPa at the glass transition temperature in order to allow processing of large samples with relevance for industrial applications. In line with previous reports, we find an increasing fraction of tetrahedral boron, density, and hardness but a decreasing crack resistance and brittleness upon isostatic compression. Interestingly, a strong linear correlation between plastic (irreversible) compressibility and initial trigonal boron content is demonstrated, as the trigonal boron units are the ones most disposed for structural and topological rearrangements upon network compaction. A linear correlation is also found between plastic compressibility and the relative change in hardness with pressure, which could indicate that the overall network densification is responsible for the increase in hardness. Finally, we find that the micromechanical properties exhibit significantly different composition dependences before and after pressurization. The findings have important implications for tailoring microscopic and macroscopic structures of glassy materials and thus their properties through the hot isostatic compression method.

Infrared and x-ray photoelectron spectroscopic studies on sodium borosilicate glass interacted with thermally oxidized aluminides formed on alloy 690

International Nuclear Information System (INIS)

Yusufali, C.; Dutta, R.S.; Dey, G.K.; Kshirsagar, R.J.; Jagannath; Mishra, R.K.

2012-01-01

Thermally oxidized aluminides formed on Ni-Cr-Fe based superalloy 690 substrates were subjected to interaction with sodium borosilicate melt (used as matrices for immobilization of high-level radioactive liquid waste) at 1248 K for 192 hours. After the interaction, Fourier-transform infrared (FT-IR) spectroscopy analysis of glass samples indicated the incorporation of Al in the glass network. X-ray photoelectron spectroscopy (XPS) of glass specimens revealed modified glass structure. (author)

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

International Nuclear Information System (INIS)

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

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

Preparation method and thermal properties of samarium and europium-doped alumino-phosphate glasses

Energy Technology Data Exchange (ETDEWEB)

Sava, B.A., E-mail: savabogdanalexandru@yahoo.com [National Institute of Research and Development for Optoelectronics, Department for Optospintronics, 409 Atomistilor Street, P.O. Box MG – 5, RO-77125 Magurele (Romania); Elisa, M., E-mail: astatin18@yahoo.com [National Institute of Research and Development for Optoelectronics, Department for Optospintronics, 409 Atomistilor Street, P.O. Box MG – 5, RO-77125 Magurele (Romania); Boroica, L., E-mail: boroica_lucica@yahoo.com [National Institute for Lasers, Plasma and Radiation Physics, 77125 Magurele (Romania); Monteiro, R.C.C., E-mail: rcm@fct.unl.pt [Center of Materials Research/Institute for Nanostructures, Nanomodelling and Nanofabrication, (CENIMAT/I3N), Department of Materials Sciences, Faculty of Sciences and Technology, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal)

2013-12-01

Highlights: • Improved preparation method of rare-earth-doped phosphate glasses was done. • Working and annealing temperatures were lower than for undoped phosphate glass. • Doped glass viscosity is also lower and has quasi-linear variation with temperature. • Exothermic peak appears at about 555 °C and 685 °C, due to devitrification in glass. -- Abstract: The present work investigates alumino-phosphate glasses from Li{sub 2}O–BaO–Al{sub 2}O{sub 3}–La{sub 2}O{sub 3}–P{sub 2}O{sub 5} system containing Sm{sup 3+} and Eu{sup 3+} ions, prepared by two different ways: a wet raw materials mixing route followed by evaporation and melt-quenching, and by remelting of shards. The linear thermal expansion coefficient measured by dilatometry is identical for both rare-earth-doped phosphate glasses. Comparatively to undoped phosphate glass the linear thermal expansion coefficient increases with 2 × 10{sup −7} K{sup −1} when dopants are added. The characteristic temperatures very slowly decrease but can be considered constant with atomic weight, atomic number and f electrons number of the doping ions in the case of T{sub g} (vitreous transition temperature) and T{sub sr} (high annealing temperature) but slowly increase in the case of T{sub ir} (low annealing temperature–strain point) and very slowly increase, being practically constant in the case of T{sub D} (dilatometric softening temperature). Comparatively to undoped phosphate glass the characteristic temperatures of Sm and Eu-doped glasses present lower values. The higher values of electrical conductance for both doped glasses, comparatively to usual soda-lime-silicate glass, indicate a slightly reduced stability against water. The viscosity measurements, showed a quasi-linear variation with temperature the mean square deviation (R{sup 2}) being ranged between 0.872% and 0.996%. The viscosity of doped glasses comparatively to the undoped one is lower at the same temperature. Thermogravimetric

Comparison of radiation and quenching rate effects on the structure of a sodium borosilicate glass

International Nuclear Information System (INIS)

Peuget, Sylvain; Maugeri, Emilio-Andrea; Mendoza, Clement; Fares, Toby; Bouty, Olivier; Jegou, Christophe; Charpentier, Thibault; Moskura, Melanie

2013-01-01

The effects of quenching rate and irradiation on the structure of a sodium borosilicate glass were compared using 29 Si, 11 B, and 23 Na nuclear magnetic resonance and Raman spectroscopy. Quenching rate ranging from 0.1 to 3 * 10 4 K min -1 was studied. Various irradiation conditions were performed, i.e. gold-ion irradiation in a multi-energy mode (from 1 to 6.75 MeV), and Kr and Xe ion irradiations with energy of 74 and 92 MeV, respectively. In pile irradiation with thermal neutron flux was performed as well, to study the effect of alpha radiation from the nuclear reaction 10 B(n,α) 7 Li. Both irradiation and high quenching rate induce similar local order modification of the glass structure, mainly a decrease of the mean boron coordination and an increase of Q 3 units. Nevertheless, the variations observed under irradiation are more pronounced than the ones induced by the quenching rate. Moreover, some important modifications of the glass medium range order, i.e. the emergence of the D2 band associated to three members silica rings and a modification of the Si-O-Si angle distribution were only noticed after irradiation. These results suggest that the irradiated structure is certainly not exactly the one obtained by a rapidly quenched equilibrated melt, but rather a more disordered structure that was weakly relaxed during the very rapid quenching phase following the energy deposition step. Raman spectroscopy showed a similar irradiated structure whereas the glass evolutions were controlled by the electronic energy loss in the ion track formation regime for Kr-ion irradiation or by the nuclear energy loss for Au and OSIRIS irradiation. The similar irradiated structure despite different irradiation routes, suggests that the final structural state of this sodium borosilicate glass is mainly controlled by the glass reconstruction after the energy deposition step. (authors)

Preparation and nonlinear optical properties of indium nanocrystals in sodium borosilicate glass by the sol–gel route

International Nuclear Information System (INIS)

Zhong, Jiasong; Xiang, Weidong; Zhao, Haijun; Chen, Zhaoping; Liang, Xiaojuan; Zhao, Wenguang; Chen, Guoxin

2012-01-01

Graphical abstract: The sodium borosilicate glass doped with indium nanocrystals have been successfully prepared by sol–gel methods. And the indium nanocrystals in tetragonal crystal system have formed uniformly in the glass, and the average diameter of indium nanocrystals is about 30 nm. The third-order optical nonlinear refractive index γ, absorption coefficient β, and susceptibility χ (3) of the glass are determined to be −4.77 × 10 −16 m 2 /W, 2.67 × 10 −9 m/W, and 2.81 × 10 −10 esu, respectively. Highlights: ► Indium nanocrystals embedded in glass matrix have been prepared by sol–gel route. ► The crystal structure and composition are investigated by XRD and XPS. ► Size and distribution of indium nanocrystals is determined by TEM. ► The third-order optical nonlinearity is investigated by using Z-scan technique. -- Abstract: The sodium borosilicate glass doped with indium nanocrystals have been successfully prepared by sol–gel route. The thermal stability behavior of the stiff gel is investigated by thermogravimetric (TG) and differential thermal (DTA) analysis. The crystal structure of the glass is characterized by X-ray powder diffraction (XRD). Particle composition is determined by X-ray photoelectron spectroscopy (XPS). Size and distribution of the nanocrystals are characterized by transmission electron microscopy (TEM) as well as high-resolution transmission electron microscopy (HRTEM). Results show that the indium nanocrystals in tetragonal crystal structure have formed in glass, and the average diameter is about 30 nm. Further, the glass is measured by Z-scan technique to investigate the nonlinear optical (NLO) properties. The third-order NLO coefficient χ (3) of the glass is determined to be 2.81 × 10 −10 esu. The glass with large third-order NLO coefficient is promising materials for applications in optical devices.

Proving the role of boron in the structure of fly-ash/borosilicate glass based geopolymers

Czech Academy of Sciences Publication Activity Database

Taveri, Gianmarco; Toušek, J.; Bernardo, E.; Toniolo, N.; Boccaccini, A. R.; Dlouhý, Ivo

2017-01-01

Roč. 200, AUG (2017), s. 105-108 ISSN 0167-577X EU Projects: European Commission(XE) 642557 - CoACH Institutional support: RVO:68081723 Keywords : Fly-ash * Borosillicate * Geopolymerization * Spectroscopy * NMR * FTIR Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 2.572, year: 2016 http://www.sciencedirect.com/science/article/pii/S0167577X1730650X

Influence of iron ions on the structural properties of Zn-borosilicate glasses

International Nuclear Information System (INIS)

Music, S.; Gotic, M.; Popovic, S.

1989-01-01

The objectives of this study were to determine the influence of iron ions on the appearance of crystalline phases in Zn-borosilicate glasses, and to obtain information about valence state and coordination of iron ions. The systems Na 2 O-ZnO-B 2 O 3 -SiO 2 and ZnO-B 2 O 3 -SiO 2 were doped with α-Fe 2 O 3 . X-ray diffraction, IR spectroscopy and 57 Fe Moessbauer spectroscopy were used as experimental techniques. (author) 32 refs.; 5 figs.; 5 tabs

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

International Nuclear Information System (INIS)

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

1989-11-01

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

Silicate glasses. Chapter 1

International Nuclear Information System (INIS)

Lutze, W.

1988-01-01

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

A Raman spectroscopy study on the effects of intermolecular hydrogen bonding on water molecules absorbed by borosilicate glass surface

Science.gov (United States)

Li, Fabing; Li, Zhanlong; Wang, Ying; Wang, Shenghan; Wang, Xiaojun; Sun, Chenglin; Men, Zhiwei

2018-05-01

The structural forms of water/deuterated water molecules located on the surface of borosilicate capillaries have been first investigated in this study on the basis of the Raman spectral data obtained at different temperatures and under atmospheric pressure for molecules in bulk and also for molecules absorbed by borosilicate glass surface. The strongest two fundamental bands locating at 3063 cm-1 (2438 cm-1) in the recorded Raman spectra are assigned here to the Osbnd H (Osbnd D) bond stretching vibrations and they are compared with the corresponding bands observed at 3124 cm-1 (2325 cm-1) in the Raman spectrum of ice Ih. Our spectroscopic observations have indicated that the structure of water and deuterated water molecules on borosilicate surface is similar to that of ice Ih (hexagonal phase of ice). These observations have also indicated that water molecules locate on the borosilicate surface so as to construct a bilayer structure and that strong and weak intermolecular hydrogen bonds are formed between water/deuterated molecules and silanol groups on borosilicate surface. In accordance with these findings, water and deuterated water molecules at the interface of capillary have a higher melting temperature.

Coordination Environments of Highly Charged Cations (Ti, Cr, and Light REE's) in Borosilicate Glass/Melts to 1120C

Energy Technology Data Exchange (ETDEWEB)

Farges, Francois; /Museum Natl. Hist. Natur. /Stanford U., Geo. Environ. Sci.; Brown, Gordon E., Jr.; /Stanford U., Geo. Environ Sci. /SLAC, SSRL

2007-01-02

The local environments around Ti, Cr, and several light rare-earth elements (La, Ce, and Nd) were investigated by in-situ XANES spectroscopy in a number of complex borosilicate glasses and melts (to 1120 C) that are used for nuclear waste storage. Examination of the high-resolution XANES spectra at the Ti K-edge shows that the average coordination of Ti changes from {approx}5 to {approx}4.5. Cr is dominantly trivalent in the melts studied. However, its average coordination is probably lower in the melt (tetrahedral ?) as revealed by the more intense Cr-K pre-edge feature. Ce also changes its average valence from dominantly +4 to +3.5 upon glass melting. These changes are reversible at T{sub g}, the glass transition temperature ({approx}500-550 C for these glasses). In contrast, the local environments of Nd, Pr, and La are unaffected by melting. Therefore, structural reorganization of these borosilicate glass/melts above T{sub g} is variable, not only in terms of valence (as for Ce) but also speciation (Ti and Cr). Both the ability of B to adopt various coordination geometries (triangular and tetrahedral) and the chemical complexity of the glass/melts explain these changes.

Investigating the effect of V{sub 2}O{sub 5} addition on sodium barium borosilicate glasses

Energy Technology Data Exchange (ETDEWEB)

Halder, Rumu, E-mail: rumuhalder24feb@gmail.com; Sengupta, Pranesh; Dey, G. K. [Materials Science Division, Bhabha Atomic Research Centre, Mumbai-700 085 (India); Sudarsan, V. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai-700 085 (India); Kaushik, C. P. [Waste Management Division, Bhabha Atomic Research Centre, Mumbai-700 085 (India)

2016-05-23

V{sub 2}O{sub 5} doped sodium barium borosilicate glasses were characterized by photoluminescence spectroscopy and electron probe microanalyzer (EPMA). The glass remains homogeneous for lower concentration of V{sub 2}O{sub 5} but a phase separation is observed when V{sub 2}O{sub 5} doping is increased beyond 5 mol%. Detailed microanalysis reveals that the phase separated glass consists of a phase containing V, Ba and Si and a separate Si rich phase within the glass matrix. The luminescence study demonstrated that at low concentration the vanadium mainly interacts with the structural units of B/Si while at higher concentrations, V-O-V/ V-O{sup −} Na{sup +}/Ba{sup 2+} linkages are formed.

Effect of various lead species on the leaching behavior of borosilicate waste glass

International Nuclear Information System (INIS)

Lehman, R.L.; Kuchinski, F.A.

1984-01-01

A borosilicate nuclear waste glass was static leached in pure water, silicate water, and brine solution. Three different forms of lead were included in specified corrosion cells to assess the extent to which various lead species alter the leaching behavior of the glass. Weight loss data indicated that Pb/sub m/ amd PbO greatly reduce the weight loss of glass when leached in pure water, and similar effects were noted in silicate and brine. Si concentrations, which were substantial in the glass-alone leachate, were reduced to below detection limits in all pure water cells containing a lead form. Lead concentration levels in the leachate were controlled by lead form solubility and appeared to be a significant factor in influencing apparent leaching behavior. Surface analysis revealed surface crystals, which probably formed when soluble lead in the leachate reacted with dissolved or activated silica at the glass surface. The net effect was to reduce the lease of some glass constituents to the leachate, although it was not clear whether the actual corrosion of the glass surface was reduced. Significantly different corrosion inhibiting effects were noted among lead metal and two forms of lead oxide. 9 refs., 7 figs., 3 tabs

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.

Volatilization from borosilicate glass melts of simulated Savannah River Plant waste

International Nuclear Information System (INIS)

Wilds, G.W.

1979-01-01

Laboratory scale studies determined the rates at which the semivolatile components sodium, boron, lithium, cesium, and ruthenium volatilized from borosilicate glass melts that contained simulated Savannah River Plant waste sludge. Sodium and boric oxides volatilize as the thermally stable compound sodium metaborate, and accounted for approx. 90% of the semivolatiles that evolved. The amounts of semivolatiles that evolved increased linearly with the logarithm of the sodium content of the glass-forming mixture. Cesium volatility was slightly suppressed when titanium dioxide was added to the melt, but was unaffected when cesium was added to the melt as a cesium-loaded zeolite rather than as a cesium carbonate solution. Volatility of ruthenium was not suppressed when the glass melt was blanketed with a nonoxidizing atmosphere. Trace quantities of mercury were removed from vapor streams by adsorption onto a silver-exchanged zeolite. A bed containing silver in the ionic state removed more than 99.9% of the mercury and had a high chemisorption capacity. Beds of lead-, copper-, and copper sulfide-exchanged zeolite-X and also an unexchanged zeolite-X were tested. None of these latter beds had high removal efficiency and high chemisorption capacity

Volatilization from borosilicate glass melts of simulated Savannah River Plant waste

International Nuclear Information System (INIS)

Wilds, G.W.

1978-01-01

Laboratory scale studies determined the rates at which the semivolatile components sodium, boron, lithium, cesium, and ruthenium volatilized from borosilicate glass melts that contained simulated Savannah River Plant waste sludge. Sodium and boric oxides volatilize as the thermally stable compound sodium metaborate, and accounted for approx. 90% of the semivolatiles that evolved. The amounts of semivolatiles that evolved increased linearly with the logarithm of the sodium content of the glass-forming mixture. Cesium volatility was slightly suppressed when titanium dioxide was added to the melt, but was unaffected when cesium was added to the melt as a cesium-loaded zeolite rather than as a cesium carbonate solution. Volatility of ruthenium was not suppressed when the glass melt was blanketed with a nonoxidizing atmosphere. Trace quantities of mercury were removed from vapor streams by adsorption onto a silver-exchanged zeolite. A bed containing silver in the ionic state removed more than 99.9% of the mercury and had a high chemisorption capacity. Beds of lead-, copper-, and copper sulfide-exchanged zeolite-X and also an unexchanged zeolite-X were tested. None of these latter beds had high removal efficiency and high chemisorption capacity

Borosilicate glass as a matrix for immobilization of SRP high-level waste

International Nuclear Information System (INIS)

Wicks, G.G.

1980-01-01

Approximately 22 million gallons of high-level radioactive defense waste are currently being stored in large underground tanks located on the Savannah River Plant (SRP) site in Aiken, South Carolina. One option now being considered for long-term management of this waste involves removing the waste from the tanks, chemically processing the waste, and immobilizing the potentially harmful radionuclides in the waste into a borosilicate glass matrix. The technology for producing waste glass forms is well developed and has been demonstrated on various scales using simulated as well as radioactive SRP waste. Recently, full-scale prototypical equipment has been made operational at SRP. This includes both a joule-heated ceramic melter and an in-can melter. These melters are a part of an integrated vitrification system which is under evaluation and includes a spray calciner, direct liquid feed apparatus, and various elements of an off-gas system. Two of the most important properties of the waste glass are mechanical integrity and leachability. Programs are in progress at SRL aimed at minimizing thermally induced cracking by carefully controlling cooling cycles and using ceramic liners or coatings. The leachability of SRP waste glass has been studied under many different conditions and consistently found to be low. For example, the leachability of actual SRP waste glass was found to be 10 -6 to 10 -5 g/(cm 2 )(day) initially and decreasing to 10 -9 to 10 -8 g/(cm 2 )(day) after 100 days. Waste glass is also being studied under anticipated storage conditions. In brine at 90 0 C, the leachability is about 5 x 10 -8 g/(cm 2 )(day) after 60 days. The effects of other geological media including granite, basalt, shale, and tuff are also being studied as part of the multibarrier isolation system

Optical characterization of Eu3+ and Tb3+ ions doped cadmium lithium alumino fluoro boro tellurite glasses.

Science.gov (United States)

Raju, K Vemasevana; Sailaja, S; Raju, C Nageswara; Reddy, B Sudhakar

2011-06-01

This article reports on the development and spectral results of Eu(3+) and Tb(3+) ions doped cadmium lithium alumino fluoro boro tellurite (CLiAFBT) glasses in the following composition. 40TeO2-30B2O3-10CdO-10Li2O-10AlF3 (Hostglass) (40-x)TeO2-30B2O3-10CdO-10Li2O-10AlF3-xEu2O3 (40-x)TeO2-30B2O3-10CdO-10Li2O-10AlF3-xTb4O7 where x=0.25, 0.50, 0.75, 1.0, 1.25 mol%. Glass amorphous nature and thermal properties have been studied using the XRD and DSC profiles. From the emission spectra of Eu(3+):glasses, five emission transitions have been observed at 578 nm, 592 nm, 612 nm, 653 nm, 701 nm and are assigned to the transitions (5)D(0)→(7)F(0), (7)F(1,)(7)F(2), (7)F(3) and (7)F(4), respectively, with λ(exci)=392 nm ((7)F(0)→(5)L(6)). In case of Tb(3+):glasses, four emission transitions ((5)D(4)→(7)F(6,)(7)F(5), (7)F(4) and (7)F(3)) are observed at 488 nm, 543 nm, 584 nm and 614 nm, respectively, with λ(exci)=376 nm. Decay curves and energy level diagrams have been plotted to evaluate the life times and to analyze the emission mechanism. Copyright © 2011 Elsevier B.V. All rights reserved.

Gamma ray shielding study of barium-bismuth-borosilicate glasses as transparent shielding materials using MCNP-4C code, XCOM program, and available experimental data

Energy Technology Data Exchange (ETDEWEB)

Bagheri, Reza; Yousefinia, Hassan [Nuclear Fuel Cycle Research School (NFCRS), Nuclear Science and Technology Research Institute (NSTRI), Atomic Energy Organization of Iran, Tehran (Iran, Islamic Republic of); Moghaddam, Alireza Khorrami [Radiology Department, Paramedical Faculty, Mazandaran University of Medical Sciences, Sari (Iran, Islamic Republic of)

2017-02-15

In this work, linear and mass attenuation coefficients, effective atomic number and electron density, mean free paths, and half value layer and 10th value layer values of barium-bismuth-borosilicate glasses were obtained for 662 keV, 1,173 keV, and 1,332 keV gamma ray energies using MCNP-4C code and XCOM program. Then obtained data were compared with available experimental data. The MCNP-4C code and XCOM program results were in good agreement with the experimental data. Barium-bismuth-borosilicate glasses have good gamma ray shielding properties from the shielding point of view.

Electrical characterization of strontium titanate borosilicate glass ceramics system with bismuth oxide addition using impedance spectroscopy

International Nuclear Information System (INIS)

Thakur, O.P.; Kumar, Devendra; Parkash, Om; Pandey, Lakshman

2003-01-01

The ac electrical data, measured in the frequency range 0.1 kHz-1 MHz, were used to study the electrical response of strontium titanate borosilicate glass ceramic system with bismuth oxide addition. Complex plane plots from these electrical data for various glass ceramic samples reveal contributions from simultaneously operating polarization mechanisms to overall dielectric behavior. The complex modulus (M * ) representation of electrical data for various glass ceramic samples were found to be more informative. Equivalent circuit models, which represent the electrical behavior of glass ceramic samples, were determined using complex non-linear least square (CNLS) fitting. An attempt has been made to understand the dielectric behavior of various glass ceramics in terms of contributions arising from different polarization processes occurring at glassy matrix, crystalline phases, glass to crystal interface region and blocking electrodes. Glass ceramics containing SrTiO 3 and TiO 2 (rutile) phases show thermally stable dielectric behavior

Use of molecular dynamics to model the structure of nuclear glasses

International Nuclear Information System (INIS)

Delaye, J.M.; Ghaleb, D.

