Effect of Li, Fe, and B Addition on the Crystallization Behavior of Sodium Aluminosilicate Glasses as Analogues for Hanford High Level Waste Glasses

MRS Advances ◽  
2016 ◽  
Vol 2 (10) ◽  
pp. 549-555 ◽  
Author(s):  
José Marcial ◽  
Mostafa Ahmadzadeh ◽  
John S. McCloy
Keyword(s):  
Function Analysis ◽  
High Level Waste ◽  
X Ray Diffraction ◽  
X Ray ◽  
High Sodium ◽  
Chemical Ordering ◽  
Sodium Aluminosilicate ◽  
Aluminosilicate Glasses ◽  
Heat Treated ◽  
High Level

ABSTRACTCrystallization of aluminosilicates during the conversion of Hanford high-level waste (HLW) to glass is a function of the composition of the glass-forming melt. In high-sodium, high-aluminum waste streams, the crystallization of nepheline (NaAlSiO4) removes chemically durable glass-formers from the melt, leaving behind a residual melt that is enriched in less durable components, such as sodium and boron. We seek to further understand the effect of lithium, boron, and iron addition on the crystallization of model silicate glasses as analogues for the complex waste glass. Boron and iron behave as glass intermediates which allow for crystallization when present in low additions but frustrate crystallization in high additions. In this work, we seek to compare the average structures of quenched and heat treated glasses through Raman spectroscopy, X-ray diffraction, vibrating sample magnetometry, and X-ray pair distribution function analysis. The endmembers of this study are feldspathoid-like (LiAlSiO4, NaAlSiO4, NaBSiO4, and NaFeSiO4), pyroxene-like (LiAlSi2O6, NaAlSi2O6, NaBSi2O6, and NaFeSi2O6), and feldspar-like (LiAlSi3O8, NaAlSi3O8, NaBSi3O8, and NaFeSi3O8). Such a comparison will provide further insight on the complex relationship between the average chemical ordering and topology of glass on crystallization.

Cold Crucible Vitrification of U-bearing SRS SB4 HLW Surrogate

2010 ◽  
Vol 1265 ◽  
Author(s):  
Sergey Stefanovsky ◽  
Alexander Ptashkin ◽  
Oleg Knyazev ◽  
Olga Stefanovsky ◽  
James C Marra
Keyword(s):  
High Level Waste ◽  
Cold Crucible ◽  
Savannah River ◽  
X Ray Diffraction ◽  
Alumina Crucible ◽  
X Ray ◽  
Xrd Study ◽  
Processing Facility ◽  
High Level ◽  
River Site

AbstractSavannah River Site Defense Waste Processing Facility (DWPF) Sludge Batch 4 (SB4) high level waste (HLW) simulant at 55 wt % waste loading was produced in the demountable cold crucible and cooled to room temperature in the cold crucible. Appreciable losses of Cs, S and Cl took place during the melting. A second glass sample was subjected to canister centerline cooling (CCC) regime in an alumina crucible in a resistive furnace. X-ray diffraction (XRD) study showed that the glass blocks were composed of vitreous and spinel structure phases. No separate U-bearing phases were found.

Phase Relations and Chemical Durability of Ceramics in the Pseudo-Binary System: CaZrTi2O7–GdAlO3

2003 ◽  
Vol 807 ◽  
Author(s):  
N. P. Mikhailenko ◽  
A. V. Ochkin ◽  
S. V. Stefanovsky ◽  
O. I. Kirjanova
Keyword(s):  
Electron Microscopy ◽  
Binary System ◽  
Chemical Durability ◽  
Phase Relations ◽  
High Level Waste ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ceramic Samples ◽  
High Level ◽  
System 1

ABSTRACTPhase relations in a pseudo-binary system (1-x) CaZrTi2O7- x GdAlO3 suggested for immobilization of a zirconium - rare earth – actinide fraction of high level waste were studied with X-ray diffraction and electron microscopy. Zirconolite and perovskite were found to be major phases in the ceramic samples prepared by cold pressing and sintering at 1400 and 1500 °C. At relatively low perovskite content (x < 0.5) zirconolite is the major host for Gd, which is considered as a trivalent surrogate for Am and Cm. At higher perovskite content, perovskite becomes the major host for Gd. Zirconolite is the major host phase for corrosion products (Al, Fe, Ti, Zr). Leach rates of Gd, 238Pu, and 241Am from the ceramics studied are 10−4–10−5 g/(m2d).