1997-01-01

Born-Mayer-Huggins potentials (BMH) are generally used to model oxides glasses. In this article we show how they can be used, if they can be completed by three body terms, to reproduce correctly structures of alumino-borosilicate glasses. Taking into account the parameters adjusted for the basic matrix (SiO 2 , B 2 O 3 , Na 2 O, ZrO 2 , Al 2 O 3 ) of French light water reactor waste containment glass, we have analyzed equally the structure evolutions reproduced by BMH potentials according to the modification of the composition of the glass. The principal objective of this study being the appreciation of the capability of this potentials to simulate structure evolutions in the glass; this potentials representing neither the nature of chemical bonds nor the electronic state modifications that accompany changes of coordination numbers. Globally BHM potentials, despite their limited representativeness, reproduce some experimental observations. For example: - the gradual incorporation of the boron in the silicate network; - the shorter distances between network formers and non-bridging oxygen atoms; - the visualization of boron-enriched segregation zones in a high content boron composition without aluminum. (authors)

Immobilization of simulated high-level radioactive waste in borosilicate glass: Pilot scale demonstrations

International Nuclear Information System (INIS)

Ritter, J.A.; Hutson, N.D.; Zamecnik, J.R.; Carter, J.T.

1991-01-01

The Integrated DWPF Melter System (IDMS), operated by the Savannah River Laboratory, is a pilot scale facility used in support of the start-up and operation of the Department of Energy's Defense Waste Processing Facility. The IDMS has successfully demonstrated, on an engineering scale (one-fifth), that simulated high level radioactive waste (HLW) sludge can be chemically treated with formic acid to adjust both its chemical and physical properties, and then blended with simulated precipitate hydrolysis aqueous (PHA) product and borosilicate glass frit to produce a melter feed which can be processed into a durable glass product. The simulated sludge, PHA and frit were blended, based on a product composition program, to optimize the loading of the waste glass as well as to minimize those components which can cause melter processing and/or glass durability problems. During all the IDMS demonstrations completed thus far, the melter feed and the resulting glass that has been produced met all the required specifications, which is very encouraging to future DWPF operations. The IDMS operations also demonstrated that the volatile components of the melter feed (e.g., mercury, nitrogen and carbon, and, to a lesser extent, chlorine, fluorine and sulfur) did not adversely affect the melter performance or the glass product

Energy transfer and cross-relaxation in Tb3+-doped borosilicate glasses

International Nuclear Information System (INIS)

Kim, Jung Hwan; Sol, Jung Sik

1990-01-01

Energy transfer in Tb 3+ -doped borosilicate glasses has been studied by the analysis of fluorescence intensities and lifetimes of 5 D 3 and 5 D 4 states as a function of Tb 3+ concentration. It is shown that as the Tb 3+ concentration is increased the cross-relaxation produces high population of the 5 D 4 state at the expense of 5 D 3 . It is also found that this interaction is predominantly dipole-dipole transition with critical distance of 13 A. The critical distance for energy transfer 5 D 4 5 D 3 which is responsible for the quenching of 5 D 4 emission at high concentration of Tb 3+ ions is 4.5 A. (Author)

Linear thermal expansion coefficient (at temperatures from 130 to 800 K) of borosilicate glasses applicable for coupling with silicon in microelectronics

OpenAIRE

Sinev, Leonid S.; Petrov, Ivan D.

2017-01-01

Processing results of measurements of linear thermal expansion coefficients and linear thermal expansion of two brands of borosilicate glasses --- LK5 and Borofloat 33 --- are presented. The linear thermal expansion of glass samples have been determined in the temperature range 130 to 800 K (minus 143 to 526 $\\deg$C) using thermomechanical analyzer TMA7100. Relative imprecision of indirectly measured linear thermal expansion coefficients and linear thermal expansion of both glass brands is le...

Physical, thermal, structural and optical properties of Dy3+ doped lithium alumino-borate glasses for bright W-LED

International Nuclear Information System (INIS)

Pawar, P.P.; Munishwar, S.R.; Gautam, S.; Gedam, R.S.

2017-01-01

Rare earth (RE) doped glasses have potential applications due to their emission efficiencies of 4f–4 f and 4f–5d electronic transitions. Among all the rare earths, Dy 3+ doped glasses have drawn much interest among the researchers for their intense emission in the visible region from 470 to 500 nm and around 570 to 600 nm. The physical, thermal, structural and optical properties of Dy 3+ doped lithium alumino-borate glasses (LABD glasses) have been studied for white LED (W-LED) application. The glasses were synthesized by conventional melt quench technique. X-ray diffraction spectra revealed the amorphous nature of the glass sample. An FTIR spectrum was carried out to study the glass structure and various functional groups present in the LABD glasses. Optical absorption spectra were recorded by UV–vis-NIR spectrometer. Allowed direct and indirect band gaps were obtained by Tauc's plot. Thermal parameters like glass thermal stability (∆T), Hruby's parameter (K gl ), etc. were calculated by DTA graph. Photoluminescence excitation and emission spectra's were measured at room temperature. The emission spectra shows two intense emission bands at around 482 nm (blue) and 574 nm (yellow) corresponds to the 4 F 9/2 → 6 H 15/2 and 4 F 9/2 → 6 H 13/2 transitions respectively along with one feeble band at 662 nm (red) corresponds to 4 F 9/2 → 6 H 11/2 transition. The CIE chromaticity co-ordinates were calculated for all glass samples. CIE chromaticity diagram shows glass LABD-4 containing 0.5 mol% Dy 2 O 3 with colour co-ordinates X = 0.34 and Y = 0.38 have highest emission intensity. These glasses having emission in the white region and thus can be used for bright white LED.

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

Science.gov (United States)

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

2005-10-01

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

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

International Nuclear Information System (INIS)

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

2005-01-01

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

Gamma Ray Shielding Study of Barium–Bismuth–Borosilicate Glasses as Transparent Shielding Materials using MCNP-4C Code, XCOM Program, and Available Experimental Data

Directory of Open Access Journals (Sweden)

Reza Bagheri

2017-02-01

Full Text Available In this work, linear and mass attenuation coefficients, effective atomic number and electron density, mean free paths, and half value layer and 10th value layer values of barium–bismuth–borosilicate glasses were obtained for 662 keV, 1,173 keV, and 1,332 keV gamma ray energies using MCNP-4C code and XCOM program. Then obtained data were compared with available experimental data. The MCNP-4C code and XCOM program results were in good agreement with the experimental data. Barium–bismuth–borosilicate glasses have good gamma ray shielding properties from the shielding point of view.

X-ray absorption studies of chlorine valence and local environments in borosilicate waste glasses

International Nuclear Information System (INIS)

McKeown, David A.; Gan, Hao; Pegg, Ian L.; Stolte, W.C.; Demchenko, I.N.

2011-01-01

Chlorine (Cl) is a constituent of certain types of nuclear wastes and its presence can affect the physical and chemical properties of silicate melts and glasses developed for the immobilization of such wastes. Cl K-edge X-ray absorption spectra (XAS) were collected and analyzed to characterize the unknown Cl environments in borosilicate waste glass formulations, ranging in Cl-content from 0.23 to 0.94 wt.%. Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data for the glasses show trends dependent on calcium (Ca) content. Near-edge data for the Ca-rich glasses are most similar to the Cl XANES of CaCl 2 , where Cl - is coordinated to three Ca atoms, while the XANES for the Ca-poor glasses are more similar to the mineral davyne, where Cl is most commonly coordinated to two Ca in one site, as well as Cl and oxygen nearest-neighbors in other sites. With increasing Ca content in the glass, Cl XANES for the glasses approach that for CaCl 2 , indicating more Ca nearest-neighbors around Cl. Reliable structural information obtained from the EXAFS data for the glasses is limited, however, to Cl-Cl, Cl-O, and Cl-Na distances; Cl-Ca contributions could not be fit to the glass data, due to the narrow k-space range available for analysis. Structural models that best fit the glass EXAFS data include Cl-Cl, Cl-O, and Cl-Na correlations, where Cl-O and Cl-Na distances decrease by approximately 0.16 A as glass Ca content increases. XAS for the glasses indicates Cl - is found in multiple sites where most Cl-sites have Ca neighbors, with oxygen, and possibly, Na second-nearest neighbors. EXAFS analyses suggest that Cl-Cl environments may also exist in the glasses in minor amounts. These results are generally consistent with earlier findings for silicate glasses, where Cl - was associated with Ca 2+ and Na + in network modifier sites.

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

Energy Technology Data Exchange (ETDEWEB)

Ebert, W. L.; Chemical Engineering

2006-09-30

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

Reinforcement of poly-l-lactic acid electrospun membranes with strontium borosilicate bioactive glasses for bone tissue engineering.

Science.gov (United States)

Fernandes, João S; Gentile, Piergiorgio; Martins, Margarida; Neves, Nuno M; Miller, Cheryl; Crawford, Aileen; Pires, Ricardo A; Hatton, Paul; Reis, Rui L

2016-10-15

Herein, for the first time, we combined poly-l-lactic acid (PLLA) with a strontium borosilicate bioactive glass (BBG-Sr) using electrospinning to fabricate a composite bioactive PLLA membrane loaded with 10% (w/w) of BBG-Sr glass particles (PLLA-BBG-Sr). The composites were characterised by scanning electron microscopy (SEM) and microcomputer tomography (μ-CT), and the results showed that we successfully fabricated smooth and uniform fibres (1-3μm in width) with a homogeneous distribution of BBG-Sr microparticles (bone marrow-derived mesenchymal stem cells (BM-MSCs) demonstrated that PLLA-BBG-Sr membranes promoted the osteogenic differentiation of the cells as demonstrated by increased alkaline phosphatase activity and up-regulated osteogenic gene expression (Alpl, Sp7 and Bglap) in relation to PLLA alone. These results strongly suggest that the composite PLLA membranes reinforced with the BBG-Sr glass particles have potential as an effective biomaterial capable of promoting bone regeneration. PLLA membranes were reinforced with 10% (w/w) of strontium-bioactive borosilicate glass microparticles, and their capacity to induce the osteogenic differentiation of bone marrow mesenchymal stem cells (BM-MSCs) was evaluated. These membranes presented an increased: degradability, water uptake, Young modulus and tensile strength. We also demonstrated that these membranes are non-cytotoxic and promote the attachment of BM-MSCs. The addition of the glass microparticles into the PLLA membranes promoted the increase of ALP activity (under osteogenic conditions), as well as the BM-MSCs osteogenic differentiation as shown by the upregulation of Alpl, Sp7 and Bglap gene expression. Overall, we demonstrated that the reinforcement of PLLA with glass microparticles results in a biomaterial with the appropriate properties for the regeneration of bone tissue. Copyright © 2016 Acta Materialia Inc. All rights reserved.

Processing and optical characterization of lead calcium titanate borosilicate glass doped with germanium

Science.gov (United States)

Gautam, C. R.; Das, Sangeeta; Gautam, S. S.; Madheshiya, Abhishek; Singh, Anod Kumar

2018-04-01

In this study, various compositions of lead calcium titanate borosilicate glass doped with a fixed amount of germanium were synthesized using the rapid melt quench technique. The amorphous nature of the synthesized glass was confirmed by X-ray diffraction and scanning electron microscopy analyses. The structural and optical properties were deduced using Raman, Fourier transform infrared (FTIR), and ultraviolet-visible (UV-Vis) spectroscopy. FTIR spectroscopy confirmed the presence of borate groups in triangular and tetrahedral coordination. Infrared and Raman analyses detected the vibrational bonds of Gesbnd Osbnd Ge, Bsbnd Osbnd Ge, Sisbnd Osbnd Ge, Sisbnd Osbnd Si, and Pbsbnd Osbnd Ge. The energy band gaps were evaluated for the prepared glass samples based on Tauc plots of the UV-Vis spectra. The calculated values of the optical band gap decreased from 2.91 to 2.85 eV as the PbO content increased from x = 0.0 to x = 0.7. Furthermore, the Urbach energy was studied based on the UV-Vis results to confirm the disordered structure of the glass. The calculated densities of the glass samples (1.5835 g/cm3 to 3.9184 g/cm3) increased as the concentration of PbO increased, whereas they decreased with the molar volume.

Phase evolution and dielectric properties of MgTi2O5 ceramic sintered with lithium borosilicate glass

International Nuclear Information System (INIS)

Shin, Hyunho; Shin, Hee-Kyun; Jung, Hyun Suk; Cho, Seo-Yong; Hong, Kug Sun

2005-01-01

Phase evolution, densification, and dielectric properties of MgTi 2 O 5 dielectric ceramic, sintered with lithium borosilicate (LBS) glass, were studied. Reaction between LBS glass and MgTi 2 O 5 was significant in forming secondary phases such as TiO 2 and (Mg,Ti) 2 (BO 3 )O. The glass addition was not necessarily deleterious to the dielectric properties due to the formation of TiO 2 : permittivity increased and temperature coefficient of resonance frequency could be tuned to zero with the addition of LBS glass, although the inevitable glass-induced decrease of quality factor was not retarded by the formation of TiO 2 . The sintered specimen with 10 wt% LBS fired at 950 deg. C for 2 h showed permittivity of 19.3, quality factor of 6800 GHz, and τ f of -16 ppm/ deg. C

Determination of iron redox ratio in borosilicate glasses and melts from Raman spectra

Energy Technology Data Exchange (ETDEWEB)

Cochain, B. [SCDV-Laboratoire d' Etudes de Base sur les Verres, CEA Valrho, Centre de Marcoule, 30207 Bagnols-sur-ceze (France); Physique des Mineraux et des Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris Cedex05 (France); Neuville, D.R.; Richet, P. [Physique des Mineraux et des Magmas, CNRS-IPGP, 4 place Jussieu, 75252 Paris Cedex05 (France); Henderson, G.S. [Dept of Geology, University of Toronto, 22 Russell Street, Toronto (Canada); Pinet, O. [SCDV-Laboratoire d' Etudes de Base sur les Verres, CEA Valrho, Centre de Marcoule, 30207 Bagnols-sur-ceze (France)

2008-07-01

A method is presented to determine the redox ratio of iron in borosilicate glasses and melts relevant to nuclear waste storage from an analysis of Raman spectra recorded at room or high temperature. The basis of this method is the strong variation of the spectral feature observed between 800 and 1200 cm{sup -1}, in which it is possible to assign a band to vibrational modes involving ferric iron in tetrahedral coordination whose intensity increases with iron content and iron oxidation. After baseline correction and normalization, fits to the Raman spectra made with Gaussian bands enable us to determine the proportion of ferric iron provided the redox ratio is known independently for at least two redox states for a given glass composition. This method is particularly useful for in situ determinations of the kinetics and mechanisms of redox reactions. (authors)

Determination of iron redox ratio in borosilicate glasses and melts from Raman spectra

International Nuclear Information System (INIS)

Cochain, B.; Neuville, D.R.; Richet, P.; Henderson, G.S.; Pinet, O.

2008-01-01

A method is presented to determine the redox ratio of iron in borosilicate glasses and melts relevant to nuclear waste storage from an analysis of Raman spectra recorded at room or high temperature. The basis of this method is the strong variation of the spectral feature observed between 800 and 1200 cm -1 , in which it is possible to assign a band to vibrational modes involving ferric iron in tetrahedral coordination whose intensity increases with iron content and iron oxidation. After baseline correction and normalization, fits to the Raman spectra made with Gaussian bands enable us to determine the proportion of ferric iron provided the redox ratio is known independently for at least two redox states for a given glass composition. This method is particularly useful for in situ determinations of the kinetics and mechanisms of redox reactions. (authors)

Effects of solution chemistry and atmosphere on leaching of alkali borosilicate glass

International Nuclear Information System (INIS)

Hermansson, H.P.; Christensen, H.; Clark, D.E.; Werme, L.

1983-01-01

The leaching behavior of two alkali-borosilicate glasses containing 9 wt % simulated fission products and 1.6 wt % uranium oxide has been studied. Samples were exposed to one of eight types of leachants including doubly distilled water, simulated ground silicate water, a brine solution, and solutions containing various concentrations of iron, aluminum or sodium maintained at either 25 0 C, 40 0 C or 90 0 C for up to 182 days. The most aggressive leachants were the solutions containing sodium (excluding brine) and simulated ground silicate water. These solutions increased the extent of leaching by a factor of 2 to 3 over that for distilled water for one of the glasses. A partially protective surface film rich in magnesium, potassium, and chlorine was formed on the glasses exposed to the brine solution. In order to evaluate the effects of atmosphere on leaching, samples were also immersed in doubly distilled water over which the relative concentrations of oxygen, nitrogen and carbon dioxide were varied. Increasing the carbon dioxide concentration from 0 to 50% resulted in a factor of 3 increase in the leaching rate

Development of glass ceramics for the incorporation of fission products

International Nuclear Information System (INIS)

De, A.K.; Luckscheiter, B.; Lutze, W.; Malow, G.; Schiewer, E.

1976-01-01

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

Glass microspheres for brachytherapy

International Nuclear Information System (INIS)

Prado, Miguel O.; Prastalo, Simon; Blaumann, Herman; Longhino, Juan M.; Repetto Llamazares, A.H.V.

2007-01-01

We developed the capacity to produce glass microspheres containing in their structure one or more radioactive isotopes useful for brachytherapy. We studied the various facts related with their production: (Rare earth) alumino silicate glass making, glass characterization, microspheres production, nuclear activation through (n,γ) nuclear reactions, mechanical characterization before and after irradiation. Corrosion tests in simulated human plasma and mechanical properties characterization were done before and after irradiation. (author) [es

Effect of geologic repository parameters on aqueous corrosion of nuclear glass

International Nuclear Information System (INIS)

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

1995-01-01

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

Effect of geologic repository parameters on aqueous corrosion of nuclear glass

Energy Technology Data Exchange (ETDEWEB)

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

1996-12-31

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

Local structure near actinides and nucleating elements in borosilicate glass for nuclear industry: Results of X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Petit-Maire, D.

1988-01-01

Possibilities and limits of X-ray absorption spectroscopy for cation site description in silicate glasses and possible applications for complex glasses, like glass for fission product containment, are examined. In borosilicate glasses two types of sites are evidenced for actinides at the valence 4: Coordinance 6 sites with a narrow radial distribution for the distance An-0; higher coordination (7, 8 or more) with a wider and asymmetrical radial distribution. Proportion of low coordinance sites increases when cation size decreases (Th > Np). U and Np VI and V are characterized as actinyles with a chain 0-An-0 practically linear, coordinance in a plane perpendicular to this complex is probably 5. X-ray absorption spectroscopy allows an accurate description of actinide sites in fission product glasses [fr

Effect of the kind of alkaline and rare earth ions on the structure of a glass rich in earth

International Nuclear Information System (INIS)

Quintas, Arnaud; Caurant, Daniel; Majerus, Odile; Lenoir, Marion; Dussossoy, Jean-Luc; Charpentier, Thibault; Neuville, Daniel R.; Gervais, C.

2006-01-01

In the framework of a structural study of a nuclear wastes containment glass of type alumino borosilicate and rich in rare earths, the influence of the kind of alkaline or rare earth ions is analyzed. For that, two glasses series have been prepared in which the Na + ion (respectively Ca 2+ ions) present in the standard composition is totally substituted by another alkaline ion Li + , K + , Rb + or Cs + (respectively another rare earth ion Mg 2+ , Sr 2+ or Ba 2+ ). These glasses, analyzed by optical absorption, Raman and 27 Al or 11 B NMR spectroscopies have revealed the strong impact of the kind of the modifying ion as well as the structure of the vitreous lattice (variation of the ratio BO 3 /BO 4 and local variations of the polymerization degree) than the local surroundings of the rare earth (decrease of the covalency degree of the bond Nd-O with the increase of the field force of the modifying ion). (O.M.)

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

International Nuclear Information System (INIS)

Wen, Hongli; Tanner, Peter A.

2015-01-01

Graphical abstract: Photographs of undoped (SiO 2 ) 50 (Na 2 O) 25 (B 2 O 3 ) 25 (SiNaB) glass and transition metal ion-doped (TM) 0.5 (SiO 2 ) 49.5 (Na 2 O) 25 (B 2 O 3 ) 25 glass samples. - Highlights: • 3d transition metal ion (from Ti to Zn) doped SiO 2 -Na 2 O-B 2 O 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 2 -Na 2 O-B 2 O 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

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

International Nuclear Information System (INIS)

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

1986-01-01

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

GLASS FABRICATION AND PRODUCT CONSISTENCY TESTING OF LANTHANIDE BOROSILICATE FRIT X COMPOSITION FOR PLUTONIUM DISPOSITION

Energy Technology Data Exchange (ETDEWEB)

Marra, J

2006-11-15

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 the preferred option 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 in the late 1990's. 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. Recent FY05 studies have further investigated the LaBS Frit B formulation as well as development of a newer LaBS formulation denoted as LaBS Frit X. The objectives of this present task were to fabricate plutonium loaded LaBS Frit X glass and perform corrosion 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 X 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). The glass was thoroughly 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 using quenched Pu Frit X glass with varying exposed surface areas. Effects of isothermal and can-in-canister heat treatments on the Pu Frit X glass were also investigated. Another series of PCTs were performed on these different heat-treated Pu Frit X glasses. Leachates from all these PCTs

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)

Ghezal, A.

1987-09-01

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

A new glass option for parenteral packaging.

Science.gov (United States)

Schaut, Robert A; Peanasky, John S; DeMartino, Steven E; Schiefelbein, Susan L

2014-01-01

Glass is the ideal material for parenteral packaging because of its chemical durability, hermeticity, strength, cleanliness, and transparency. Alkali borosilicate glasses have been used successfully for a long time, but they do have some issues relating to breakage, delamination, and variation in hydrolytic performance. In this paper, alkali aluminosilicate glasses are introduced as a possible alternative to alkali borosilicate glasses. An example alkali aluminosilicate glass is shown to meet the compendial requirements, and to have similar thermal, optical, and mechanical attributes as the current alkali borosilicate glasses. In addition, the alkali aluminosilicate performed as well or better than the current alkali borosilicates in extractables tests and stability studies, which suggests that it would be suitable for use with the studied liquid product formulation. The physical, mechanical, and optical properties of glass make it an ideal material for packaging injectable drugs and biologics. Alkali borosilicate glasses have been used successfully for a long time for these applications, but there are some issues. In this paper, alkali aluminosilicate glasses are introduced as a possible alternative to alkali borosilicate glasses. An example alkali aluminosilicate glass is shown to meet the requirements for packaging injectable drugs and biologics, and to be suitable for use with a particular liquid drug. © PDA, Inc. 2014.

Specialty glass development for radiation shielding windows and nuclear waste immobilization

International Nuclear Information System (INIS)

Mandal, S.; Ghorui, S.; Roy Chowdhury, A.; Sen, R.; Chakraborty, A.K.; Sen, S.; Maiti, H.S.

2015-01-01

The technology of two important varieties of specialty glasses, namely high density Radiation Shielding Window (RSW) glass and specialty glass beads of borosilicate composition have been successfully developed in CGCRI with an aim to meet the countries requirement. Radiation Shielding Windows used in nuclear installations, are viewing devices, which allow direct viewing into radioactive areas while still providing adequate protection to the operating personnel. The glass blocks are stabilized against damage from radiation by introducing cerium in definite proportions. Considering the essentially of developing an indigenous technology to make the country self-sufficient for this critical item, CGCRI has taken up a major programme to develop high lead containing glasses required for RSWs under a MoD with BARC. On the other hand, the specialty glass bead of specific composition and properties is a critical material required for management of radioactive waste in a closed nuclear fuel cycle that is followed by India. During reprocessing of the spent nuclear fuel, high level radio-active liquid waste (HLW) is produced containing unwanted radio isotopes some of which remain radioactive for thousands of years. The need is to immobilize them within a molecular structure so that they will not come out and be released to the ambience and thereby needs to be resolved if nuclear power is to make a significant contribution to the country's power requirement. Borosilicate glass has emerged as the material of choice for immobilization due to its unique random network structure

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

International Nuclear Information System (INIS)

Debure, M.

2012-01-01

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) [fr

In Vitro Degradation of Borosilicate Bioactive Glass and Poly(l-lactide-co-ε-caprolactone Composite Scaffolds

Directory of Open Access Journals (Sweden)

Jenna Tainio

2017-11-01

Full Text Available Composite scaffolds were obtained by mixing various amounts (10, 30 and 50 weight % [wt %] of borosilicate bioactive glass and poly(l-lactide-co-ε-caprolactone (PLCL copolymer. The composites were foamed using supercritical CO2. An increase in the glass content led to a decrease in the pore size and density. In vitro dissolution/reaction test was performed in simulated body fluid. As a function of immersion time, the solution pH increased due to the glass dissolution. This was further supported by the increasing amount of Ca in the immersing solution with increasing immersion time and glass content. Furthermore, the change in scaffold mass was significantly greater with increasing the glass content in the scaffold. However, only the scaffolds containing 30 and 50 wt % of glasses exhibited significant hydroxyapatite (HA formation at 72 h of immersion. The compression strength of the samples was also measured. The Young’s modulus was similar for the 10 and 30 wt % glass-containing scaffolds whereas it increased to 90 MPa for the 50 wt % glass containing scaffold. Upon immersion up to 72 h, the Young’s modulus increased and then remained constant for longer immersion times. The scaffold prepared could have great potential for bone and cartilage regeneration.

Thorium reactions in borosilicate-glass/water systems

International Nuclear Information System (INIS)

Rai, D.; Hess, N.J.; Felmy, A.R.; Moore, D.A.; Yui, M.

2005-01-01

Studies were conducted on the dissolution of Th-doped borosilicate glass, a complex assemblage of 24 different elements in various proportions, in a wide range of pH values (0.5 to 12) and carbonate (as high as 6.2 m) and bicarbonate (as high as 1.0 m) concentrations, and as a function of time to determine whether the observed thorium concentrations exhibit an equilibrium phenomenon and to ascertain whether existing thermodynamic data can be used to interpret these results. Measurable Th concentrations were observed in either the very acidic (pH 0.5 to 4) solutions or alkaline solutions containing relatively high carbonate/bicarbonate concentrations. Steady state Th concentrations were reached over time from both the oversaturation and undersaturation directions, indicating that Th concentrations are controlled by an equilibrium solubility phenomenon. The XRD, EXAFS, and thermodynamic analyses of solubility data failed to definitively identify the nature of the solubility-controlling solid in this complex system; however, the data suggests that the solubility-controlling solid most likely involves the Th-silicate phase and that the observed Th concentrations are up to many orders of magnitude lower than in equilibrium with ThO 2 (am). The solubility study also showed that existing thermodynamic data for carbonato complexes of Th can be used to reliably predict Th concentrations in relatively dilute to concentrated carbonate/bicarbonate solutions. (orig.)

Color centers of a borosilicate glass induced by 10 MeV proton, 1.85 MeV electron and 60Co-γ ray

Science.gov (United States)

Du, Jishi; Wu, Jiehua; Zhao, Lili; Song, Lixin

2013-05-01

Optical absorption spectra, electron paramagnetic resonance (EPR) spectra, Raman spectra of a borosilicate glass after irradiation by 10 MeV proton, 1.85 MeV electron and 60Co-γ ray were studied. The process of irradiation inducing color centers in the glass was discussed. The band gap of the glass before and after 60Co-γ ray irradiation was studied using Mott and Davis's theory, and it was found that calculated change of the band gap introduced a paradox, because Mott and Davis's theory on the band gap cannot be adopted in the study on the irradiated glass.

Physical, thermal, structural and optical properties of Dy{sup 3+} doped lithium alumino-borate glasses for bright W-LED

Energy Technology Data Exchange (ETDEWEB)

Pawar, P.P.; Munishwar, S.R.; Gautam, S.; Gedam, R.S., E-mail: rupesh_gedam@rediffmail.com

2017-03-15

Rare earth (RE) doped glasses have potential applications due to their emission efficiencies of 4f–4 f and 4f–5d electronic transitions. Among all the rare earths, Dy{sup 3+} doped glasses have drawn much interest among the researchers for their intense emission in the visible region from 470 to 500 nm and around 570 to 600 nm. The physical, thermal, structural and optical properties of Dy{sup 3+} doped lithium alumino-borate glasses (LABD glasses) have been studied for white LED (W-LED) application. The glasses were synthesized by conventional melt quench technique. X-ray diffraction spectra revealed the amorphous nature of the glass sample. An FTIR spectrum was carried out to study the glass structure and various functional groups present in the LABD glasses. Optical absorption spectra were recorded by UV–vis-NIR spectrometer. Allowed direct and indirect band gaps were obtained by Tauc's plot. Thermal parameters like glass thermal stability (∆T), Hruby's parameter (K{sub gl}), etc. were calculated by DTA graph. Photoluminescence excitation and emission spectra's were measured at room temperature. The emission spectra shows two intense emission bands at around 482 nm (blue) and 574 nm (yellow) corresponds to the {sup 4}F{sub 9/2}→{sup 6}H{sub 15/2} and {sup 4}F{sub 9/2}→{sup 6}H{sub 13/2} transitions respectively along with one feeble band at 662 nm (red) corresponds to {sup 4}F{sub 9/2}→{sup 6}H{sub 11/2} transition. The CIE chromaticity co-ordinates were calculated for all glass samples. CIE chromaticity diagram shows glass LABD-4 containing 0.5 mol% Dy{sub 2}O{sub 3} with colour co-ordinates X = 0.34 and Y = 0.38 have highest emission intensity. These glasses having emission in the white region and thus can be used for bright white LED.

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)

Wegner, S.; Van Wullen, L.; Tricot, G.; Tricot, G.

2010-01-01

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 27 Al and 31 P 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 11 B MAS, 29 Si MAS and in situ 29 Si{ 11 B} REAPDOR NMR spectroscopy. (authors)

Enhanced mechanical properties of single walled carbon nanotube-borosilicate glass composite due to cushioning effect and localized plastic flow

Directory of Open Access Journals (Sweden)

Sujan Ghosh

2011-12-01

Full Text Available A borosilicate glass composite has been fabricated incorporating Single Wall Carbon Nanotubes (SWCNT in the glass matrix by melt-quench technique. Hardness and the fracture toughness of the composite, were found to increase moderately with respect to the base glass. Interestingly one can observe accumulation of SWCNT bundles around the crack zone though no such accumulation was observed in the crack free indentation zone. The enhanced hardness of the composite was discussed by correlating the cushioning as well as toughening behavior of the agglomerated SWCNT bundles. On the other hand enhanced plastic flow was proposed to be the prime reason for the accumulation of SWCNT bundles around the crack, which increases the toughness of the composite by reducing the crack length. Moreover to ascertain the enhanced plasticity of the composite than that of the glass we calculated the recovery resistance of glass and the composite where recovery resistance of composite was found to be higher than that of the glass.

Luminescence properties of Dy3+ doped lithium zinc borosilicate glasses for photonic applications

Directory of Open Access Journals (Sweden)

N. Jaidass

2018-03-01

Full Text Available Different concentrations of Dy3+ ions doped lithium zinc borosilicate glasses of chemical composition (30-x B2O3 - 25 SiO2 -10 Al2O3 -30 LiF - 5 ZnO - x Dy2O3 (x = 0, 0.1, 0.5, 1.0 and 2.0 mol% were prepared by the melt quenching technique. The prepared glasses were investigated through X-ray diffraction, optical absorption, photoluminescence and decay measurements. Intensities of absorption bands expressed in terms of oscillator strengths (f were used to determine the Judd-Ofelt (J-O intensity parameters Ωλ (λ = 2, 4 and 6. The evaluated J-O parameters were used to determine the radiative parameters such as transition probabilities (AR, total transition probability rate (AT, radiative lifetime (τR and branching ratios (βR for the excited 4F9/2 level of Dy3+ ions. The chromaticity coordinates determined from the emission spectra were found to be located in the white light region of CIE chromaticity diagram. Keywords: Condensed matter physics, Engineering, Materials science

An enhanced resolution of the structural environment of zirconium in borosilicate glasses

International Nuclear Information System (INIS)

Jollivet, P.; Angeli, F.; Bergeron, B.; Gin, S.; Calas, G.; Galoisy, L.; Ruffoni, M.P.; Trcera, N.

2013-01-01

The short- and medium-range local environment of zirconium was determined by Zr L 2,3 -edge and K-edge XANES and by Zr K-edge EXAFS in borosilicate glasses with 1 to 8 mol% ZrO 2 . Regardless of the ZrO 2 content of the glass, Zr is six-coordinated in octahedra with Zr-O distances of 2.09 Angstroms. In the glasses containing 8 mol% ZrO 2 , the octahedra are more distorted than at lower ZrO 2 content. Enhanced resolution in the real space is achieved by recording Zr K-edge EXAFS spectra over a broad energy range, enabling to get access k-values up to 20 Angstroems -1 with a high signal to noise ratio. This allows discriminate between the various second neighbor contributions. A correct fit is based on four Si and two B. This local structure around Zr derived from that of zircono-silicates such as elpidite, in which two Si are replaced by two B. The Zr-Si distances increase from 3.63 ± 0.02 to 3.67 ± 0.01 Angstroms, as Zr-B distances remain constant within uncertainties, as ZrO 2 content increases. Two Na are situated at 3.64 ± 0.03 Angstroms from Zr, ensuring charge compensation of the ZrO 6 sites. Increasing the CaO content from 4 to 8 mol% does not lead to any structural change around Zr. (authors)

Dynamic fracture and fragmentation patterns of borosilicate laminate glasses

Directory of Open Access Journals (Sweden)

Gómez del Río, T.

2009-10-01

Full Text Available The dynamic behaviour of laminate borosilicate glasses (BSG with polyvinylbutiral (PVB interfaces (0,38 mm located at different distances from the impact point have been studied and compared with monolithic glass. The mechanical behaviour under impact loads have been studied using a compression split Hopkinson pressure bar (SHPB. In these experiments, the stress-strain curves of the materials at high loading rates and the capability of transmitting and reflecting the impact energy have been determined. The influence of the position of the interface on the fragmentation statistics of the SHPB recovered fragments has also been considered and analysed according to the published theoretical models.

En este trabajo se ha estudiado los comportamientos dinámicos de un vidrio monolítico de borosilicato y varios laminados de cristal de borosilicato (BSG con intercaras de polyvinylbutiral (PVB (0,38 mm situados a diferentes distancias respecto del punto de impacto. Los resultados de las diferentes configuraciones de laminados se han comparado con el vidrio monolítico. El comportamiento mecánico bajo cargas de impacto se han estudiado realizando ensayos de compresión con una barra Hopkinson (SHPB. A partir de estos experimentos se obtienen las curvas tensión-deformación de los materiales a altas velocidades de carga y su capacidad de transmitir y reflejar la energía del impacto. La influencia de la posición de la interfaz en las estadísticas de la fragmentación de los fragmentos recuperados también se ha considerado y analizado de acuerdo a los modelos teóricos publicados.

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.

Glass Ceramic Formulation Data Package

International Nuclear Information System (INIS)

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

2012-01-01

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

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)

Doping influence by some transition elements on the irradiation effects in nuclear waste glasses

International Nuclear Information System (INIS)

Florent, Olivier

2006-06-01

High-level waste glasses are submitted to auto-irradiation. Modelling it using external irradiations on simple glasses revealed defects production and non negligible structural changes. This thesis aims at determining the impact of a more complex composition on these effects, especially the influence of adding polyvalent transition metals. Silicate, soda-lime and alumino-borosilicate glasses are doped with different iron, chromium and manganese concentrations then β irradiated at different doses up to 10 9 Gy. Non doped glasses show an increase of their density and polymerisation coupled with a molecular oxygen and point defects production. Adding 0.16 mol% Fe decreases the amount of defects by 85 % and all irradiation effects. A Fe 3+ reduction is also observed by EPR, optical absorption and indirectly by Raman spectroscopy. A higher than 0.32 mol% Fe concentration causes complete blockage of the evolution of polymerisation, density and defect production. The same results are obtained on chromium or manganese doped glasses. An original in situ optical absorption device shows the quick decrease of Fe 3+ amount to a 25 % lower level during irradiation. Stopping irradiation causes a lower decrease of 65 %, suggesting a dynamic (h 0 /e-) consuming equilibrium. He + and Kr 3+ ions and γ irradiated glasses tend to confirm these phenomena for all kind of irradiation with electronic excitations. (author)

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

International Nuclear Information System (INIS)

Davis, Linda L.; Darab, John G.; Qian, Maoxu; Zhao, Donggao; Palenik, Christopher S.; Li, Hong; Strachan, Denis M.; Li, Liyu

2003-01-01

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

Utilization of Cs137 to generate a radiation barrier for weapons grade plutonium immobilized in borosilicate glass canisters. Revision 1

International Nuclear Information System (INIS)

Jardine, L.J.; Armantrout, G.A.; Collins, L.F.

1995-01-01

One of the ways recommended by a recent National Academy of Sciences study to dispose of excess weapons-grade plutonium is to encapsulate the plutonium in a glass in combination with high-level radioactive wastes (HLW) to generate an intense radiation dose rate field. The objective is to render the plutonium as difficult to access as the plutonium contained in existing US commercial spent light-water reactor (LWR) fuel until it can be disposed of in a permanent geological repository. A radiation dose rate from a sealed canister of 1,000 rem/h (10 Sv/h) at 1 meter for at least 30 years after fabrication was assumed in this paper to be a radiation dose comparable to spent LWR fuel. This can be achieved by encapsulating the plutonium in a borosilicate glass with an adequate amount of a single fission product in the HLWS, namely radioactive Cs 137 . One hundred thousand curies of Cs 137 will generate a dose rate of 1,000 rem/h (10 Sv/h) at 1 meter for at least 30 years when imbedded into canisters of the size proposed for the Savannah River Site's vitrified high-level wastes. The United States has a current inventory of 54 MCi of CS 137 that has been separated from defense HLWs and is in sealed capsules. This single curie inventory is sufficient to spike 50 metric tons of excess weapons-grade plutonium if plutonium can be loaded at 5.5 wt% in glass, or 540 canisters. Additional CS 137 inventories exist in the United States' HLWs from past reprocessing operations, should additional curies be required. Using only one fission product, CS 137 , rather than the multiple chemical elements and compounds in HLWs to generate a high radiation dose rate from a glass canister greatly simplifies the processing engineering retirement for encapsulating plutonium in a borosilicate glass

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

International Nuclear Information System (INIS)

Cafe, Arven I.; Liamzon, Angelie J.

2011-03-01

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)

Solubility of actinides and surrogates in nuclear glasses

International Nuclear Information System (INIS)

Lopez, Ch.

2003-01-01

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 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)

Temperature and Vibration Dependence of the Faraday Effect of Gd₂O₃ NPs-Doped Alumino-Silicate Glass Optical Fiber.

Science.gov (United States)

Ju, Seongmin; Kim, Jihun; Linganna, Kadathala; Watekar, Pramod R; Kang, Seong Gu; Kim, Bok Hyeon; Boo, Seongjae; Lee, Youjin; An, Yong Ho; Kim, Cheol Jin; Han, Won-Taek

2018-03-27

All-optical fiber magnetic field sensor based on the Gd₂O₃ nano-particles (NPs)-doped alumino-silicate glass optical fiber was developed, and its temperature and vibration dependence on the Faraday Effect were investigated. Uniformly embedded Gd₂O₃ NPs were identified to form in the core of the fiber, and the measured absorption peaks of the fiber appearing at 377 nm, 443 nm, and 551 nm were attributed to the Gd₂O₃ NPs incorporated in the fiber core. The Faraday rotation angle (FRA) of the linearly polarized light was measured at 650 nm with the induced magnetic field by the solenoid. The Faraday rotation angle was found to increase linearly with the magnetic field, and it was about 18.16° ± 0.048° at 0.142 Tesla (T) at temperatures of 25 °C-120 °C, by which the estimated Verdet constant was 3.19 rad/(T∙m) ± 0.01 rad/(T∙m). The variation of the FRA with time at 0.142 T and 120 °C was negligibly small (-9.78 × 10 -4 °/min). The variation of the FRA under the mechanical vibration with the acceleration below 10 g and the frequency above 50 Hz was within 0.5°.

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

International Nuclear Information System (INIS)

Rebiscoul, D.; Bruguier, F.; Gin, S.; Magnin, V.

2012-01-01

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 m 2 .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)

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

Science.gov (United States)

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

2017-10-01

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

Color centers of a borosilicate glass induced by 10 MeV proton, 1.85 MeV electron and 60Co-γ ray

International Nuclear Information System (INIS)

Du, Jishi; Wu, Jiehua; Zhao, Lili; Song, Lixin

2013-01-01

Optical absorption spectra, electron paramagnetic resonance (EPR) spectra, Raman spectra of a borosilicate glass after irradiation by 10 MeV proton, 1.85 MeV electron and 60 Co-γ ray were studied. The process of irradiation inducing color centers in the glass was discussed. The band gap of the glass before and after 60 Co-γ ray irradiation was studied using Mott and Davis's theory, and it was found that calculated change of the band gap introduced a paradox, because Mott and Davis's theory on the band gap cannot be adopted in the study on the irradiated glass. - Highlights: ► All the three types of irradiation induce the same types of color centers. ► Calculated change of the band gap introduced a paradox. ► Mott and Davis's theory on band gap cannot be adopted in the irradiated glass

Laser-assisted fabrication of gold nanoparticle-composed structures embedded in borosilicate glass

Directory of Open Access Journals (Sweden)

Nikolay Nedyalkov

2017-11-01

Full Text Available We present results on laser-assisted formation of two- and three-dimensional structures comprised of gold nanoparticles in glass. The sample material was gold-ion-doped borosilicate glass prepared by conventional melt quenching. The nanoparticle growth technique consisted of two steps – laser-induced defect formation and annealing. The first step was realized by irradiating the glass by nanosecond and femtosecond laser pulses over a wide range of fluences and number of applied pulses. The irradiation by nanosecond laser pulses (emitted by a Nd:YAG laser system induced defect formation, expressed by brown coloration of the glass sample, only at a wavelength of 266 nm. At 355, 532 and 1064 nm, no coloration of the sample was observed. The femtosecond laser irradiation at 800 nm also induced defects, again observed as brown coloration. The absorbance spectra indicated that this coloration was related to the formation of oxygen deficiency defects. After annealing, the color of the irradiated areas changed to pink, with a corresponding well-defined peak in the absorbance spectrum. We relate this effect to the formation of gold nanoparticles with optical properties defined by plasmon excitation. Their presence was confirmed by high-resolution TEM analysis. No nanoparticle formation was observed in the samples irradiated by nanosecond pulses at 355, 532 and 1064 nm. The optical properties of the irradiated areas were found to depend on the laser processing parameters; these properties were studied based on Mie theory, which was also used to correlate the experimental optical spectra and the characteristics of the nanoparticles formed. We also discuss the influence of the processing conditions on the characteristics of the particles formed and the mechanism of their formation and demonstrate the fabrication of structures composed of nanoparticles inside the glass sample. This technique can be used for the preparation of 3D nanoparticle systems

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

International Nuclear Information System (INIS)

Bonfils, J. de

2007-09-01

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 3+ and Nd 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 13 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)

Visible and near infrared up-conversion luminescence in Yb3+/Tm3+ co-doped yttria-alumino-silicate glass based optical fibers

International Nuclear Information System (INIS)

Halder, Arindam; Chandra Paul, Mukul; Wadi Harun, Sulaiman; Kumar Bhadra, Shyamal; Bysakh, Sandip; Das, Shyamal; Pal, Mrinmay

2013-01-01

We report blue light up-conversion (UC) emission in Yb–Tm co-doped nano-phase separated yttria-alumino-silicate (YAS) glass based D-shaped with low-index cladding optical fibers. Y 2 O 3 creates an environment of nano structured YAS glass phases with Yb and Tm rich zone into the core glass which confirmed from TEM analyses. This kind of glass host assists in distributing of Yb and Tm rich zone uniformly throughout the core region. Yb and Tm doped regions exist mainly into nano YAS phases, defined as RE rich nano YAS-RE phases. All samples exhibit UC luminescence peaks at 483 nm, 650 nm and 817 nm for Tm 3+ and 1044 nm for Yb 3+ under excitation by 975 nm laser light. In such type of nano-engineered glass–ceramic based host, almost all the Yb ions transferred its energy to the nearer Tm ions. In particular 483 nm emission is attributed to 1 G 4 → 3 H 6 transition through a three step resonance energy transfer (ET) from excited Yb 3+ . The highest emission intensity is obtained with a concentration of 0.5 wt% Tm 3+ and 2.0 wt% Yb 3+ . The ET between Yb 3+ and Tm 3+ is increased with increase of Yb 3+ concentration with respect to Tm 3+ . The experimental fluorescence life-times of Tm 3+ upconversion emission at visible wavelengths into such kind of fiber is reported under 975 nm pump excitation. The present study is important for development of an efficient tunable 483 nm fluorescence light source. -- Highlights: • We report nano-phase separated YAS glass host based Yb–Tm co-doped optical fibers. • Almost all the Yb transferred its energy to the neighboring Tm ions. • We report strong UC luminescence peaks at 483 nm and 817 nm wavelengths. • We report third ET coefficient as 1.6723 Hz for such kind of Yb–Tm codoped fiber. • We report suitable fiber as an efficient tunable 483 nm fluorescence light source

Dissolution of lanthanide alumino-silicate oxynitride glasses

Science.gov (United States)

Bois, L.; Barré, N.; Guillopé, S.; Guittet, M. J.; Gautier-Soyer, M.; Duraud, J. P.; Trocellier, P.; Verdier, P.; Laurent, Y.