Effect of Molybdenum and Ruthenium on the Crystallization Tendency of a New Nuclear Glass Containing High Rare-earth Concentration

2010 ◽  
Vol 1265 ◽  
Author(s):  
Daniel Caurant ◽  
Nolwenn Chouard ◽  
Odile Majerus ◽  
Jean-Luc Dussossoy ◽  
Aurelien Ledieu ◽  
...  
Keyword(s):  
Room Temperature ◽  
Nucleating Agent ◽  
High Level Waste ◽  
Optical Absorption Spectroscopy ◽  
Thermal Treatments ◽  
X Ray Diffraction ◽  
X Ray ◽  
High Level ◽  
The Impact ◽  
Crystallization Tendency

AbstractThe impact of Nd2O3, MoO3 and RuO2 addition on the competition between the crystallization of apatite Ca2Nd8(SiO4)6O2 and powellite CaMoO4 phases which both may appear in High Level Waste nuclear glass (under certain specific conditions of cooling and glass composition) has been studied on a simplified composition belonging to the system SiO2-Na2O-CaO-Al2O3-B2O3. X-ray diffraction (at room temperature and high temperature) and scanning electron microscopy measurements have been performed on five glasses under two different thermal treatments. We show that RuO2 acts as a nucleating agent for apatite. Moreover, neodymium and molybdenum cations seem to be very close in the glassy network as Nd2O3 addition stops the phase separation of molybdates and inhibits the crystallization of CaMoO4. On the contrary, MoO3 seems to favor the crystallization of apatite. For several samples, the evolution of the distribution of Nd3+ cations after crystallization was followed by optical absorption spectroscopy.

STRUCTURAL INVESTIGATION OF GADOLINIUM DOPED YTTRIUM-ALUMINOSILICATE GLASSES AND VITROCERAMICS

2008 ◽  
Vol 22 (12) ◽  
pp. 1933-1939
Author(s):  
S. SIMON
Keyword(s):  
Electron Paramagnetic Resonance ◽  
Structural Changes ◽  
Structural Investigation ◽  
Differential Analysis ◽  
X Ray Diffraction ◽  
Paramagnetic Resonance ◽  
X Ray ◽  
Aluminosilicate Glasses ◽  
Heat Treated ◽  
Electron Paramagnetic

Structural changes induced by heat treatment of yttrium-aluminosilicate glasses doped with gadolinium were studied by thermal differential analysis, X-ray diffraction and Gd 3+ electron paramagnetic resonance (EPR). A small amount of yttrium was replaced by gadolinium in the host glass because yttrium and gadolinium cations are quite similar, and gadolinium can be used as a structural sensor by electron paramagnetic resonance measurements. EPR results evidence small changes in the surroundings of Gd 3+ ions in the heat treated samples, as compared with the as prepared ones.

Zirconolite-Based Ceramic Formulations for Immobilization of Zr-REE-Actinide Fraction of HLW

2004 ◽  
Vol 824 ◽  
Author(s):  
A.V. Ochkin ◽  
S.V. Stefanovsky ◽  
A.G. Ptashkin ◽  
N.S. Mikhailenko ◽  
O.I. Kirjanova
Keyword(s):  
Electron Microscopy ◽  
Solid Solution ◽  
Scanning Electron Microscopy ◽  
High Level Waste ◽  
X Ray Diffraction ◽  
Controlled Cooling ◽  
X Ray ◽  
Transmission Electron ◽  
High Level ◽  
Scanning Electron

AbstractTwo ceramics for immobilization of a Zr-REE-actinide fraction of high level waste (HLW) based on zirconolite or/and pyrochlore structures with minor brannerite/lucasite, and fluorite-structured dioxide-based solid solution, were synthesized and characterized. The samples were produced by melting of oxide mixtures at 1500 °C followed by controlled cooling for crystallization. Phase compositions of the samples obtained and waste elements partitioning among co-existing phases were investigated in detail using powder X-ray diffraction, scanning electron microscopy with energy dispersive spectroscopy, and transmission electron microscopy. Cerium enters cerianite-based solid solution, lucasite (if present), and to a lesser extent, pyrochlore and zirconolite. Europium and gadolinium enter predominantly zirconolite and pyrochlore. The highest uranium concentrations were found in a uraninite-based cubic solid solution or pyrochlore and zirconolite.