2000-01-01

The aqueous corrosion behavior of lanthanide aluminosilicate glasses has been studied under static conditions ( T=96°C, duration=1 and 3 months, glass surface area/leachate volume, S/ V=0.3 cm -1) by means of solution and solid analyses. It was found that these glasses exhibit a high chemical durability. The influence of yttrium, magnesium and nitrogen, which are supposed to improve the mechanical properties, on the chemical durability, has been investigated. After a one-month experiment, lanthanum and yttrium releases were found to be about 10 -7 mol l -1, while silicon and aluminum releases were about 10 -5 mol l -1. Yttrium seems to improve the chemical durability. The presence of nitrogen does not seem to modify the glass constituents releases, but seems to improve the surface state of the altered glass. XPS experiments reveal that lanthanum and yttrium are more concentrated near the surface (20-30 Å) of the glass after the leaching test.

Waste glass corrosion modeling: Comparison with experimental results

International Nuclear Information System (INIS)

Bourcier, W.L.

1993-11-01

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

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

International Nuclear Information System (INIS)

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

1993-04-01

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

Spent fuel from nuclear research reactors immobilized in sintered glass

International Nuclear Information System (INIS)

Mateos, P.; Russo, D.O.; Rodriguez, D.; Heredia, A.; Sanfilippo, M.; Sterba, M.

2002-01-01

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)

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

Energy Technology Data Exchange (ETDEWEB)

Windisch, Charles F.; Pierce, Eric M.; Burton, Sarah D.; Bovaird, Chase C.

2011-03-24

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

Heat accumulation during high repetition rate ultrafast laser interaction: Waveguide writing in borosilicate glass

International Nuclear Information System (INIS)

Zhang, Haibin; Eaton, Shane M; Li, Jianzhao; Herman, Peter R

2007-01-01

During high repetition rate (>200 kHz) ultrafast laser waveguide writing, visible heat modified zones surrounding the formed waveguide occur as a result of heat accumulation. The radii of the heat-modified zones increase with the laser net fluence, and were found to correlate with the formation of low-loss and cylindrically symmetric optical waveguides. A numerical thermal model based on the finite difference method is applied here to account for cumulative heating and diffusion effects. The model successfully shows that heat propagation and accumulation accurately predict the radius of the 'heat modified' zones observed in borosilicate glass waveguides formed across a wide range of laser exposure conditions. Such modelling promises better control of thermal effects for optimizing the fabrication and performance of three-dimensional optical devices in transparent materials

Optical absorption and gamma-radiation-shielding parameter studies of Tm3+-doped multicomponent borosilicate glasses

Science.gov (United States)

Lakshminarayana, G.; Sayyed, M. I.; Baki, S. O.; Lira, A.; Dong, M. G.; Kaky, Kawa M.; Kityk, I. V.; Mahdi, M. A.

2018-05-01

Different concentrations (0.1‒2.0 mol%) of Tm3+-doped multicomponent borosilicate glasses with 10 mol% Li2O (alkali) or MgO (alkaline) have been synthesized and their optical absorption and radiation shielding features were studied. For both Li2O and MgO series 0.5 mol% Tm3+-doped glass samples, the evaluated Ωλ ( λ = 2, 4, and 6) Judd-Ofelt (JO) intensity parameters from experimental oscillator strengths were used in estimating the radiative transition probabilities ( A R), branching ratios ( β R), and radiative lifetimes ( τ R) for several emission transitions. Using the XCOM software, the mass attenuation coefficients ( µ/ ρ) for all the fabricated glasses were evaluated within the 0.015‒10 MeV energy range. Also, the ( µ/ ρ) values were calculated at 0.356, 0.662, 1.173, and 1.33 MeV photon energies by MCNP5 simulation code and the results were compared with those obtained by XCOM. The ( µ/ ρ) values for Li2O, as well as MgO series glasses, increase with the addition of Tm2O3 and these values for MgO series glasses are slightly higher with respect to Li2O series glasses. From the ( µ/ ρ) values, effective atomic number ( Z eff), half-value layer (HVL), and mean free path (MFP) were calculated and the HVL and MFP results revealed that high-energy photons have more penetration into a glass sample compared to low-energy photons. Further, geometric progression (GP) fitting method was utilized to calculate the exposure buildup factor (EBF) within the 0.015‒15 MeV energy range. The 2.0 mol% Tm2O3-doped glasses show a better ability to attenuate gamma-rays in comparison to other glass samples, so the addition of Tm2O3 content leads to improvement of the shielding efficiency of the prepared glasses.

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-01-01

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

A novel low cost polyvinyl alcohol-Nafion-borosilicate membrane separator for microbial fuel cell

Energy Technology Data Exchange (ETDEWEB)

Tiwari, B.R. [Department of Civil Engineering, Indian Institute of Technology, Kharagpur, 721302 (India); Noori, Md.T. [Department of Agriculture and Food Engineering, Indian Institute of Technology, Kharagpur, 721302 (India); Ghangrekar, M.M., E-mail: ghangrekar@civil.iitkgp.ernet.in [Department of Civil Engineering, Indian Institute of Technology, Kharagpur, 721302 (India)

2016-10-01

Composite membranes were developed from PVA-borosilicate (MP) and PVA-Nafion-borosilicate (MPN) for application in microbial fuel cells (MFCs). The membranes were characterized in terms of water uptake, PBS uptake, oxygen diffusion and proton conductivity. Proton conductivity for MPN (0.07 Scm{sup −1}) was found to be higher as compared to that of MP (0.03 Scm{sup −1}). Oxygen diffusion coefficient for MPN was 1.47 fold lower than that for MP. As a result, MFC with PVA-Nafion-borosilicate membrane exhibited maximum power density of 6.8 Wm{sup −3}, which was 151% higher than the power produced by MFC having PVA-borosilicate membrane and it was comparable with MFC using Nafion 117 (7.1 Wm{sup −3}) membrane separator. This study demonstrates that borosilicate glass membrane incorporated with PVA-Nafion matrix can be a suitable alternative to costly polymeric membrane to increase power output of MFC. Using such membranes MFC can be fabricated at around 11 fold reduced cost as compared to Nafion 117. - Highlights: • Novel membranes using PVA and borosilicate composite were fabricated. • Proton diffusion for MPN was comparable with Nafion117. • MFC-PN produced power density comparable to MFC with Nafion 117 membrane. • MPN was fabricated at almost 11 times reduced cost than Nafion 117 membranes.

Recovery of palladium, cesium, and selenium from heavy metal alkali borosilicate glass by combination of heat treatment and leaching processes

Energy Technology Data Exchange (ETDEWEB)

Xu, Zhanglian; Okada, Takashi, E-mail: t-okada@u-fukui.ac.jp; Nishimura, Fumihiro; Yonezawa, Susumu

2017-06-05

Highlights: • A separation technique of both noble and less noble metal from glass is studied. • Via reductive heat treatment, 80% of palladium is extracted in liquid bismuth. • Sodium–potassium-rich materials with cesium and selenium are phase separated. • From the materials, over 80% of cesium and selenium are extracted in water. - Abstract: Reductive heat-treatment and leaching process were applied to a simulated lead or bismuth soda-potash-borosilicate glass with palladium, cesium, and selenium to separate these elements. In the reductive heat treatment, palladium is extracted in liquid heavy metal phase generated by the reduction of the heavy metal oxides, whereas cesium and selenium are concentrated in phase separated Na–K-rich materials on the glass surface. From the materials, cesium and selenium can be extracted in water, and the selenium extraction was higher in the treatment of the bismuth containing glass. The chemical forms of palladium in the glass affected the extraction efficiencies of cesium and selenium. Among the examined conditions, in the bismuth glass treatment, the cesium and selenium extraction efficiencies in water were over 80%, and that of palladium in liquid bismuth was over 80%.

Effects of Sb2O3 on the Mechanical Properties of the Borosilicate Foam Glasses Sintered at Low Temperature

Directory of Open Access Journals (Sweden)

Chenxi Zhai

2014-01-01

Full Text Available The physical properties and microstructure of a new kind of borosilicate foam glasses with different Sb2O3 doping content are comprehensively investigated. The experimental results show that appropriate addition of Sb2O3 has positive impact on the bulk porosity and compressive strength of the foam glass. It is more suitable in this work to introduce 0.9 wt.% Sb2O3 into the Na2O-K2O-B2O3-Al2O3-SiO2 basic foam glass component and sinter at 775°C. And the obtained foam glasses present much more uniform microstructure, large pore size, and smooth cell walls, which bring them with better performance including a lower bulk density, low water absorption, and an appreciable compressive strength. The microstructure analysis indicates that, with the increase of the content of Sb2O3 additives, the cell size tends to increase at first and then decreases. Larger amounts of Sb2O3 do not change the crystalline phase of foam glass but increase its vitrification. It is meaningful to prepare the foam glass at a relatively low temperature for reducing the heat energy consumption.

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

Energy Technology Data Exchange (ETDEWEB)

Mohd Fadzil, Syazwani, E-mail: mfsyazwani86@postech.ac.kr [Division of Advanced Nuclear Engineering, Pohang University of Science and Technology, 790784 Pohang, Gyeongbuk (Korea, Republic of); School of Applied Physics, Faculty of Science and Technology, The National University of Malaysia, 43650 Bandar Baru Bangi, Selangor (Malaysia); Hrma, Pavel [Division of Advanced Nuclear Engineering, Pohang University of Science and Technology, 790784 Pohang, Gyeongbuk (Korea, Republic of); Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA (United States); Schweiger, Michael J.; Riley, Brian J. [Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA (United States)

2015-10-15

Pyroprocessing is are processing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl–KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the glass matrix at high loadings. Crystallization that occurs in waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (T{sub L}): 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% RE{sub 2}O{sub 3}) while possessing an acceptable chemical durability. - Highlights: • We investigated crystallization in borosilicate glasses containing rare earth oxides. • New crystallinity and durability data are shown for glasses proposed in the literature. • Both liquidus temperature and chemical durability increased as the waste loading increased.

Standardization of a PIGE methodology for simultaneous quantification of low Z elements in barium borosilicate glass samples

International Nuclear Information System (INIS)

Chhillar, S.; Acharya, R.; Dasari, K.B.; Pujari, P.K.; Mishra, R.K.; Kaushik, C.P.

2013-01-01

In order to standardize particle induced gamma-ray emission (PIGE) methodology for simultaneous quantification of light elements, analytical sensitivities of Li, F, B, Na, Al and Si were evaluated using 4 MeV proton beam ( ∼ 10 nA current) using 3 MV Pelletron at IOP, Bhubaneswar. The PIGE method was validated by determining all six elements in a synthetic sample in graphite matrix and applied to two barium borosilicate glass (BaBSG) samples. The prompt γ-rays emitted from inelastic scattering or nuclear reactions of corresponding isotopes were measured using a 60% HPGe coupled to MCA and the current normalized count rates were used for concentration calculation. (author)

Characteristics of borosilicate waste glass form for high-level radioactive waste

Energy Technology Data Exchange (ETDEWEB)

Kim, Seung Soo; Chun, Kwan Sik; Choi, Jong Won; Kang, Chul Hyung

2001-03-01

Basic data, required for the design and the performance assessment of a repository of HLW, suchas the chemical composition and the characteristics of the borosilicate waste glass have been identified according to the burn-ups of spent PWR fuels. The diemnsion of waste canister is 430mm in diameter and 1135mm in length, and the canister should hold less than 2kwatts of heat from their decay of radionuclides contained in the HLW. Based on the reprocessing of 5 years-cooled spent fuel, one canister could hold about 11.5wt.% and 10.8wt.% of oxidized HLW corresponding to their burn-ups of 45,000MWD/MTU and 55,000MWD/MTU, respectively. These waste forms have been recommanded as the reference waste forms of HLW. The characteristics of these wastes as a function of decay time been evaluated. However, after a specific waste form and a specific site for the disposal would be selected, the characteristics of the waste should be reevaluated under the consideration of solidification period, loaded waste, storage condition and duration, site circumstances for the repository system and its performance assessment.

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)

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

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

Energy Technology Data Exchange (ETDEWEB)

Kim, Miae [Department of Materials Science and Engineering and Division of Advanced Nuclear Engineering, Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk, 790-784 (Korea, Republic of); Heo, Jong, E-mail: jheo@postech.ac.kr [Department of Materials Science and Engineering and Division of Advanced Nuclear Engineering, Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk, 790-784 (Korea, Republic of); Department of Materials Engineering, Adama Science and Technology University (ASTU), PO Box 1888, Adama (Ethiopia)

2015-12-15

Glass-ceramics containing calcium neodymium(cerium) oxide silicate [Ca{sub 2}Nd{sub 8-x}Ce{sub x}(SiO{sub 4}){sub 6}O{sub 2}] 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{sup −6} g m{sup −2} for Ce ion and 2.19·10{sup −6} g m{sup −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. - Highlights: • Glass-ceramic wasteforms containing Ca{sub 2}Nd{sub 8-x}Ce{sub x}(SiO{sub 4}){sub 6}O{sub 2} crystals were synthesized to immobilize lanthanide wastes. • Maximum lanthanide oxide waste loading was >26.8 wt.%. • Ce and Nd ions were highly partitioned inside Ca–Nd–silicate crystals compared to glass matrix. • Amounts of Ce and Nd ions released in the material characterization center-type 1 were below the detection limit (0.1 ppb). • Normalized release values performed by a PCT were 2.64• 10{sup −6} g m{sup −2} for Ce ions and 2.19• 10{sup −6} g m{sup −2} for Nd ions.

VARIABILITY STUDY TO DETERMINE THE SOLUBILITY OF IMPURITIES IN PLUTONIUM-BEARING, LANTHANIDE BOROSILICATE GLASS

Energy Technology Data Exchange (ETDEWEB)

Fox, K; Elizabeth Hoffman, E; Charles Crawford, C; Tommy Edwards, T; David Best, D; James Marra, J

2007-09-26

This study focuses on the development of a compositional envelope that describes the retention of various impurities in lanthanide borosilicate (LaBS) glass for vitrification and immobilization of excess, defense-related plutonium. A limited amount of impurity data for the various plutonium sources is available and projections were made through analysis of the available information. These projections were used to define types and concentrations of impurities in the LaBS glass compositions to be fabricated and tested. Sixty surrogate glass compositions were developed through a statistically designed approach to cover the anticipated ranges of concentrations for several impurity species expected in the plutonium feeds. An additional four glass compositions containing actual plutonium oxide were selected based on their targeted concentrations of metals and anions. The glasses were fabricated and characterized in the laboratory and shielded cells facility to determine the degree of retention of the impurity components, the impact of the impurities on the durability of each glass, and the degree of crystallization that occurred, both upon quenching and slow cooling. Overall, the LaBS glass system appears to be very tolerant of most of the impurity types and concentrations projected in the plutonium waste stream. For the surrogate glasses, the measured CuO, Ga{sub 2}O{sub 3}, Na{sub 2}O, NiO, and Ta{sub 2}O{sub 5} concentrations fell very close to their target values across the ranges of concentrations targeted in this study for each of these components. The measured CaO and PbO concentrations were consistently higher than the targeted values. The measured Cr{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} concentrations were very close to the targets except for the one highest targeted value for each of these components. A solubility limit may have been approached in this glass system for K{sub 2}O and MgO. The measured Cl{sup -}, F{sup -}, SeO{sub 2} and SO{sub 4}{sup 2

Chemical and mechanical performance properties for various final waste forms -- PSPI scoping study

International Nuclear Information System (INIS)

Farnsworth, R.K.; Larsen, E.D.; Sears, J.W.; Eddy, T.L.; Anderson, G.L.

1996-09-01

The US DOE is obtaining data on the performance properties of the various final waste forms that may be chosen as primary treatment products for the alpha-contaminated low-level and transuranic waste at the INEL's Transuranic Storage Area. This report collects and compares selected properties that are key indicators of mechanical and chemical durability for Portland cement concrete, concrete formed under elevated temperature and pressure, sulfur polymer cement, borosilicate glass, and various forms of alumino-silicate glass, including in situ vitrification glass and various compositions of iron-enriched basalt (IEB) and iron-enriched basalt IV (IEB4). Compressive strength and impact resistance properties were used as performance indicators in comparative evaluation of the mechanical durability of each waste form, while various leachability data were used in comparative evaluation of each waste form's chemical durability. The vitrified waste forms were generally more durable than the non-vitrified waste forms, with the iron-enriched alumino-silicate glasses and glass/ceramics exhibiting the most favorable chemical and mechanical durabilities. It appears that the addition of zirconia and titania to IEB (forming IEB4) increases the leach resistance of the lanthanides. The large compositional ranges for IEB and IEB4 more easily accommodate the compositions of the waste stored at the INEL than does the composition of borosilicate glass. It appears, however, that the large potential variation in IEB and IEB4 compositions resulting from differing waste feed compositions can impact waste form durability. Further work is needed to determine the range of waste stream feed compositions and rates of waste form cooling that will result in acceptable and optimized IEB or IEB4 waste form performance. 43 refs

Development and radiation stability of glasses for highly radioactive wastes

International Nuclear Information System (INIS)

Hall, A.R.; Dalton, J.T.; Hudson, B.; Marples, J.A.C.

1976-01-01

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 1050 0 C. 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 100 0 C 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 200 0 C. (author)

Leaching of the simulated borosilicate waste glasses and spent nuclear fuel under a repository condition

International Nuclear Information System (INIS)

Kim, Seung Soo; Chun, Kwan Sik; Kang, Chul Hyung; Suh, Hang Suk

2002-12-01

Leaching behaviors of simulated waste glass and spent fuel, contacted on bentonite blocks, in synthetic granitic groundwater were investigated in this study. The leach rate of boron from borosilicate waste glass between the compacted bentonite blocks reached about 0.03 gm-2day-1 at 1500 days, like as that of molybdenum. However, the concentration of uranium in leachate pass through bentonite blocks was less than their detection limits of 2 μg/L and whose yellow amorphous compound was found on the surface of glass contacted with the bentonite blocks. The leaching mechanism of waste glasses differed with their composition. The release rate of cesium from PWR spent fuel in the simulated granitic water without bentonite was leas than $1.0x10 -5 fraction/day after 300 days. The retardation factor of cesium by a 10 -mm thickness of bentonite block was more than 100 for 4-years leaching time. The cumulative release fraction of uranium for 954 days was 0.016% (1.7x10 -7 fraction/day) in granitic water without bentonite. The gap inventory of cesium for spent fuel G23-J11 was 0.15∼0.2%. However, the release of cesium from C15-I08 was 0.9% until 60 days and has being continued after that. Gap inventories of strontium and iodine in G23-J11 were 0.033% and below 0.2%, respectively. The sum of fraction of cesium in gap and grain boundary of G23-J11 was suggested below 3% and less

Waste glass corrosion modeling: Comparison with experimental results

International Nuclear Information System (INIS)

Bourcier, W.L.

1994-01-01

Models for borosilicate glass dissolution must account for the processes of (1) kinetically-controlled network dissolution, (2) precipitation of secondary phases, (3) ion exchange, (4) rate-limiting diffusive transport of silica through a hydrous surface reaction layer, and (5) specific glass surface interactions with dissolved cations and anions. Current long-term corrosion models for borosilicate glass employ a rate equation consistent with transition state theory embodied in a geochemical reaction-path modeling program that calculates aqueous phase speciation and mineral precipitation/dissolution. These models are currently under development. Future experimental and modeling work to better quantify the rate-controlling processes and validate these models are necessary before the models can be used in repository performance assessment calculations

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

International Nuclear Information System (INIS)

Chen, Daqin; Wan, Zhongyi; Zhou, Yang; Chen, Yan; Yu, Hua; Lu, Hongwei; Ji, Zhenguo; Huang, Ping

2015-01-01

Highlights: • Na 5 Gd 9 F 32 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 Na 5 Gd 9 F 32 lattice. • Luminescent color could be tuned by controlling glass crystallization temperature. - Abstract: Lanthanide-activated cubic Na 5 Gd 9 F 32 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 Na 5 Gd 9 F 32 lattice was in situ formed without the requirement of long-range ionic diffusion. Impressively, such fabricated glass ceramic co-doped with Yb 3+ /Er 3+ 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

Glass containing radioactive nuclear waste

International Nuclear Information System (INIS)

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

1985-01-01

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

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

International Nuclear Information System (INIS)

Kruger, A.A.; Heo, J.; Xu, K.; Choi, J.K.; Hrma, P.R.; Um, W.

2011-01-01

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.

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)

Oxide glass structure evolution under swift heavy ion irradiation

International Nuclear Information System (INIS)

Mendoza, C.; Peuget, S.; Charpentier, T.; Moskura, M.; Caraballo, R.; Bouty, O.; Mir, A.H.; Monnet, I.; Grygiel, C.; Jegou, C.

2014-01-01

Highlights: • Structure of SHI irradiated glass is similar to the one of a hyper quenched glass. • D2 Raman band associated to 3 members ring is only observed in irradiated glass. • Irradiated state seems slightly different to an equilibrated liquid quenched rapidly. - Abstract: The effects of ion tracks on the structure of oxide glasses were examined by irradiating a silica glass and two borosilicate glass specimens containing 3 and 6 oxides with krypton ions (74 MeV) and xenon ions (92 MeV). Structural changes in the glass were observed by Raman and nuclear magnetic resonance spectroscopy using a multinuclear approach ( 11 B, 23 Na, 27 Al and 29 Si). The structure of irradiated silica glass resembles a structure quenched at very high temperature. Both borosilicate glass specimens exhibited depolymerization of the borosilicate network, a lower boron coordination number, and a change in the role of a fraction of the sodium atoms after irradiation, suggesting that the final borosilicate glass structures were quenched from a high temperature state. In addition, a sharp increase in the concentration of three membered silica rings and the presence of large amounts of penta- and hexacoordinate aluminum in the irradiated 6-oxide glass suggest that the irradiated glass is different from a liquid quenched at equilibrium, but it is rather obtained from a nonequilibrium liquid that is partially relaxed by very rapid quenching within the ion tracks

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

International Nuclear Information System (INIS)

Magnin, M.

2009-09-01

Molybdenum oxide immobilization (MoO 3 , 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 MoO 3 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 SiO 2 -B 2 O 3 - Na 2 O-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 ( 95 Mo, 29 Si, 11 B, 23 Na 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 (CaMoO 4 , Na 2 MoO 4 ) that depend on the evolution of MoO 3 , CaO and B 2 O 3 contents were correlated with changes of sodium and calcium cations proportions in the

Effect of the kind of alkaline and rare earth ions on the structure of a glass rich in earth; Effet de la nature des ions alcalins et alcalino-terreux sur la structure d un verre riche en terre

Energy Technology Data Exchange (ETDEWEB)

Quintas, Arnaud; Caurant, Daniel; Majerus, Odile [Laboratoire de Chimie Appliquee de l Etat Solide, UMR 7574, ENSCP, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05, (France); Lenoir, Marion; Dussossoy, Jean-Luc [Commissariat a l Energie Atomique, Centre d Etudes de la Vallee du Rhone, DIEC/SCDV/LEBM, 30207 Bagnols-sur-Ceze, (France); Charpentier, Thibault [Service de Chimie Moleculaire, DSM/DRECAM/CEA Saclay, 91191 Gif-sur-Yvette Cedex, (France); Neuville, Daniel R. [Laboratoire de Physique des Mineraux et des Magmas, UMR 7047-CNRS-IPGP, Universite Pierre et Marie Curie, 4 place Jussieu, 75252 Paris Cedex 05, (France); Gervais, C. [Laboratoire de Chimie de la matiere condensee, UMR7574, Universite Pierre et Marie Curie, 4 place Jussieu, F-75252 Paris Cedex 05, (France)

2006-07-01

In the framework of a structural study of a nuclear wastes containment glass of type alumino borosilicate and rich in rare earths, the influence of the kind of alkaline or rare earth ions is analyzed. For that, two glasses series have been prepared in which the Na{sup +} ion (respectively Ca{sup 2+} ions) present in the standard composition is totally substituted by another alkaline ion Li{sup +}, K{sup +}, Rb{sup +} or Cs{sup +} (respectively another rare earth ion Mg{sup 2+}, Sr{sup 2+} or Ba{sup 2+}). These glasses, analyzed by optical absorption, Raman and {sup 27}Al or {sup 11}B NMR spectroscopies have revealed the strong impact of the kind of the modifying ion as well as the structure of the vitreous lattice (variation of the ratio BO{sub 3}/BO{sub 4} and local variations of the polymerization degree) than the local surroundings of the rare earth (decrease of the covalency degree of the bond Nd-O with the increase of the field force of the modifying ion). (O.M.)

Relative leach behavior of waste glasses and naturally occurring glasses

International Nuclear Information System (INIS)

Adams, P.B.

1979-01-01

Simulated nuclear waste glasses of the sodium-borosilicate type with a low waste loading and of the zinc-borosilicate type with a high waste loading have been compared with obsidians. The resuls indicate that the waste glasses would corrode in normal natural environments at a rate of about 0.1 μm per year at 30 0 C and about 5 μm per year at 90 0 C, compared with obsidians which seem to corrode at, or less than, about 0.01 μm per year at 30 0 C and less than 1 μm per year at 90 0 C. Activation energies for reactions of the two waste glasses with pure water are about 20 kcal/g-mol. 3 figures, 7 tables

Immobilization of Uranium Silicides in Sintered Glass

International Nuclear Information System (INIS)

Mateos, P.; Russo, D.O.; Heredia, A.D.; Sanfilippo, M.

2003-01-01

High activity nuclear spent fuels vitrification by fusion is a well known technology which has industrial scale in France, England, Japan, EEUU. Borosilicates glasses are used in this process.Sintered glasses are an alternative to the immobilization task in which there is also a wide experience around the world.The available technics are: cold pressing and sintering , hot-pressing and hot isostatic pressing.This work compares Borosilicates and Iron silicates sintered glasses behaviour when different ammounts of nuclear simulated waste is added

Crystal growth in zinc borosilicate glasses

Science.gov (United States)

Kullberg, Ana T. G.; Lopes, Andreia A. S.; Veiga, João P. B.; Monteiro, Regina C. C.

2017-01-01

Glass samples with a molar composition (64+x)ZnO-(16-x)B2O3-20SiO2, where x=0 or 1, were successfully synthesized using a melt-quenching technique. Based on differential thermal analysis data, the produced glass samples were submitted to controlled heat-treatments at selected temperatures (610, 615 and 620 °C) during various times ranging from 8 to 30 h. The crystallization of willemite (Zn2SiO4) within the glass matrix was confirmed by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Under specific heat-treatment conditions, transparent nanocomposite glass-ceramics were obtained, as confirmed by UV-vis spectroscopy. The influence of temperature, holding time and glass composition on crystal growth was investigated. The mean crystallite size was determined by image analysis on SEM micrographs. The results indicated an increase on the crystallite size and density with time and temperature. The change of crystallite size with time for the heat-treatments at 615 and 620 °C depended on the glass composition. Under fixed heat-treatment conditions, the crystallite density was comparatively higher for the glass composition with higher ZnO content.

Simulating the physicochemical properties of borosilicate and lanthanum borosilicate glasses using a polarizable force field

International Nuclear Information System (INIS)

Pacaud, Fabien

2016-01-01

as result of the nuclear waste vitrification, the knowledge and understanding of the dynamic and structural properties of glasses, including the behavior of radionuclides, is important (in liquid and solid phases). It can influence the glass waste properties, the lifetime of the vitrification process and the amount of radionuclides introduced in the glass matrix. Molecular dynamic simulations have been done to study the influence of the glass matrix composition into the structural and dynamic properties of the glass. a simplified glass, with 3 major oxides of the R7T7 glass such as SiO_2, B_2O_3 and Na_2O, have been used to simulate the R7T7 industrial nuclear glass (a 30 oxides glass). The inclusion of La_2O_3 allows us to simulate the impact of fission products and minor actinides into the properties of the glass matrix. Both systems, the SiO_2-B_2O_3-Na_2O and SiO_2-B_2O_3-Na_2O-La_2O_3, allow us to study the sodium and lanthanum effect on the properties of the glass. During this work, a polarizable force field has been developed to do these simulations. The results obtained at room temperature let us reproduce the experimental results of the structure, the distribution of BIII/BIV and the density. a study has been done on the viscosity and electrical conductivity of the liquid. The distribution BIV/BIII and the influence of the structural changes on the density along with the temperature have also been observed with thermal quenching. The current limits of this approach are also described. (author) [fr

Immobilization of Uranium Silicide in Sintered Iron-Phosphate Glass

International Nuclear Information System (INIS)

Mateos, Patricia; Russo, Diego; Rodriguez, Diego; Heredia, A; Sanfilippo, M.; Sterba, Mario

2003-01-01

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 U 3 O 8 , the amount of U 3 O 8 was calculated to simulate an isotopic dilution of 4%.This material was mixed with powdered iron-phosphate glass (in wt.%: 64,9 P 2 O 5 ; 22,7 Fe 2 O 3 ; 8,1 Al 2 O 3 ; 4,3 Na 2 O) 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

Preliminary results of durability testing with borosilicate glass compositions

International Nuclear Information System (INIS)

Adel-Hadadi, M.; Adiga, R.; Barkatt, Aa.

1987-01-01

This is a report on the first year of research conducted at the Vitreous State Laboratory of the Catholic University of America in support of the West Valley Demonstration Project. One objective is the vitrification of liquid waste generated by previous nuclear fuel reprocessing. This work has been directed principally at the problem of glass composition optimization. This has necessitated the development of a coordinated program of glass production, durability measurements, and processability assessment. A small-scale continuous melter has been constructed for melting uranium and thorium containing glasses and for studying glass processing characteristics. Glass viscosities have been measured over a range of temperatures. A large number of glasses have also been produced in small crucible melts. Glass durability has been assessed using four types of leach tests: MCC-3, MCC-1, IAEA/ISO, and pulsed-flow tests. Extensive data from these tests are reported. The data have led to the design of very durable glasses (comparable to the Savannah River Laboratory Defense Waste Reference Glass) which have the requisite waste loading and processing characteristics. 14 refs., 4 figs., 77 tabs

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)

Jantzen, C.M.

1991-01-01

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

Emission analysis of Tb3+ -and Sm3+ -ion-doped (Li2 O/Na2 O/K2 O) and (Li2 O + Na2 O/Li2 O + K2 O/K2 O + Na2 O)-modified borosilicate glasses.

Science.gov (United States)

Naveen Kumar Reddy, B; Sailaja, S; Thyagarajan, K; Jho, Young Dahl; Sudhakar Reddy, B

2018-05-01

Four series of borosilicate glasses modified by alkali oxides and doped with Tb 3+ and Sm 3+ ions were prepared using the conventional melt quenching technique, with the chemical composition 74.5B 2 O 3 + 10SiO 2 + 5MgO + R + 0.5(Tb 2 O 3 /Sm 2 O 3 ) [where R = 10(Li 2 O /Na 2 O/K 2 O) for series A and C, and R = 5(Li 2 O + Na 2 O/Li 2 O + K 2 O/K 2 O + Na 2 O) for series B and D]. The X-ray diffraction (XRD) patterns of all the prepared glasses indicate their amorphous nature. The spectroscopic properties of the prepared glasses were studied by optical absorption analysis, photoluminescence excitation (PLE) and photoluminescence (PL) analysis. A green emission corresponding to the 5 D 4 → 7 F 5 (543 nm) transition of the Tb 3+ ions was registered under excitation at 379 nm for series A and B glasses. The emission spectra of the Sm 3+ ions with the series C and D glasses showed strong reddish-orange emission at 600 nm ( 4 G 5/2 → 6 H 7/2 ) with an excitation wavelength λ exci = 404 nm ( 6 H 5/2 → 4 F 7/2 ). Furthermore, the change in the luminescence intensity with the addition of an alkali oxide and combinations of these alkali oxides to borosilicate glasses doped with Tb 3+ and Sm 3+ ions was studied to optimize the potential alkali-oxide-modified borosilicate glass. Copyright © 2017 John Wiley & Sons, Ltd.

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

International Nuclear Information System (INIS)

Debure, M.; Frugier, P.; GIN, S.; De Windt, L.; Michau, N.

2012-01-01

easily 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 m 2 /g and 100 m 2 /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 pH 90deg.C and the higher the glass alteration. As shown in Fig. 1, the pH 90deg.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 pH 90deg.C of 5.2, whereas the test made with the glass alone led to a pH 90deg.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

Corrosion of simulated nuclear waste glass

International Nuclear Information System (INIS)

Music, S.; Ristic, M.; Gotic, M.; Foric, J.

1988-01-01

In this study the preparation and characterization of borosilicate glasses of different chemical composition were investigated. Borosilicate glasses were doped with simulated nuclear waste oxides. The chemical corrosion in water of these glasses was followed by measuring the leach rates as a function of time. It was found that a simulated nuclear waste glass with the chemical composition (weight %), 15.61% Na 2 O, 10.39% B 2 O 3 , 45.31% SiO 2 , 13.42% ZnO, 6.61% TiO 2 and 8.66% waste oxides, is characterized by low melting temperature and with good corrosion resistance in water. Influence of passive layers on the leaching behaviour of nuclear waste glasses is discussed. (author) 20 refs.; 7 figs.; 4 tabs

Development of an ASTM standard glass durability test, the Product Consistency Test (PCT), for high level radioactive waste glass

International Nuclear Information System (INIS)

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

1994-01-01

The nation's first, and the world's largest, facility to immobilize high-level nuclear waste in durable borosilicate glass has started operation at the Savannah River Site (SRS) in Aiken, South Carolina. The product specifications on the glass wasteform produced in the Defense Waste Processing Facility (DWPF) required extensive characterization of the glass product before actual production began and for continued characterization during production. To aid in this characterization, a glass durability (leach) test was needed that was easily reproducible, could be performed remotely on highly radioactive samples, and could yield results rapidly. Several standard leach tests were examined with a variety of test configurations. Using existing tests as a starting point, the DWPF Product Consistency Test (PCT was developed in which crushed glass samples are exposed to 90 ± 2 degree C deionized water for seven days. Based on extensive testing, including a seven-laboratory round robin and confirmatory testing with radioactive samples, the PCT is very reproducible, yields reliable results rapidly, and can be performed in shielded cell facilities with radioactive samples

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

International Nuclear Information System (INIS)

Dabbs, T.P.; Lawn, B.R.; Kelly, P.L.

1982-01-01

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)

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

International Nuclear Information System (INIS)

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

1989-01-01

This patent describes lead-iron phosphate glasses containing a high level of Fe 2 O 3 for use as a storage medium for high-level radioactive nuclear waste. By combining lead-iron phosphate glass with various types of simulated high-level nuclear waste, a highly corrosion resistant, homogeneous, easily processed glass can be formed. For corroding solutions at 90 0 C, with solution pH values in the range between 5 and 9, the corrosion rate of the lead-iron phosphate nuclear waste glass is at least 10 2 to 10 3 times lower than the corrosion rate of a comparable borosilicate nuclear waste glass. The presence of Fe 2 O 3 in forming the lead-iron phosphate glass is critical. The lead-iron phosphate waste glasses can be prepared with minimal modification of the technology developed for processing borosilicate glass nuclear wasteforms

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

International Nuclear Information System (INIS)

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

2015-01-01

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

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

International Nuclear Information System (INIS)

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

1984-01-01

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

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

International Nuclear Information System (INIS)

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

1995-01-01

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

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

International Nuclear Information System (INIS)

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

2004-01-01

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

Structural role of molybdenum in nuclear glasses: an EXAFS study

International Nuclear Information System (INIS)

Calas, G.; Le Grand, M.; Galoisy, L.; Ghaleb, D.

2003-01-01

The Mo environment has been investigated in inactive nuclear glasses using extended X-ray absorption spectroscopy (XAS). Mo is present in a tetrahedron coordinated to oxygen in the form of molybdate groups [MoO 4 ] 2- (d(Mo-O)=1.78 A). This surrounding is not affected by the presence of noble metal phases in the nuclear glass. Relying on the XAS results, on the bond-valence model and on molecular dynamics simulations of a simplified borosilicate model glass, we show that these groups are not directly linked to the borosilicate network but rather located within alkali and alkaline-earth rich domains in the glass. This specific location in the glass network is a way to understand the low solubility of Mo in glasses melted under oxidizing conditions. It also explains the possible phase separation of a yellow phase enriched in alkali molybdates in molten nuclear glasses or the nucleation of calcium molybdates during thermal aging of these glasses. Boron coordination changes in the molten and the glassy states may explain the difference in the composition of the crystalline molybdates, as they exert a direct influence on the activity of alkalis in borosilicate glasses and melts

Development of alumino-silicate refractories in Ghana

International Nuclear Information System (INIS)

Kisiedu, A. K.; Tetteh, D.M.B.; Obiri, H. A.; Brenya, E. F.; Ayensu, A.

2008-01-01

Alumino-silicate (bauxite), andalusite, kaolin and clay were investigated for suitability in production of alumina, mullite and fireclay brick refractories. The raw materials were characterized by X-ray diffraction, differential thermal and silicate analyses. The x-ray diffraction analysis of alumina and mullite refractories fired at 1450 0 C, and fireclay bricks fired at 1350 0 C, indicated presence of corundum and alpha-alumina crystals. The values of thermal (fired) shrinkage, crushing, strength, porosity, water absorption and bulk density determined were 31.1%, 2.3 x 10 3 kg/m 3 , 4.86 x 10 6 N/m 2 and 13.2 % for mullite; 30.2%, 2.4 x 10 3 kg/m 3 , 3.20 x 10 6 N/m 2 and W = 12.8 % for alumina; and 25.2 %, 2.1 x 10 3 kg/m 3 , 2.61 x 10 6 N/m 2 and W = 11.8% for fireclay, respectively. Bauxite, andalusite and special kaolin were identified as potential raw materials for developing alumina and mullite refractories for construction of high temperature kilns and furnaces operating at 1350 0 C. The clay and kaolin minerals could be used to produce fireclay refractories for construction of incinerators operating at maximum temperatures of about 1000 0 C. The performance of the refractories was demonstrated by producing bricks to construct kilns and incinerators for the ceramic industry and hospitals. (au)

Taylor impact of glass rods

International Nuclear Information System (INIS)

Willmott, G.R.; Radford, D.D.

2005-01-01

The deformation and fracture behavior of soda-lime and borosilicate glass rods was examined during classic and symmetric Taylor impact experiments for impact pressures to 4 and 10 GPa, respectively. High-speed photography and piezoresistive gauges were used to measure the failure front velocities in both glasses, and for impact pressures below ∼2 GPa the failure front velocity increases rapidly with increasing pressure. As the pressure was increased above ∼3 GPa, the failure front velocities asymptotically approached maximum values between the longitudinal and shear wave velocities of each material; at ∼4 GPa, the average failure front velocities were 4.7±0.5 and 4.6±0.5 mm μs -1 for the soda-lime and borosilicate specimens, respectively. The observed mechanism of failure in these experiments involved continuous pressure-dependent nucleation and growth of microcracks behind the incident wave. As the impact pressure was increased, there was a decrease in the time to failure. The density of cracks within the failed region was material dependent, with the more open-structured borosilicate glass showing a larger fracture density

Doping influence by some transition elements on the irradiation effects in nuclear waste glasses; Influence du dopage par certains elements de transition sur les effets d'irradiation dans des verres d'interet nucleaire

Energy Technology Data Exchange (ETDEWEB)

Florent, Olivier

2006-06-15

High-level waste glasses are submitted to auto-irradiation. Modelling it using external irradiations on simple glasses revealed defects production and non negligible structural changes. This thesis aims at determining the impact of a more complex composition on these effects, especially the influence of adding polyvalent transition metals. Silicate, soda-lime and alumino-borosilicate glasses are doped with different iron, chromium and manganese concentrations then {beta} irradiated at different doses up to 10{sup 9} Gy. Non doped glasses show an increase of their density and polymerisation coupled with a molecular oxygen and point defects production. Adding 0.16 mol% Fe decreases the amount of defects by 85 % and all irradiation effects. A Fe{sup 3+} reduction is also observed by EPR, optical absorption and indirectly by Raman spectroscopy. A higher than 0.32 mol% Fe concentration causes complete blockage of the evolution of polymerisation, density and defect production. The same results are obtained on chromium or manganese doped glasses. An original in situ optical absorption device shows the quick decrease of Fe{sup 3+} amount to a 25 % lower level during irradiation. Stopping irradiation causes a lower decrease of 65 %, suggesting a dynamic (h{sup 0}/e-) consuming equilibrium. He{sup +} and Kr{sup 3+} ions and {gamma} irradiated glasses tend to confirm these phenomena for all kind of irradiation with electronic excitations. (author)

Calcium titanium silicate based glass-ceramic for nuclear waste immobilisation

Science.gov (United States)

Sharma, K.; Srivastav, A. P.; Goswami, M.; Krishnan, Madangopal

2018-04-01

Titanate based ceramics (synroc) have been studied for immobilisation of nuclear wastes due to their high radiation and thermal stability. The aim of this study is to synthesis glass-ceramic with stable phases from alumino silicate glass composition and study the loading behavior of actinides in glass-ceramics. The effects of CaO and TiO2 addition on phase evolution and structural properties of alumino silicate based glasses with nominal composition x(10CaO-9TiO2)-y(10Na2O-5 Al2O3-56SiO2-10B2O3); where z = x/y = 1.4-1.8 are reported. The glasses are prepared by melt-quench technique and characterized for thermal and structural properties using DTA and Raman Spectroscopy. Glass transition and peak crystallization temperatures decrease with increase of CaO and TiO2 content, which implies the weakening of glass network and increased tendency of glasses towards crystallization. Sphene (CaTiSiO5) and perovskite (CaTiO3) crystalline phases are confirmed from XRD which are well known stable phase for conditioning of actinides. The microsturcture and elemental analysis indicate the presence of actinide in stable crystalline phases.

Lanthanide-activated Na{sub 5}Gd{sub 9}F{sub 32} nanocrystals precipitated from a borosilicate glass: Phase-separation-controlled crystallization and optical property

Energy Technology Data Exchange (ETDEWEB)

Chen, Daqin, E-mail: dqchen@hdu.edu.cn [College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou 350002 (China); Wan, Zhongyi; Zhou, Yang [College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Chen, Yan, E-mail: chenyan@hdu.edu.cn [College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Yu, Hua; Lu, Hongwei; Ji, Zhenguo [College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018 (China); Huang, Ping, E-mail: phuang@fjirsm.ac.cn [Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou 350002 (China)

2015-03-15

Highlights: • Na{sub 5}Gd{sub 9}F{sub 32} 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 Na{sub 5}Gd{sub 9}F{sub 32} lattice. • Luminescent color could be tuned by controlling glass crystallization temperature. - Abstract: Lanthanide-activated cubic Na{sub 5}Gd{sub 9}F{sub 32} 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 Na{sub 5}Gd{sub 9}F{sub 32} lattice was in situ formed without the requirement of long-range ionic diffusion. Impressively, such fabricated glass ceramic co-doped with Yb{sup 3+}/Er{sup 3+} 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.

White-Beam X-ray Diffraction and Radiography Studies on High-Boron Containing Borosilicate Glass at High Pressures

Science.gov (United States)

Ham, Kathryn; Vohra, Yogesh; Kono, Yoshio; Wereszczak, Andrew; Patel, Parimal

Multi-angle energy-dispersive x-ray diffraction studies and white-beam x-ray radiography were conducted with a cylindrically shaped (1 mm diameter and 0.7 mm high) high-boron content borosilicate glass sample (17.6% B2O3) to a pressure of 13.7 GPa using a Paris-Edinburgh (PE) press at Beamline 16-BM-B, HPCAT of the Advanced Photon Source. The measured structure factor S(q) to large q = 19 Å-1, is used to determine information about the internuclear bond distances between various species of atoms within the glass sample. Sample pressure was determined with gold as a pressure standard. The sample height as measured by radiography showed an overall uniaxial compression of 22.5 % at 13.7 GPa with 10.6% permanent compaction after decompression to ambient conditions. The reduced pair distribution function G(r) was extracted and Si-O, O-O, and Si-Si bond distances were measured as a function of pressure. Raman spectroscopy of pressure recovered sample as compared to starting material showed blue-shift and changes in intensity and widths of Raman bands associated with silicate and B3O6 boroxol rings. US Army Research Office under Grant No. W911NF-15-1-0614.

Durability testing with West Valley borosilicate glass composition- Phase II

International Nuclear Information System (INIS)

Macedo, P.B.; Finger, S.M.; Barkatt, A.A.; Pegg, I.L.; Feng, X.; Freeborn, W.P.

1988-06-01

This report presents the research performed by the Catholic University of America Vitreous State Laboratory (VSL) during FY 1987 in support of the West Valley Demonstration Project (WVDP) nuclear waste vitrification process. A principal objective of this work is the optimization of the glass composition be used for the vitrification of the liquid high-level waste generated at West Valley during nuclear fuel reprocessing. This report discusses (1) the experimental investigations to optimize the reference glass composition (the current leading candidates are WVCM-50 and ATM-10) for the WVDP vitrification process; (2) the systematic experimental investigation performed to determine the effects of compositional variations in WVCM-50 and WV-205 reference glasses on their viscosity and durability (including initial results of long-term leach tests of WVCM-50 under repository conditions); (3) the development of short-time and predictive leach tests; (4) the development of a process model for the West Valley vitrification process which predicts the range of glass compositions which may be encountered during normal operations and the effects of deviations in process control parameters; and (5) the development of product models for predicting the durability and viscosity of nuclear waste glasses

Study of the environment and optical properties of Ti3+ ions formed under ionizing irradiations in oxide glasses

International Nuclear Information System (INIS)

Lombard, Pierre

2009-10-01

We studied by Electron Paramagnetic Resonance (EPR), by EPR simulation, by Raman spectroscopy and by photoluminescence the Ti 3+ ions formed under β-irradiation from 3, 37 * 10 5 to 1, 68 * 10 9 Gy in SiO 2 - Na 2 O - TiO 2 and SiO 2 - Al 2 0 3 - B 2 O 3 - Na 2 O - TiO 2 glasses. We demonstrate the existence of three different Ti 3+ sites in silicate glasses and three other Ti 3+ sites in alumino-borosilicate glasses. One of theses sites is common to both kind of glasses. Moreover, we associate theses sites to three different titanium environment: (VI)Ti 3+ (octahedral), (V)Ti 3+ square pyramid and may be (V)Ti 3+ trigonal bi - pyramid. The existence of theses sites is determined by the total integrated dose and by the [Na]/[Ti] ratio. We propose a definition of this ratio in the special case of SiO 2 - Al 2 O 3 - B 2 O 3 - Na 2 O - TiO 2 glasses. Last, under 266 nm excitation, we observe at room temperature an emission band at 500 nm attributed to Ti 4+ ions. Under a 532 nm excitation, we observe an emission band at 590 nm with a short lifetime (hundred of ns) attributed either to Ti 3+ ions or to an irradiation defect formed near a Ti 4+ ion. Our study demonstrate that is possible to control by the chemical composition and the integrated dose the Ti 3+ environment and the emission properties of this ion in an oxide glass. (author)

Investigation of lead-iron-phosphate glass for SRP waste

International Nuclear Information System (INIS)

Jantzen, C.M.

1986-10-01

The search for a host solid for the immobilization of nuclear waste has focused on various vitreous waste forms. Recently, lead-iron-phosphate (LIP) glasses have been proposed for solidification of all types of HLLW. Investigation of this glass for vitrification of SRP waste demonstrated that the phosphate glass is incompatible with the current borosilicate glass technology. The durability of LIP glasses in deionized water was comparable to current borosilicate waste glass formulations, and the LIP glass has a low melt temperature. However, many of the defense waste constituents have low solubility in the phosphate melt, producing an inhomogeneous product. Also, the LIP melt is highly corrosive which prevents the use of current melter materials, in particular Inconel 690, and thus requires more exotic materials of construction such as platinum

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

International Nuclear Information System (INIS)

Leece, Alicia K.; Heidari, Pedram; Yokell, Daniel L.; Mahmood, Umar

2013-01-01

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 68 Ga-chloride and 68 Ga-DOTATOC ([ 68 Ga] Ga-DOTA-D-Phe1-Tyr3-octreotide) retention in the reaction vial after labeling. Methods: 68 Gallium labeling of DOTATOC was conducted by adding 68 Ga-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 68 Ga-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 (p 68 Ga-chloride. Conclusion: For applications involving the labeling of peptides such as 68 Ga-DOTATOC, the CZ CCS compared to the glass CCS, results in an improved recovery of product. - Highlights: • We examined the adhesion of 68 Ga-DOTATOC to glass and CZ CCS. • The adhesion of the 68 Ga-DOTATOC was 10% less in CZ CCS compared to glass CCS. • Overall recovery of 68 Ga-DOTATOC reaction solution is higher in CZ CCS than glass CCS. • Adhesion to the CCS is due to 68 Ga-DOTATOC, not 68 Ga-chloride

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 (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.

Development Of Glass Matrices For HLW Radioactive Wastes

International Nuclear Information System (INIS)

Jantzen, C.

2010-01-01

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 99 , Cs 137 , and I 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.

Prediction of waste glass melt rates

International Nuclear Information System (INIS)

Lee, L.

1987-01-01

Under contract to the Department of Energy, the Du Pont Company has begun construction of a Defense Waste Processing Facility to immobilize radioactive wastes now stored as liquids at the Department of Energy's Savannah River Plant. The immobilization process solidifies waste sludge by vitrification into a leach-resistant borosilicate glass. Development of this process has been the responsibility of the Savannah River Laboratory. As part of the development, a simple model was developed to predict the melt rates for the waste glass melter. This model is based on an energy balance for the cold cap and gives very good agreement with melt rate data obtained from experimental campaigns in smaller scale waste glass melters

Studies on γ-ray induced structural changes in Nd{sup 3+} doped lead alumino silicate glasses by means of thermoluminescence for dosimetric applications in high dose ranges

Energy Technology Data Exchange (ETDEWEB)

Sundara Rao, M. [Department of Physics, Acharya Nagarjuna University, Nagarjuna Nagar 522 510, Guntur, A.P. (India); Gandhi, Y. [Department of Physics, Kakani Venkata Ratnam College, Nandigama 521 185, A.P. (India); Sanyal, Bhaskar [Food Technology Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Bhargavi, K. [Department of Physics, Acharya Nagarjuna University, Nagarjuna Nagar 522 510, Guntur, A.P. (India); Piasecki, M. [Institute of Physics, J. Dlugosz University, Ul. Armii Krajowej 13/15, 42-201 Czestochowa (Poland); Veeraiah, N., E-mail: nvr8@rediffmail.com [Department of Physics, Acharya Nagarjuna University, Nagarjuna Nagar 522 510, Guntur, A.P. (India)

2014-12-15

Graphical abstract: TL glow curves of PbO–SiO{sub 2}:Nd{sup 3+} glasses mixed with different concentrations of Al{sub 2}O{sub 3} exposed to γ-rays of dose 5.0 kGy. - Highlights: • TL studies of Nd{sup 3+} ions doped lead alumino silicate glasses were carried out. • Highest TL output was observed in the glasses mixed with 10 mol% of Al{sub 2}O{sub 3}. • Different mechanisms responsible for TL emission were discussed. • Near linearity of the dose response was observed in the dose range of 1.0–3.0 kGy. • These glasses may be useful as dosimeters in processing perishable food commodities. - Abstract: Thermoluminescence (TL) studies on PbO–Al{sub 2}O{sub 3}–SiO{sub 2}:Nd{sup 3+} glasses mixed with varying concentrations of Al{sub 2}O{sub 3} exposed to γ-rays of dose in the range 0–5.0 kGy were carried out. The TL emission exhibited a dosimetric peak at about 185 °C. The TL output under the glow peak increased with increasing Al{sub 2}O{sub 3} and also with the γ-ray dose. The mechanisms responsible for TL emission and enhancement of TL output with increase in the concentration of Al{sub 2}O{sub 3} were quantitatively discussed in terms of induced structural defects in the vicinity of Nd{sup 3+} ions due to interaction of γ-rays with the glass network in the scenario of varying concentration of Al{sub 2}O{sub 3}. The dose response of these glass samples exhibited linear behavior in the medium dose range viz., 1.0–3.0 kGy. Finally, it is concluded that the glass containing the highest concentration of Al{sub 2}O{sub 3} exhibits high TL output and such glasses are useful for dosimetry in the range 1.0–3.0 kGy and hence these glasses may be useful for dosimetry in such high range of doses required for commercial radiation processing of perishable food commodities to extend their shelf-lives.

Challenges in commercial manufacture of radiation shielding glasses

International Nuclear Information System (INIS)

Gupta, R.K.

2011-01-01

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

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

International Nuclear Information System (INIS)

Goldschmidt, F.

1991-01-01

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

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)

Glasses and ceramics for immobilisation of radioactive wastes for disposal

International Nuclear Information System (INIS)

Johnson, K.D.B.; Marples, J.A.C.

1979-05-01

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)

Sintering-alkaline processing of borosilicate ores of Tajikistan

International Nuclear Information System (INIS)

Nazarov, F.A.

2018-01-01

The aim of the work is to study the processes of decomposition of boron-containing ore by sintering with NaOH, finding the optimal parameters of the decomposition process, studying the kinetics of processes and developing the technological foundations for ore processing. The processes of borosilicate ore processing were studied by sintering with NaOH. Possible mechanisms of chemical reactions of the process of sintering-alkaline decomposition of boron-containing ore are established, the results of which are substantiated by physicochemical methods of analysis. A principal technological scheme for processing of borosilicate ores by a sintering-alkaline method has been developed. In the first chapter, data on alkaline and caking processes for processing boron-containing and aluminium comprising raw materials are available in the literature. Based on this, the directions of our own research are outlined. The second chapter is devoted to the study of the chemical and mineralogical compositions of borosilicate ores and their concentrates with the help of X-ray phase and chemical analysis methods, the stoichiometric calculation of the formation of aluminum, iron, and boron salts has been carried out, and a thermodynamic analysis of the processes of sintering borosilicate ores with alkali has been considered. The third chapter presents the results of a study of sintering-alkaline method of processing of initial borosilicate ore of the Ak-Arkhar Deposit and its concentrate without calcination and after calcination. The kinetics of sintering of borosilicate ores with sodium hydroxide was studied. The optimal conditions of borosilicate ore sintering before and after the preliminary calcination with alkali were determined. Optimal parameters of the sintering process have been found: sintering temperature 800-8500 deg C, duration of the process - 60 minutes, mass ratio of NaOH to raw materials 2: 1. The conditions for sintering of borosilicate concentrate with alkali have been

Properties of sodium borosilicate glasses/Al2O3 sintered composites containing fluorides. Gan Fukkabutsu hokei san natoriumu garasu to alumina fukugo shoketsutai no bussei

Energy Technology Data Exchange (ETDEWEB)

Ryu, Bonggi; Yasui, I [The Univ. of Tokyo, Tokyo (Japan). Inst. of Industrial Science

1993-06-01

Glass/alumina sintered composites were synthesized from sodium borosilicate glass powder containing fluorides like AlF3 and NaF3, and Al2O3, and change in material properties was examined. Glass compositions of B2O3 and Na2O greatly affected the crystal phase and material properties. Nephelin crystal phase was extracted by the reaction of Na2O, NaF2, SiO2 and Al2O3 when B/Na<1. Coefficient of thermal expansion increased with the increase of Na/Si ratio. The residual amount of fluorides of sintered materials in nitrogen atmosphere was higher than that of air, and differed with the type of fluoride. The F[sup -] of NaF is bonded with Si of glass network and forms quiet stable glass structure, whereas, F[sup -] of AlF3 reacts with Si[sup 4+] forming SiF4 which is vaporized. Sintering temperature and dielectric constant of sintered materials containing fluoride was lower than the sintered materials without fluorides addition, however, at a sintering temperature range of 100 to 150[degree]C, it was inferred that this was because of the increase in voids due to SiF4 formed in the reaction. 16 refs., 17 figs., 3 tabs.

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.

Baseline Glass Development for Combined Fission Products Waste Streams

International Nuclear Information System (INIS)

Crum, Jarrod V.; Billings, Amanda Y.; Lang, Jesse B.; Marra, James C.; Rodriguez, Carmen P.; Ryan, Joseph V.; Vienna, John D.

2009-01-01

Borosilicate glass was selected as the baseline technology for immobilization of the Cs/Sr/Ba/Rb (Cs), lanthanide (Ln) and transition metal fission product (TM) waste steams as part of a cost benefit analysis study.(1) Vitrification of the combined waste streams have several advantages, minimization of the number of waste forms, a proven technology, and similarity to waste forms currently accepted for repository disposal. A joint study was undertaken by Pacific Northwest National Laboratory (PNNL) and Savannah River National Laboratory (SRNL) to develop acceptable glasses for the combined Cs + Ln + TM waste streams (Option 1) and Cs + Ln combined waste streams (Option 2) generated by the AFCI UREX+ set of processes. This study is aimed to develop baseline glasses for both combined waste stream options and identify key waste components and their impact on waste loading. The elemental compositions of the four-corners study were used along with the available separations data to determine the effect of burnup, decay, and separations variability on estimated waste stream compositions.(2-5) Two different components/scenarios were identified that could limit waste loading of the combined Cs + LN + TM waste streams, where as the combined Cs + LN waste stream has no single component that is perceived to limit waste loading. Combined Cs + LN waste stream in a glass waste form will most likely be limited by heat due to the high activity of Cs and Sr isotopes.

Aqueous solutions/nuclear glasses interactions

International Nuclear Information System (INIS)

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

1991-01-01

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

Radionuclides containment in nuclear glasses. An overview

Energy Technology Data Exchange (ETDEWEB)

Gin, Stephane; Jollivet, Patrick; Tribet, Magaly; Peuget, Sylvain; Schuller, Sophie [CEA Marcoule, Bagnols-sur-Ceze (France). DE2D SEVT

2017-07-01

Radioactive waste vitrification has been carried out industrially in several countries for nearly 40 years. Research into the formulation and long term behavior of high and intermediate level waste glasses, mainly borosilicate compositions, is still continuing in order to (i) safely condition new types of wastes and (ii) design and demonstrate the safety of the disposal of these long-lived waste forms in a deep geological repository. This article presents a summary of current knowledge on the formulation, irradiation resistance and the chemical durability of these conditioning materials, with a special focus on the fate of radionuclides during glass processing and aging. It is shown that, apart from the situation for certain elements with very low incorporation rate in glass matrices, vitrification in borosilicate glass can enable waste loadings of up to ∝20 wt% while maintaining the glass homogeneity for geological time scales and guaranteeing a high stability level in spite of irradiation and water contact.

Energy transfer processes in Yb{sup 3+}-Tm{sup 3+} co-doped sodium alumino-phosphate glasses with improved 1.8 {mu}m emission

Energy Technology Data Exchange (ETDEWEB)

Camargo, Andrea S S de; Terra, Idelma A A; Nunes, Luiz Antonio de O; Li, M Siu [Instituto de Fisica de Sao Carlos, Universidade de Sao Paulo, 13560-970, Sao Carlos-SP (Brazil)], E-mail: andreasc@ifsc.usp.br

2008-06-25

Sodium alumino-phosphate glasses co-doped with Yb{sup 3+} and Tm{sup 3+} ions have been prepared with notably low OH{sup -} content, and characterized from the viewpoint of their spectroscopic properties. In these glasses, Yb{sup 3+} acts as an efficient sensitizer of excitation energy at 0.98 {mu}m-which can be provided by high power and low cost diode lasers, and subsequently undergoes non-resonant energy transfer to Tm{sup 3+} ions ({sup 2}F{sub 5/2}, {sup 3}H{sub 6} {yields} {sup 2}F{sub 7/2}, {sup 3}H{sub 5}). Through this process, the emitting level {sup 3}F{sub 4} is rapidly populated, generating improved emission at 1.8 {mu}m ({sup 3}F{sub 4} {yields} {sup 3}H{sub 6}). In order to guarantee the efficiency of such favorable energy transfer, energy losses via multiphonon decay, Yb-Yb radiative trapping, and non-radiative transfer to OH{sup -} groups were evaluated, and minimized when possible. The dipole-dipole energy transfer microscopic parameters corresponding to Yb{sup 3+} {yields} Tm{sup 3+}, Yb{sup 3+} {yields} Yb{sup 3+} and Tm{sup 3+} {yields} Tm{sup 3+} transfers, calculated by the Foerster-Dexter model, are C{sub Yb-Tm} = 2.9 x 10{sup -40} cm{sup 6} s{sup -1}, C{sub Yb-Yb} = 42 x 10{sup -40} cm{sup 6} s{sup -1} and C{sub Tm-Tm} = 43 x 10{sup -40} cm{sup 6} s{sup -1}, respectively.

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}.

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)

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

Science.gov (United States)

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

2018-01-01

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

Formation enthalpy of alkali-borosilicate glass

International Nuclear Information System (INIS)

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

1991-01-01

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

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

International Nuclear Information System (INIS)

Johnson, K.D.B.

1979-01-01

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

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

Plutonium Solubility In High-Level Waste Alkali Borosilicate Glass

International Nuclear Information System (INIS)

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

2011-01-01

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 ∼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 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 3 3 of glass or about 600 g Pu/canister). Based on historical process throughput data, this level was considered to represent a reasonable upper bound for Pu loading based on the ability to provide Pu containing feed to the DWPF. The task elements included evaluating the distribution of Pu in the glass (e.g. homogeneity), evaluating crystallization within the glass, evaluating select glass properties (with surrogates), and evaluating durability using the Product Consistency Test -- Method A (PCT-A). The behavior of Pu in the melter was evaluated using paper studies and corresponding analyses of DWPF melter pour samples.The results of the testing indicated that at 1 wt % Pu in the glass, the Pu was homogeneously distributed and did not result in any formation of plutonium-containing crystalline phases as long as the glass was prepared under 'well-mixed' conditions. The incorporation of 1 wt

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

International Nuclear Information System (INIS)

Linard, Y.; Advocat, Th.

2000-01-01

No fundamental thermodynamic data, such as the entropy Δ f S T) and enthalpy Δ f H 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 B 2 O 3 -SiO 2 --Na 2 O (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: Al 2 O 3 , CaO, ZrO 2 , Ce 2 O 3 , Li 2 O and Fe 2 O 3 , and non-radioactive surrogate fission product oxides. - A second using another BSN ternary glass to which Al 2 O 3 , 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 Δ f S T) and Δ f S 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 S conf (T g ) 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

Limiting of photo induced changes in amorphous chalcogenide/alumino-silicate nanomultilayers

International Nuclear Information System (INIS)

Charnovych, S.; Nemec, P.; Nazabal, V.; Csik, A.; Allix, M.; Matzen, G.; Kokenyesi, S.

2011-01-01

Highlights: → Amorphous chalcogenides were investigated in this work. → Photo-induced effects were investigated in the created thin films. → Limiting of photo induced changes in amorphous chalcogenide/alumino-silicate nanomultilayers have been studied. - Abstract: Photo induced changes in amorphous As 20 Se 80 /alumino-silicate nanomultilayers (NML) produced by pulsed laser deposition (PLD) method have been studied in this work. The aim was to investigate the photo induced optical and surface relief changes due to the band gap illumination under the size- and hard cover limited conditions. It was observed that the hard cover layer on the surface of the uniform film or alumino-silicate sub-layers in the NML structure influences the photo darkening and restricts surface relief formations in As 20 Se 80 film or in the related NML compared with this effect in a pure chalcogenide layer. The influence of hard layers is supposed to be connected with limiting the free volume formation at the initial stage of the transformation process, which in turn limits the atomic movement and so the surface relief formation.

Standard specification for beaded process glass pipe and fittings

CERN Document Server

American Society for Testing and Materials. Philadelphia

2002-01-01

1.1 This specification covers chemically resistant, low expansion Type-I borosilicate glass, Class A, (see Specification E 438) used to manufacture beaded end flanged-glass pipe and fittings for pressure and vacuum applications.

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.

Theoretical predictions for glass flow into an evacuated canister

International Nuclear Information System (INIS)

Routt, K.R.; Crow, K.R.

1983-01-01

Radioactive waste currently stored at the Savannah River Plant in liquid form is to be immobilized by incorporating it into a borosilicate glass. The glass melter for this process will consist of a refractory lined, steel vessel operated at a glass temperature of 1150 0 C. At the end of a two-year projected melter lifetime, the glass inside the melter is to be drained prior to disposition of the melter vessel. One proposed technique for accomplishing this drainage is by sucking the glass into an evacuated canister. The theoretical bases for design of an evacuated canister for draining a glass melter have been developed and tested. The theoretical equations governing transient and steady-state flow were substantiated with both a silicone glass simulant and molten glass

Influence of iron ions on the structural properties of some inorganic glasses

International Nuclear Information System (INIS)

Music, S.; Gotic, M.; Popovic, S.; Grzeta, B.

1987-01-01

The effects of iron on the structural properties of Zn-borosilicate glass and Pb-metaphosphate glass were studied using x-ray diffraction, 57 Fe Moessbauer spectroscopy and IR spectroscopy. At high concentration of iron the crystallization of zinc ferrite in the glass matrix takes place. X-ray diffraction and 57 Fe Moessbauer spectroscopy showed that the amount of zinc ferrite in Zn-borosilicate glass decreases. In Pb-metaphosphate glass doped with high concentration of α-Fe 2 O 3 , the crystallization of Fe 3 (PO 4 ) 2 is pronounced. The assignments of IR band positions and the corresponding interpretation are given. The importance of this study for the technology of vitrification of high-level radioactive wastes is emphasized. (author) 31 refs.; 6 figs,.; 6 tabs

Physical and chemical characterization of borosilicate glasses containing Hanford high-level wastes

International Nuclear Information System (INIS)

Kupfer, M.J.; Palmer, R.A.

1980-10-01

Scouting studies are being performed to develop and evaluate silicate glass forms for immobilization of Hanford high-level wastes. Detailed knowledge of the physical and chemical properties of these glasses is required to assess their suitability for long-term storage or disposal. Some key properties to be considered in selecting a glass waste form include leach resistance, resistance to radiation, microstructure (includes devitrification behavior or crystallinity), homogeneity, viscosity, electrical resistivity, mechanical ruggedness, thermal expansion, thermal conductivity, density, softening point, annealing point, strain point, glass transformation temperature, and refractive index. Other properties that are important during processing of the glass include volatilization of glass and waste components, and corrosivity of the glass on melter components. Experimental procedures used to characterize silicate waste glass forms and typical properties of selected glass compositions containing simulated Hanford sludge and residual liquid wastes are presented. A discussion of the significance and use of each measured property is also presented

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

International Nuclear Information System (INIS)

Delorme, L.

1998-01-01

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 SiO 2 -B 2 O 3 -Al 2 O 3 -αNa 2 O-(1-alpha)Li 2 O-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 B III and B IV sites near 700 deg.C, and the change of coordination number B IV- B III 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 NaBO 2 (g), LiBO 2 (g) and Na 2 (BO 2 )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 Na 2 O and Li 2 O, which maintains the total vapor pressure on a quasi-constant lever up to α=0.27. (author)

Introduction - Acid decomposition of borosilicate ores

International Nuclear Information System (INIS)

Mirsaidov, U.M.; Kurbonov, A.S.; Mamatov, E.D.

2015-01-01

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.

Characterization of damage created by alpha disintegrations in radionuclear waste glass

International Nuclear Information System (INIS)

Jacquet-Francillon, N.; Mueller, P.

1990-01-01

Study of thermostimulated luminescence of an alpha irradiated glass used as radionuclear waste glass has revealed the formation of a structural defect induced by alpha irradiation. To detect this structural modification the thermostimulated signal of an alpha irradiated sample is recorded under certain conditions. The nature of generated defects has been established using synthetic glasses of more simple composition such as silica or boro-silicate glasses. Results obtained with these simple glasses are transposed to alpha irradiated radionuclear waste glass. The problem is to see how autoirradiated glass could evolve in time. For this purpose actinide-doped glasses are now being fabricated and specific thermostimulated luminescence equipment has been developed for this purpose

Assessment of methods for immobilizing reprocessed radioactive waste

Science.gov (United States)

Murthy, M. K.; Baranyi, A. D.

1980-05-01

Nuclear waste forms presently used for the disposal of high level wastes and other potential waste forms under development were studied. The following waste forms were considered: Borosilicate glass, high silica glass, glassceramics, supercalcine ceramics, synroc ceramics, borosilicate glass beads in a metal matrix, supercalcine and synroc ceramics in a metal matrix and coated ceramics. The best developed wasteform, both in terms of overall product quality and process development, is monolithic borosilicate glass. However, hydrothermal instability is a major concern. Borosilicate glass in metal matrix waste form has better properties than monolithic borosilicate glass waste form. The process was proven on a pilot scale. Hence, it is considered very close to monolithic glass in terms of overall development. The product qualities of the other waste forms are better than borosilicate glass. However, process development for these alternative waste forms is still in a conceptual stage.

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

Fabrication of Silicon Nitride Dental Core Ceramics with Borosilicate Veneering material

International Nuclear Information System (INIS)

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

2011-01-01

Silicon nitride (Si 3 N 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 3 N 4 ceramic as a dental core material. The white Si 3 N 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 3 N 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 3 N 4 specimens represented the synthetic dental core were paintbrush coated by a veneer paste composed of borosilicate glass powder ( 2 O 3 - partial stabilized zirconia) and 30 wt% of polyvinyl alcohol (5 wt% solution). After coating the veneer on the Si 3 N 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 -6 deg. 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.

Phase separation in an ionomer glass

DEFF Research Database (Denmark)

Pedersen, Malene Thostrup; Tian, K.V.; Dobó-Nagy, C.

2015-01-01

The G338 ionomer glass is a fluoro-alumino-silicate system, which is used as the powder component of glass ionomer cements (GICs) in dental applications. However, despite progress in understanding the nature of this glass, chemical identity of its separated amorphous phases has not yet been...... amorphous phases in G388 are Ca/Na-Al-Si-O, Ca-Al-F and Ca-P-O-F phases, respectively. However, the exact chemical compositions of the three phases still require further exploration. The results of this work are important for understanding the impact of phase separation within ionomer glasses on the setting...... conclusively determined. In this work, we identify these phases by performing differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses on both the as-received glass and heat-treated samples. We detected three glass transitions in the as-received G338 glass during DSC upscaning, implying...

Separation of Th and U using borosilicate glasses

International Nuclear Information System (INIS)

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

2010-01-01

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

The effects of sulfate content on crystalline phase, microstructure, and chemical durability of zirconolite−barium borosilicate glass-ceramics

Energy Technology Data Exchange (ETDEWEB)

Wu, Lang, E-mail: lang.wu@163.com [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Wang, Xin; Li, Huidong; Teng, Yuancheng [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Peng, Long [Sichuan Province Key Laboratory of Information Materials and Devices Application, Chengdu University of Information Technology, Chengdu 610225 (China)

2016-09-15

The effects of sulfate content on structure and chemical durability of barium borosilicate glass-ceramics were studied. The results show that the glass-ceramics with 0–1.10 mol% SO{sub 3} possess mainly CaZrTi{sub 2}O{sub 7}-2M phase along with a small amount of CaZrTi{sub 2}O{sub 7}-3T and ZrO{sub 2} phases. The hexagonal CaZrTi{sub 2}O{sub 7}-3T crystals crystallize on the surface of glass-ceramics. For the samples with 1.24–1.55 mol% SO{sub 3}, the main crystalline phases are CaTiSiO{sub 5} and CaZrTi{sub 2}O{sub 7}-2M in the bulk, while a separate sulfate layer containing Na{sub 2}SO{sub 4} and BaSO{sub 4} is observed on the surface. X-ray fluorescence analysis indicates that about 2/3 of the SO{sub 3} originally added has been lost by volatility. The normalized mass loss (NL{sub i}) for Na, B, Ca elements remains almost unchanged (∼10{sup −2} g/m{sup 2}) after 7 days for the samples with 0–1.10 mol% SO{sub 3}. The NL{sub i} for both Na and B increases gradually after 7 days when the SO{sub 3} content is 1.24 mol%. - Highlights: • Strip-shaped CaZrTi{sub 2}O{sub 7}-2M and plate-like CaTiSiO{sub 5} crystals crystallize in the bulk. • CaZrTi{sub 2}O{sub 7}-3T crystals crystallize on the surface for samples with 0–1.10 mol% SO{sub 3}. • A separate sulfate layer crystallizes on the surface when SO{sub 3} exceeds solubility.

Leaching TC-99 from DWPF glass in simulated geologic repository groundwaters

International Nuclear Information System (INIS)

Bibler, N.E.; Jurgensen, A.R.

1986-01-01

The purpose was to determine if DWPF glass in geologic groundwaters would immobilize Tc-99 as well as it does other elements. A previous study (using a borosilicate glass of a very different composition from DWPF glass) indicated that Tc-99 leached rapidly from the glass suggesting that glass may not be a good matrix for immobilizing Tc-99. It was suggested that the Tc-99 had migrated to vesicles in the glass while the glass was still molten. To determine if borosilicate glass was a good immobilizing matrix for Tc-99, this study was performed using DWPF glass. The leaching of Tc-99 was compared to other elements in the glass. It was shown that rapid leaching will not occur with SRP glass. The leach rate for Tc-99 was nearly identical to that for B, a matrix element in the glass. Another objective was to compare the release of Tc-99 under oxidizing and reducing conditions with other elements in the glass. In the tests described here, even though the glass was dissolving more under reducing conditions as a result of abnormally high pH values, less Tc-99 appeared in solution

Synthesis, electrical and magnetic properties of sodium borosilicate glasses containing Co-ferrites nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Othman, H.A. [Department of Physics, Faculty of Science, Menoufia University, Shibin El-Kom 32511, Menoufia (Egypt); Eltabey, M.M. [Department of Basic Engineering Science, Faculty of Engineering, Menoufia University, Shibin El-Kom, Menoufia (Egypt); Department of Physics, Faculty of Science, Jazan University (Saudi Arabia); Ibrahim, Samia E.; El-Deen, L.M. Sharaf; Elkholy, M.M. [Department of Physics, Faculty of Science, Menoufia University, Shibin El-Kom 32511, Menoufia (Egypt)

2017-02-01

Co-ferrites nanoparticles that have been prepared by the co-precipitation method were added to sodium borosilicate (Na{sub 2}O–B{sub 2}O{sub 3}–SiO{sub 2}) glass matrix by the solid solution method and they were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and magnetization measurements. (XRD) revealed the formation of the Co-ferrite magnetic crystalline phase embedded in an amorphous matrix in all the samples. The investigated samples by (TEM) showed the formation of the cobalt ferrite nanoparticles with a spherical shape and highly monodispersed with an average size about 13 nm. IR data revealed that the BO{sub 3} and BO{sub 4} are the main structural units of these samples network. IR spectra of the investigated samples showed the characteristic vibration bands of Co-ferrite. Composition and frequency dependent dielectric properties of the prepared samples were measured at room temperature in the frequency range 100–100 kHz. The conductivity was found to increase with increasing cobalt ferrite content. The variations of conductivity and dielectric properties with frequency and composition were discussed. Magnetic hysteresis loops were traced at room temperature using VSM and values of saturation magnetization M{sub S} and coercive field H{sub C} were determined. The obtained results revealed that a ferrimagnetic behavior were observed and as Co-ferrite concentration increases the values of M{sub S} and H{sub C} increase from 2.84 to 8.79 (emu/g) and from 88.4 to 736.3 Oe, respectively.

Benefits and drawbacks of zinc in glass ionomer bone cements

International Nuclear Information System (INIS)

Brauer, Delia S; Hill, Robert G; Gentleman, Eileen; Stevens, Molly M; Farrar, David F

2011-01-01

Glass polyalkenoate (ionomer) cements (GPCs) based on poly(acrylic acid) and fluoro-alumino-silicate glasses are successfully used in a variety of orthopaedic and dental applications; however, they release small amounts of aluminium, which is a neurotoxin and inhibits bone mineralization in vivo. Therefore there has been significant interest in developing aluminium-free glasses containing zinc for forming GPCs because zinc can play a similar structural role in the glass, allowing for glass degradation and subsequent cement setting, and is reported to have beneficial effects on bone formation. We created zinc-containing GPCs and characterized their mechanical properties and biocompatibility. Zinc-containing cements showed adhesion to bone close to 1 MPa, which was significantly greater than that of zinc-free cements ( 2+ or more resulted in cell death. In summary, we demonstrate that while zinc-containing GPCs possess excellent mechanical properties, they fail basic biocompatibility tests, produce an acute cytotoxic response in vitro, which may preclude their use in vivo.

Structure and properties of alumino-boro-silicate glasses and melts

Science.gov (United States)

neuville, D. R.; Florian, P.; Cadars, S.; Massiot, D.

2012-12-01

The relationship between physical properties and structure of glasses and melts in the system MO-T2O3-SiO2 (with M= Na2, Ca and T= Al, B) are technologically and geologically important, in particular to understand the microscopic origin of the configurational thermodynamic properties. The connection of these network former is fundamental to understand the physical properties of magmatic liquids. The configurational properties of melts and glasses provide fundamental information needed to characterize magmatic processes. A principal difficulty, however is to link the "macroscopic" configurational entropy with the structure of melts. This has been done by combining viscometry with Raman and NMR spectroscopy studies. From the viscosity measurements at low and high temperatures, we have obtained the configurational entropy, Sconf (log η = Ae + Be/TSconf, were η is the viscosity, T the temperature and Ae, Be two constants). Silicon, aluminum, and boron are 3 network formers playing different role on the silicate network, whereas Si is the strongest network former in coordination 4, 5 or 6 as a function of T, P; Al can play different function as a network former in 4- or 5-fold coordination and probably as a network modifier in 6 fold coordination. Boron observed in 3 or 4 fold coordination is always a network former but for very "fragile" glasses. For the glass the Al/B substitution produce a small decrease of the molar volume while this substitution produced a strong decrease of viscosity and glass transition temperature while the fragility of the network is less affected by this chemical change. Raman spectra show significant change in the D1 and D2 bands. NMR spectroscopies show also significant change as a function of chemical change and temperature. All this observations will be discussed and interpreted in order to link microscopic versus macroscopic changes.

Effect of Gd2O3 doping on structure and boron volatility of borosilicate glass sealants in solid oxide fuel cells-A study on the La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode

Science.gov (United States)

Zhang, Qi; Tan, Shengwei; Ren, Mengyuan; Yang, Hsiwen; Tang, Dian; Chen, Kongfa; Zhang, Teng; Jiang, San Ping

2018-04-01

Boron volatility is one of the most important properties of borosilicate-based glass sealants in solid oxide fuel cells (SOFCs), as boron contaminants react with lanthanum-containing cathodes, forming LaBO3 and degrading the activity of SOFCs. Here, we report that the reaction between the volatile boron and a La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode during polarization can be significantly reduced by doping aluminoborosilicate glass with Gd2O3. Specifically, the Gd cations in glass with 2 mol.% Gd2O3 dissolve preferentially in the borate-rich environment to form more Gd-metaborate structures and promote the formation of calcium metaborate (CaB2O4); they also condense the B-O network after heat treatment, which suppresses poisoning by boron contaminants on the LSCF cathode. The results provide insights into design and development of a reliable sealing glass for SOFC applications.

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

Energy Technology Data Exchange (ETDEWEB)

Sonavane, M S; Mishra, P.K., E-mail: maheshss@barc.gov.in [Nuclear Recycle Board, Bhabha Atomic Research Centre, Mumbai (India); Mandal, S; Barik, S; Roy Chowdhury, A; Sen, R [Central Glass and Ceramic Institute, Kolkata (India)

2012-10-15

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)

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)

Sonavane, M.S.; Mishra, P.K.; Mandal, S.; Barik, S.; Roy Chowdhury, A.; Sen, R.

2012-01-01

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)

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

International Nuclear Information System (INIS)

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

1996-01-01

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

A statistically designed matrix to evaluate solubility, impurity tolerance, and thermal stability of plutonium-bearing glasses

International Nuclear Information System (INIS)

Peeler, D.K.; Meaker, T.F.; Edwards, T.B.; McIntyre, D.S.

1997-01-01

In support of the Department of Energy's (DOE) Office of Fissile Material Disposition (OFDM) Program, Westinghouse Savannah River Company (WSRC) is evaluating a unique lanthanide borosilicate glass to immobilize excess plutonium and other heavy metals. The lanthanide borosilicate (LaBS) glass system met all FY96 programmatic planning objectives. Those objectives were focused on (1) demonstrating 10 wt% Pu solubility, and (2) meeting preliminary product performance criteria. Although 10 wt% Pu solubility was demonstrated with product performance exceeding high level waste glasses based on PCT results, the LaBS system was not optimized

Sulphate solubility and sulphate diffusion in oxide glasses: implications for the containment of sulphate-bearing nuclear wastes

International Nuclear Information System (INIS)

Lenoir, M.

2009-09-01

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 SiO 2 -B 2 O 3 -R 2 O (R = Li, Na, K, Cs), SiO 2 -B 2 O 3 -BaO and V 2 O 5 -B 2 O 3 -BaO systems. These compositions allowed us to study the influence of the nature of network-modifying ions (Li + , Na + , K + , Cs + or Ba 2+ ) 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)

Savannah River Laboratory's operating experience with glass melters

International Nuclear Information System (INIS)

Brown, F.H.; Randall, C.T.; Cosper, M.B.; Moseley, J.P.

1982-01-01

The Department of Energy, with recommendations from the Du Pont Company, is proposing that a Defense Waste Processing Facility be constructed at the Savannah River Plant to immobilize radioactive The immobilization process is designed around the solidification of waste sludge in borosilicate glass. The Savannah River Laboratory, who is responsible for the solidification process development program, has completed an experimental program with one large-scale glass melter and just started up another melter. Experimental data indicate that process requirements can easily be met with the current design. 7 figures

Thermokinetic model of borosilicate glass dissolution: contextual affinity

International Nuclear Information System (INIS)

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

1989-01-01

Short and long-term geochemical interactions of R7T7 nuclear glass with water at 100 0 C were simulated with the DISSOL thermokinetic computer code. Both the dissolved glass quantity and the resulting water composition, saturation states and mineral quantities produced were calculated as a function of time. The rate equation used in the simulation was first proposed by Aagaard and Helgeson. It simulates a gradually diminishing dissolution rate as the reaction affinity diminishes. The best agreement with 1-year experimental data was obtained with a reaction affinity calculated from silica activity (Grambow's hypothesis) rather than taking into account the activity of all the glass components as proposed by Jantzen and Plodinec. The concept of residual affinity was introduced by Grambow to express the fact that the glass dissolution rate does not cease. We prefer to replace the term residual affinity by contextual affinity, which expresses the influence on the dissolution rate of three factors: the solution chemistry, the metastability of SiO 2 (m), and the possible precipitation of certain aluminosilicates such as zeolites. 19 refs

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

International Nuclear Information System (INIS)

Tait, J.C.

1993-05-01

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

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

Science.gov (United States)

Boatner, Lynn A.; Sales, Brian C.

1989-01-01

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

Thermokinetic model of borosilicate glass dissolution: Contextual affinity

International Nuclear Information System (INIS)

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

1990-01-01

Short and long-term geochemical interactions of R7T7 nuclear glass with water at 100C were simulated with the DISSOL thermokinetic computer code. Both the dissolved glass quantity and the resulting water composition, saturation states and mineral quantities produced were calculated as a function of time. The rate equation used in the simulation was first proposed by Aagaard and Hegelson: v = k + · S · a( H + ) -n · (1 - e -(A/RT) ). It simulates a gradually diminishing dissolution rate as the reaction affinity diminishes. The best agreement with 1-year experimental data was obtained with a reaction affinity calculated from silica activity (Grambow's hypothesis) rather than taking into account the activity of all the glass components as proposed by Jantzen and Plodinec. The concept of residual affinity was introduced by Grambow to express the fact that the glass dissolution rate does not cease. The authors prefer to replace the term residual affinity by contextual affinity, which expresses the influence on the dissolution rate of three factors: the solution chemistry, the metastability of SiO 2 (m), and the possible precipitation of certain aluminosilicates such as zeolites

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

International Nuclear Information System (INIS)

Aegerter, M.A.; Santos, D.I. dos; Ventura, P.C.S.

1984-01-01

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 Na 2 O - B 2 O 3 - SiO 2 . 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.) [pt

Ceramics and glasses for radioactive waste storage

International Nuclear Information System (INIS)

Baudin, G.

1984-06-01

Borosilicate glasses are mainly choosen for the confinement of fission products; industrial plants are either in operation (AVM) or in construction. Studies of ceramics as a matrix haven't received real application [fr

Electrical resistivities of glass melts containing simulated SRP waste sludges

International Nuclear Information System (INIS)

Wiley, J.R.

1978-08-01

One option for the long-term management of radioactive waste at the Savannah River Plant is to solidify the waste in borosilicate glass by using a continuous, joule-heated, ceramic melter. Electrical resistivities that are needed for melter design were measured for melts of two borosilicate, glass-forming mixtures, each of which was combined with various amounts of several simulated-waste sludges. The simulated sludge spanned the composition range of actual sludges sampled from SRP waste tanks. Resistivities ranged from 6 to 10 ohm-cm at 500 0 C. Melt composition and temperature were correlated with resistivity. Resistivity was not a simple function of viscosity. 15 figures, 4 tables

Solidification of HLLW by glass-ceramic process

International Nuclear Information System (INIS)

Oguino, N.; Masuda, S.; Tsunoda, N.; Yamanaka, T.; Ninomiya, M.; Sakane, T.; Nakamura, S.; Kawamura, S.

1979-01-01

The compositions of glass-ceramics for the solidification of HLLW were studied, and the glass-ceramics in the diopside system was concluded to be the most suitable. Compared with the properties of HLW borosilicate glasses, those of diopside glass-ceramic were thought to be almost equal in leach rate and superior in thermal stability and mechanical strength. It was also found that the glass in this system can be crystallized simply by pouring it into a thermally insulated canister and then allowing it to cool to room temperature. 2 figures, 5 tables

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

Energy Technology Data Exchange (ETDEWEB)

Tait, J C

1993-05-01

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

Development and evaluation of candidate high-level waste forms

International Nuclear Information System (INIS)

Bernadzikowski, T.A.

1981-01-01

Some seventeen candidate waste forms have been investigated under US Department of Energy programs as potential media for the immobilization and geologic disposal of the high-level radioactive wastes (HLW) resulting from chemical processing of nuclear reactor fuels and targets. Two of these HLW forms were selected at the end of fiscal year (FY) 1981 for intensive development if FY 1982 to 1983. Borosilicate glass was continued as the reference form. A crystalline ceramic waste form, SYNROC, was selected for further product formulation and process development as the alternative to borosilicate glass. This paper describes the bases on which this decision was made

ION EXCHANGE IN GLASS-CERAMICS

Directory of Open Access Journals (Sweden)

George Halsey Beall

2016-08-01

Full Text Available In the past few years ion-exchange in glasses has found a renewed interest with a lot of new development and research in industrial and academic labs and the commercialization of materials with outstanding mechanical properties. These glasses are now widely used in many electronic devices including hand-held displays and tablets. The exchange is generally conducted in a bath of molten salt below the transition temperature of the glass. The exchange at the surface of an alkali ion by a bigger one brings compressive stress at the surface. The mechanical properties are dependent on the stress level at the surface and the depth of penetration of the bigger ion. As compared to glasses, glass-ceramics have the interest to display a wide range of aspects (transparent to opaque and different mechanical properties (especially higher modulus and toughness. There has been little research on ion-exchange in glass-ceramics. In these materials the mechanisms are much more complex than in glasses because of their polyphasic nature: ion-exchange generally takes place mostly in one phase (crystalline phase or residual glass. The mechanism can be similar to what is observed in glasses with the replacement of an ion by another in the structure. But in some cases this ion-exchange leads to microstructural modifications (for example amorphisation or phase change.This article reviews these ion-exchange mechanisms using several transparent and opaque alumino-silicate glass-ceramics as examples. The effect of the ion exchange in the various glass-ceramics will be described, with particular emphasis on flexural strength.

On fluidization of borosilicate glasses in intense radiation fields - 16055

International Nuclear Information System (INIS)

Ojovan, Michael; Moebus, Guenter; Tsai, Jim; Cook, Stuart; Yang, Guang

2009-01-01

The viscosity is rate-limiting for many processes in glassy materials such as homogenisation and crystallisation. Changes in the viscous flow behaviour in conditions of long-term irradiation are of particular interest for glassy materials used in nuclear installations as well as for nuclear waste immobilising glasses. We analyse the viscous flow behaviour of oxide amorphous materials in conditions of electron-irradiation using the congruent bond lattice model of oxide materials accounting for the flow-mediating role of broken bonds termed configurons. An explicit equation of viscosity was obtained which is in agreement with experimental data for non-irradiated glasses and shows for irradiated glasses, first, a significant decrease of viscosity, and, second, a stepwise reduction of the activation energy of flow. An equation for glass-transition temperature was derived which shows that irradiated glasses have lower glass transition temperatures. Intensive electron irradiation of glasses causes their fluidization due to non-thermal bond breaking and can occur below the glass transition temperature. Due to surface tension forces fluidization of glasses at enough high electron flux densities can result in modification of nano-size volumes and particles such as those experimentally observed under TEM electron beams. (authors)

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)

Effects of beta/gamma radiation on nuclear waste glasses

International Nuclear Information System (INIS)

Weber, W.J.

1997-01-01

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 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)

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

International Nuclear Information System (INIS)

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

1983-05-01

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

Test Summary Report Vitrification Demonstration of an Optimized Hanford C-106/AY-102 Waste-Glass Formulation

International Nuclear Information System (INIS)

Goles, Ronald W.; Buchmiller, William C.; Hymas, Charles R.; MacIsaac, Brett D.

2002-01-01

In order to further the goal of optimizing Hanford?s HLW borosilicate flowsheet, a glass formulation effort was launched to develop an advanced high-capacity waste form exhibiting acceptable leach and crystal formation characteristics. A simulated C-106/AY-102 waste envelop inclusive of LAW pretreatment products was chosen as the subject of these nonradioactive optimization efforts. To evaluate this optimized borosilicate waste formulation under continuous dynamic vitrification conditions, a research-scale Joule-heated ceramic melter was used to demonstrate the advanced waste form?s flowsheet. The main objectives of this melter test was to evaluate (1) the processing characteristics of the newly formulated C-106/AY-102 surrogate melter-feed stream, (2) the effectiveness of sucrose as a glass-oxidation-state modifier, and (3) the impact of this reductant upon processing rates

Immobilization of radioactive waste in glass matrices

International Nuclear Information System (INIS)

Wicks, G.G.

1978-01-01

A promising process for long-term management of high-level radioactive waste is to immobilize the waste in a borosilicate glass matrix. Among the most important criteria characterizing the integrity of the large-scale glass-waste forms are that they possess good chemical stability (including low leachability), thermal stability, mechanical integrity, and high radiation stability. Fulfillment of these criteria ensures the maximum margin of safety of glass-waste products, following solidification, handling, transportation, and long-term storage

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.

Source fabrication and lifetime for Li⁺ ion beams extracted from alumino-silicate sources

Energy Technology Data Exchange (ETDEWEB)

Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W

2012-03-05

A space-charge-limited beam with current densities (J) exceeding 1 mA/cm² have been measured from lithium alumino-silicate ion sources at a temperature of ~1275 °C. At higher extraction voltages, the source appears to become emission limited with J ≥ 1.5 mA/cm², and J increases weakly with the applied voltage. A 6.35 mm diameter source with an alumino-silicate coating, ≤0.25 mm thick, has a measured lifetime of ~40 h at ~1275 °C, when pulsed at 0.05 Hz and with pulse length of ~6 μs each. At this rate, the source lifetime was independent of the actual beam charge extracted due to the loss of neutral atoms at high temperature. Finally, the source lifetime increases with the amount of alumino-silicate coated on the emitting surface, and may also be further extended if the temperature is reduced between pulses.

Source fabrication and lifetime for Li⁺ ion beams extracted from alumino-silicate sources

Energy Technology Data Exchange (ETDEWEB)

Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.

2012-04-01

A space-charge-limited beam with current densities (J) exceeding 1 mA/cm² have been measured from lithium alumino-silicate ion sources at a temperature of ~1275 °C. At higher extraction voltages, the source appears to become emission limited with J ≥ 1.5 mA/cm², and J increases weakly with the applied voltage. A 6.35 mm diameter source with an alumino-silicate coating, ≤0.25 mm thick, has a measured lifetime of ~40 h at ~1275 °C, when pulsed at 0.05 Hz and with pulse length of ~6 μs each. At this rate, the source lifetime was independent of the actual beam charge extracted due to the loss of neutral atoms at high temperature. Finally, the source lifetime increases with the amount of alumino-silicate coated on the emitting surface, and may also be further extended if the temperature is reduced between pulses.

Influence of P2O5 and Al2O3 content on the structure of erbium-doped borosilicate glasses and on their physical, thermal, optical and luminescence properties

International Nuclear Information System (INIS)

Bourhis, Kevin; Massera, Jonathan; Petit, Laeticia; Ihalainen, Heikki; Fargues, Alexandre; Cardinal, Thierry; Hupa, Leena; Hupa, Mikko; Dussauze, Marc; Rodriguez, Vincent; Boussard-Plédel, Catherine; Bureau, Bruno; Roiland, Claire; Ferraris, Monica

2015-01-01

Highlights: • Reorganization of the glass structure induced by the addition of P 2 O 5 or Al 2 O 3 . • Emission properties related to the presence of P or Al in the Er 3+ coordination shell. • Declustering observed upon addition of P 2 O 5 . • No declustering upon addition of Al 2 O 3 . - Abstract: The effect of P 2 O 5 and/or Al 2 O 3 addition in Er-doped borosilicate glasses on the physical, thermal, optical, and luminescence properties is investigated. The changes in these glass properties are related to the glass structure modifications induced by the addition of P 2 O 5 and/or Al 2 O 3 , which were probed by FTIR, 11 B MAS NMR and X-ray photoelectron spectroscopies. Variations of the polymerization degree of the silicate tetrahedra and modifications in the [3] B/ [4] B ratio are explained by a charge compensation mechanism due to the formation of AlO 4 , PO 4 groups and the formation of Al-O-P linkages in the glass network. From the absorption and luminescence properties of the Er 3+ ions at 980 nm and 1530 nm, declustering is suspected for the highest P 2 O 5 concentrations while for the highest Al 2 O 3 concentrations no declustering is observed

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.

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

International Nuclear Information System (INIS)

Mishra, R.K.; Kaushik, C.P.

2011-01-01

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)

Development of iodine waste forms using low-temperature sintering glass

International Nuclear Information System (INIS)

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

2010-01-01

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

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

International Nuclear Information System (INIS)

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

1986-01-01

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

Vanadium and Chromium Redox Behavior in borosilicate Nuclear Waste Glasses

International Nuclear Information System (INIS)

McKeown, D.; Muller, I.; Gan, H.; Feng, Z.; Viragh, C.; Pegg, I.

2011-01-01

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. V 2 O 5 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-CO 2 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: V 4+ /V total ranges from 8 to 35%, while Cr 3+ /Cr total can range from 15 to 100% and even to population distributions including Cr 2+ . 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 V 4+ populations increase after initial bubbling, but as bubbling time increases, V 4+ populations drop to near the level of the parent glass, while Cr becomes more reduced to the point of having increasing Cr 2+ populations.

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.

Evaluation of long term leaching of borosilicate glasses

International Nuclear Information System (INIS)

Lanza, F.; Parnisari, E.

1978-01-01

For the evaluation of long term hazard of glass, data on long term glass leaching are needed. Moreover for long term leaching a model of homogeneous dissolution seems reasonable and ask for confirmation. Tests were performed at 30 0 , 80 0 , 100 0 , using an apparatus of the Soxhlet type, to 3.600 hours. Results were obtained as a weight loss and analysed following a relation with time composed by a parabolic and a linear part. Analysis of the surface layer using energy dispersion X ray spectrometry were performed. A critical analysis of the results and of the apparatus is presented

11B nutation NMR study of powdered borosilicates

International Nuclear Information System (INIS)

Woo, Ae Ja; Yang, Kyung Hwa; Han, Duk Young

1998-01-01

In this work, we applied the 1D 11 B nutation NMR method for the analysis of the local structural environments in powdered borosilicates (SiO 2 -B 2 O 3 ). Spin dynamics during a rf irradiation for spin I=3/2 was analytically calculated with a density matrix formalism. Spectral simulation programs were written in MATLAB on a PC. Two borosilicates prepared by the sol-gel process at different stabilization temperature were used for the 1D 11 B nutation NMR experiment. The 11 B NMR parameters, quadrupole coupling constants (e 2 qQ/h) and asymmetry parameters (η), for each borosilicate were extracted from the nonlinear least-squares fitting. The effects of heat treatments on the local structures of boron sites in borosilicates were discussed

Gamma radiation induced changes in nuclear waste glass containing Eu

Science.gov (United States)

Mohapatra, M.; Kadam, R. M.; Mishra, R. K.; Kaushik, C. P.; Tomar, B. S.; Godbole, S. V.

2011-10-01

Gamma radiation induced changes were investigated in sodium-barium borosilicate glasses containing Eu. The glass composition was similar to that of nuclear waste glasses used for vitrifying Trombay research reactor nuclear waste at Bhabha Atomic Research Centre, India. Photoluminescence (PL) and electron paramagnetic resonance (EPR) techniques were used to study the speciation of the rare earth (RE) ion in the matrix before and after gamma irradiation. Judd-Ofelt ( J- O) analyses of the emission spectra were done before and after irradiation. The spin counting technique was employed to quantify the number of defect centres formed in the glass at the highest gamma dose studied. PL data suggested the stabilisation of the trivalent RE ion in the borosilicate glass matrix both before and after irradiation. It was also observed that, the RE ion distributes itself in two different environments in the irradiated glass. From the EPR data it was observed that, boron oxygen hole centre based radicals are the predominant defect centres produced in the glass after irradiation along with small amount of E’ centres. From the spin counting studies the concentration of defect centres in the glass was calculated to be 350 ppm at 900 kGy. This indicated the fact that bulk of the glass remained unaffected after gamma irradiation up to 900 kGy.

Toward a consistent model for glass dissolution

International Nuclear Information System (INIS)

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

1994-01-01

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

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

International Nuclear Information System (INIS)

Jardine, L.J.; Carlton, R.E.; Steindler, M.J.

1981-05-01

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

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

International Nuclear Information System (INIS)

Kieu, L.-H.

2011-01-01

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) [fr

Composition dependence of spontaneous crystallization of phosphosilicate glass melts during cooling

DEFF Research Database (Denmark)

Liu, S.J.; Zhu, C.F.; Zhang, Y.F.

2012-01-01

Crystallization behavior of alumino-phospho-silicate melts during cooling is studied by means of the differential scanning calorimetry, X-ray diffractometry and viscometry. The results show a pronounced impact of alkaline earth oxide, alkali oxide and fluoride on the crystal type and crystallizat......Crystallization behavior of alumino-phospho-silicate melts during cooling is studied by means of the differential scanning calorimetry, X-ray diffractometry and viscometry. The results show a pronounced impact of alkaline earth oxide, alkali oxide and fluoride on the crystal type...... and crystallization degree. It is found that adding NaF into the studied compositions slightly decreases melt fragility and improves both the glass-forming ability and melt workability. This effect is associated with the unique structural role of NaF compared to the other modifier oxides. It is also found...

Fracture during cooling of cast borosilicate glass containing nuclear wastes

International Nuclear Information System (INIS)

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

1981-09-01

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

Characterization of projected DWPF glasses heat treated to simulate canister centerline cooling

International Nuclear Information System (INIS)

Marra, S.L.; Jantzen, C.M.

1992-05-01

Liquid high-level nuclear waste will be immobilized at the Savannah River Site (SRS) by vitrification in borosilicate glass. The glass will be produced 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 Preliminary 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 (PCI) was used to determine the durability of the heat-treated glasses

Borosilicate glasses for the high activity waste vetrification

International Nuclear Information System (INIS)

Cantale, C.; Donato, A.; Guidi, G.

1984-01-01

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

An assessment of methods for immobilizing reprocessed radioactive waste

International Nuclear Information System (INIS)

Murthy, M.K.; Baranyi, A.D.

1980-05-01

Nuclear waste forms presently used for the disposal of high-level wastes and other potential waste forms under development were studied using information available in the literature and by visits to the laboratories. The following waste forms were considered: Borosilicate glass, high-silica glass, glassceramics, supercalcine ceramics, synroc ceramics, borosilicate glass beads in a metal matrix, supercalcine and synroc ceramics in a metal matrix and coated ceramics. The following conclusions have been reached: To date the best developed wasteform, both in terms of overall product quality and process development, is monolithic borosilicate glass. However, hydrothermal instability is a major concern. Borosilicate glass in metal matrix waste form has better properties than monolithic borosilicate glass waste form. The process has been proven on a pilot scale. Hence, it is considered very close to monolithic glass in terms of overall development. The product qualities of the other waste forms are better than borosilicate glass. However, process development for these alternative waste forms is still in a conceptual stage. The technological basis for processing ceramic waste forms exists in a well developed state. Nevertheless, adaptation of the technology to continuous hot-cell operation, although feasible, has not been demonstrated. In view of the product potential of ceramic waste forms it is felt that their development should be given emphasis at this time. (auth)

Fiscal 1999 technical achievement report. Development project on international standards for supporting new industry (Standardization of method for evaluating physical properties of new glass at high temperatures); 1999 nendo shinki sangyo shiengata kokusai hyojun kaihatsu jigyo seika hokokusho. New glass koon bussei no hyoka hoho no hyojunka

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

In the manufacture and processing of high quality glass to be used with electronic devices and displays, values representing its physical properties at high temperatures, such as viscosity, density, cubical expansion coefficient, and surface tension are necessary. Studies were conducted about techniques for evaluating physical values of such high temperature molten materials, and efforts were under way to develop the research results into international standards. Techniques for measuring physical values of high temperature molten soda ash based glass were improved for higher precision, and techniques for evaluating physical values of high temperature molten borosilicate glass were studied. Delegates were sent to International Commission on Glass (ICG) and technical committee TC18 for joining discussion, decision was made that researchers participate in robin tests on molten glass thermal conductivity, density, and cubical expansion coefficient, and pertinent activities were launched. (NEDO)

Using process instrumentation to obviate destructive examination of canisters of HLW glass

International Nuclear Information System (INIS)

Kuhn, W.L.; Slate, S.C.

1983-01-01

An important concern of a manufacturer of packages of solidified high-level waste (HLW) is quality assurance of the waste form. The vitrification of HLW as a borosilicate glass is considered, and, based on a reference vitrification process, it is proposed that information from process instrumentation may be used to assure quality without the need for additional information obtained by destructive examining (core drilling) canisters of glass. This follows mainly because models of product performance and process behavior must be previously established in order to confidently select the desired glass formulation, and to have confidence that the process is well enough developed to be installed and operated in a nuclear facility

Processing of high-temperature simulated waste glass in a continuous ceramic melter

International Nuclear Information System (INIS)

Barnes, S.M.; Brouns, R.A.; Hanson, M.S.

1980-01-01

Recent operations have demonstrated that high-melting-point glasses and glass-ceramics can be successfully processed in joule-heated, ceramic-lined melters with minor modifications to the existing technology. Over 500 kg of simulated waste glasses have been processed at temperatures up to 1410 0 C. The processability of the two high-temperature waste forms tested is similar to existing borosilicate waste glasses. High-temperature waste glass formulations produced in the bench-scale melter exhibit quality comparing favorably to standard waste glass formulations

Behaviour of rare earth elements, as natural analogues of transuranium elements, during weathering of basaltic glasses

International Nuclear Information System (INIS)

Daux, V.; Crovisier, J.L.; Petit, J.C.

1991-01-01

Subglacial basaltic glasses from Iceland have been studied in order to investigate REE behaviour low-temperature weathering. Just as actinides accumulate in the hydrated superficial corrosion layer of borosilicate glasses, REEs are found to be enriched in the natural corrosion layer of basaltic glasses (palagonite). However, this enrichment is only relative for basaltic glasses [fr

Effect of Radiation on Silicon and Borosilicate Glass

National Research Council Canada - National Science Library

Allred, Clark

2003-01-01

.... These two glasses are commonly used as substrates for silicon microelectromechanical (MEMS) devices, and radiation-induced compaction in a substrate can have deleterious effects on device performance...

Glass formulation for phase 1 high-level waste vitrification

International Nuclear Information System (INIS)

Vienna, J.D.; Hrma, P.R.

1996-04-01

The purpose of this study is to provide potential glass formulations for prospective Phase 1 High-Level Waste (HLW) vitrification at Hanford. The results reported here will be used to aid in developing a Phase 1 HLW vitrification request for proposal (RFP) and facilitate the evaluation of ensuing proposals. The following factors were considered in the glass formulation effort: impact on total glass volume of requiring the vendor to process each of the tank compositions independently versus as a blend; effects of imposing typical values of B 2 O 3 content and waste loading in HLW borosilicate glasses as restrictions on the vendors (according to WAPS 1995, the typical values are 5--10 wt% B 2 O 3 and 20--40 wt% waste oxide loading); impacts of restricting the processing temperature to 1,150 C on eventual glass volume; and effects of caustic washing on any of the selected tank wastes relative to glass volume

Glass formulation for phase 1 high-level waste vitrification

Energy Technology Data Exchange (ETDEWEB)

Vienna, J.D.; Hrma, P.R.

1996-04-01

The purpose of this study is to provide potential glass formulations for prospective Phase 1 High-Level Waste (HLW) vitrification at Hanford. The results reported here will be used to aid in developing a Phase 1 HLW vitrification request for proposal (RFP) and facilitate the evaluation of ensuing proposals. The following factors were considered in the glass formulation effort: impact on total glass volume of requiring the vendor to process each of the tank compositions independently versus as a blend; effects of imposing typical values of B{sub 2}O{sub 3} content and waste loading in HLW borosilicate glasses as restrictions on the vendors (according to WAPS 1995, the typical values are 5--10 wt% B{sub 2}O{sub 3} and 20--40 wt% waste oxide loading); impacts of restricting the processing temperature to 1,150 C on eventual glass volume; and effects of caustic washing on any of the selected tank wastes relative to glass volume.

Atomic layer deposition of alternative glass microchannel plates

Energy Technology Data Exchange (ETDEWEB)

O' Mahony, Aileen, E-mail: aom@incomusa.com; Craven, Christopher A.; Minot, Michael J.; Popecki, Mark A.; Renaud, Joseph M.; Bennis, Daniel C.; Bond, Justin L.; Stochaj, Michael E.; Foley, Michael R.; Adams, Bernhard W. [Incom, Inc., 294 Southbridge Road, Charlton, Massachusetts 01507 (United States); Mane, Anil U.; Elam, Jeffrey W. [Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439 (United States); Ertley, Camden; Siegmund, Oswald H. W. [Space Sciences Laboratory, University of California, 7 Gauss Way, Berkeley, California 94720 (United States)

2016-01-15

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 cm{sup 2}). 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{sup −2} s{sup −1}), and low gain variation (±5%)

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

International Nuclear Information System (INIS)

Hsiung, P.

1983-01-01

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 [fr

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

International Nuclear Information System (INIS)

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

2016-01-01

Borosilicate glasses are considered for the long-term confinement of high-level nuclear wastes. External irradiations with 1 MeV He + ions and 7 MeV Au 5+ ions were performed to simulate effects produced by alpha particles and by recoil nuclei in the simulated SON68 nuclear waste glass. To better understand the structural modifications, irradiations were also carried out on a 6-oxides borosilicate glass, a simplified version of the SON68 glass (ISG glass). The mechanical and macroscopic properties of the glasses were studied as function of the deposited electronic and nuclear energies. Alpha particles and gold ions induced a volume change up to −0.7% and −2.7%, respectively, depending on the glass composition. Nano-indentations tests were used to determine the mechanical properties of the irradiated glasses. A decrease of about −22% to −38% of the hardness and a decrease of the reduced Young's modulus by −8% were measured after irradiations. The evolution of the glass structure was studied by Raman spectroscopy, and also 11 B and 27 Al Nuclear Magnetic Resonance (MAS-NMR) on a 20 MeV Kr irradiated ISG glass powder. A decrease of the silica network connectivity after irradiation with alpha particles and gold ions is deduced from the structural changes observations. NMR spectra revealed a partial conversion of BO 4 to BO 3 units but also a formation of AlO 5 and AlO 6 species after irradiation with Kr ions. The relationships between the mechanical and structural changes are also discussed. - Highlights: • Mechanical and structural properties of two borosilicate glass compositions irradiated with alpha particles and heavy ions were investigated. • Both kinds of particles induced a decrease of the hardness, reduced Young's modulus and density. • Electronic and nuclear interactions are responsible for the changes observed. • The evolution of the mechanical properties under irradiation is linked to the changes occured in the

Complexing Agents and pH Influence on Chemical Durability of Type I Molded Glass Containers.

Science.gov (United States)

Biavati, Alberto; Poncini, Michele; Ferrarini, Arianna; Favaro, Nicola; Scarpa, Martina; Vallotto, Marta

2017-01-01

. To prevent such situations, pharmaceutical and biopharmaceutical manufacturers need to understand the reasons for accelerate surface glass corrosion mainly in the case of injectables.Some drugs can contain active components with known ability to corrode glass silica networks. Sometimes these ingredients are dissolved in an alkaline medium that dramatically increases the glass corrosion and potentially causes the issue. As this action is strongly affected by time and temperature, flaking may become visible only after a long storage time. The purpose of this investigation is to verify the borosilicate glass chemical durability during controlled conditions of time and temperature when in contact with testing solutions containing different complexing agents by varying the pH. Si concentration in the extract solution is taken as an index of glass dissolution during constant autoclaving conditions for 1 h at 121 °C, which simulates approximately five years of contact at room temperature.Acetate, citrate, ethylenediaminetetraacetic acid (EDTA), phosphate, and glutarate 0.048 M or 0.024 M solutions were used at increasing pH from 5.5 to 9.0. The chemical durability of two borosilicate tubing glass vials of different glass compositions were compared with the molded one in the worst attack conditions by citric acid. Even if no delamination issue has been experienced by this study in type I molded and tubing containers, the conclusions developed can provide pharmaceutical manufacturers with useful information to prevent glass delamination risk in their processes. © PDA, Inc. 2017.

High-frequency characteristics of glass/ceramic composite and alumina multilayer structures

International Nuclear Information System (INIS)

Niwa, K.; Suzuki, H.; Yokoyama, H.; Kamechara, N.; Tsubone, K.; Tanisawa, H.; Sugiki, H.

1990-01-01

This paper reports the transmission characteristics of glass/ceramic composite (borosilicate glass/alumina) and alumina multilayer structures examined. The triplate stripline formed in the glass/ceramic multilayer shows low conductor and dielectric loss. Alumina multilayer, however, has twice the transmission loss at 10 GHz, because the resistivity of W in the alumina multilayer is higher than the Cu in the glass/ceramic multilayer. Crosstalk between striplines in the glass/ceramics is less than -80 dB up to 11 GHz and 9 GHz for alumina

Migration behaviour of Pu released from Pu-doped glass in compacted bentonite

International Nuclear Information System (INIS)

Ashida, T.; Kohara, Y.; Yui, M.

1994-01-01

In order to investigate the coupled behavior of Pu release from the waste glass and transport in bentonite, a migration experiment with compacted sodium-type bentonite saturated with distilled water was carried out at room temperature, in which Pu-doped borosilicate glass was sandwiched. Under these conditions, leaching of Pu from the glass, diffusion and sorption of Pu in the compacted bentonite occur simultaneously. (orig.)

Composition and redox control of waste glasses: Recommendation for process control limit

International Nuclear Information System (INIS)

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

1986-01-01

An electrochemical series of redox couples, originally developed for Savannah River Laboratory glass frit 131 (SRL-131) as a reference composition, has been extended to two other alkali borosilicate compositions that are candidate glasses for nuclear waste immobilization. Since no dramatic differences were ascertained in the redox chemistry of selected multivalent elements in SRL-131 versus that in Savannah River Laboratory glass frit 165 (SRL-165) and in West Valley glass number-sign 205 (WV-205), the comprehensive electrochemical series can readily be applied to a range of nuclear waste glass compositions. In order to alleviate potential problems with foaming and precipitation of insolubles during the processing of the nuclear waste in these glass melts, the [Fe 2+ ]/[Fe 3+ ] ratio of the melt should be between 0.1 and 0.5. 27 refs., 4 figs., 2 tabs

Modeling surface area to volume effects on borosilicate glass dissolution

International Nuclear Information System (INIS)

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

1992-11-01

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

Development, evaluation, and selection of candidate high-level waste forms

International Nuclear Information System (INIS)

Bernadzikowski, T.A.; Allender, J.S.; Gordon, D.E.; Gould, T.H. Jr.

1982-01-01

The seven candidate waste forms, evaluated as potential media for the immobilization and gelogic disposal of high-level nuclear wastes were borosilicate glass, SYNROC, tailored ceramic, high-silica glass, FUETAP concrete, coated sol-gel particles, and glass marbles in a lead matrix. The evaluation, completed on August 1, 1981, combined preliminary waste form evaluations conducted at Department of Energy (DOE) defense waste-sites and at independent laboratories, peer review assessments, a product performance evaluation, and a processability analysis. Based on the combined results of these four inputs, two of the seven forms, borosilicate glass and a titanate-based ceramic, SYNROC, were selected as the reference and alternative forms, respectively, for continued development and evaluation in the National HLW Program. The borosilicate glass and ceramic forms were further compared during FY-1982 on the basis of risk assessments, cost comparisons, properties comparisons, and conformance with proposed regulatory and repository criteria. Both the glass and ceramic forms are viable candidates for use at DOE defense HLW sites; they are also candidates for immobilization of commercial reprocessing wastes. This paper describes the waste form screening process, discusses each of the four major inputs considered in the selection of the two forms in 1981, and presents a brief summary of the comparisons of the two forms during 1982 and the selection process to determine the final form for SRP defense HLW