scholarly journals X-Ray Diffraction and Product Consistency Test Results for the Phase 6 Study of Nepheline Formation in High-Level Waste Glasses

2019 ◽  
Author(s):  
Charmayne Lonergan ◽  
Jared Kroll ◽  
Chloe Skidmore ◽  
Zayne Nelson ◽  
John Vienna
Keyword(s):  
High Level Waste ◽  
Test Results ◽  
X Ray Diffraction ◽  
Consistency Test ◽  
X Ray ◽  
High Level

Glass-Ceramic Waste Forms for Immobilizing Plutonium

1996 ◽  
Vol 465 ◽  
Author(s):  
T. P. O'Holleran ◽  
S. G. Johnson ◽  
S. M. Frank ◽  
M. K. Meyer ◽  
M. Noy ◽  
...  
Keyword(s):  
Glass Ceramic ◽  
High Level Waste ◽  
Processing Plant ◽  
Chemical Processing ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ceramic Waste ◽  
Waste Forms ◽  
Diffraction Patterns ◽  
High Level

ABSTRACTResults are reported on several new glass and glass-ceramic waste formulations for plutonium disposition. The approach proposed involves employing existing calcined high level waste (HLW) present at the Idaho Chemical Processing Plant (ICPP) as an additive to: 1) aid in the formation of a durable waste form and 2) decrease the attractiveness level of the plutonium from a proliferation viewpoint. The plutonium, PuO2, loadings employed were 15 wt% (glass) and 17 wt% (glass-ceramic). Results in the form of x-ray diffraction patterns, microstructure and durability tests are presented on cerium surrogate and plutonium loaded waste forms using simulated calcined HLW and demonstrate that durable phases, zirconia and zirconolite, contain essentially all the plutonium.

Effect of cooling profile on crystalline phases, oxidation state, and chemical partitioning of complex glasses

MRS Advances ◽  
2020 ◽  
Vol 5 (11) ◽  
pp. 569-579
Author(s):  
J. Marcial ◽  
O. K. Neill ◽  
M. Newville ◽  
J. V. Crum ◽  
J. McCloy
Keyword(s):  
Oxidation State ◽  
High Level Waste ◽  
Crystal Glass ◽  
Treatment Schedule ◽  
X Ray Diffraction ◽  
Chemical Partitioning ◽  
X Ray ◽  
Spatially Resolved ◽  
Isothermal Heat Treatments ◽  
High Level

Abstract:Investigations of the crystallization of aluminosilicate phases within Hanford nuclear waste glasses typically involve subjecting samples to the canister centerline cooling (CCC) schedule. This cooling schedule is representative of the slowest cooling thermal profile which these glasses will experience after the glass is poured into the high level waste (HLW) container. However, few investigations have observed how the crystallization behavior changes by varying the heat treatment schedule. In the present study, three Hanford HLW glasses are subjected to CCC and isothermal heat treatments (IHT) to better understand the evolution of phases and the chemical partitioning due to temperature schedule. Samples were characterized using electron probe microanalysis, X-ray diffraction, micro X-ray fluorescence, and micro X-ray absorption spectroscopy. From IHT, eucryptite and apatite phases were observed which were not observed during CCC. Spatially-resolved measurements demonstrated that the oxidation state of the iron was similar among glass and crystal, and we suggest a mechanism to describe the compositional fluctuations near the crystal-glass interface which influence crystallization.

scholarly journals Stable and Metastable Phase Equilibria Involving the Cu6Sn5 Intermetallic

2021 ◽  
Author(s):  
A. Leineweber ◽  
M. Löffler ◽  
S. Martin
Keyword(s):  
Phase Equilibria ◽  
Electron Backscatter Diffraction ◽  
Metastable Phase ◽  
Stable Phase ◽  
X Ray Diffraction ◽  
X Ray ◽  
Heat Treated ◽  
Ordered Phases ◽  
Backscatter Diffraction ◽  
Kinetics Of

Abstract Cu6Sn5 intermetallic occurs in the form of differently ordered phases η, η′ and η′′. In solder joints, this intermetallic can undergo changes in composition and the state of order without or while interacting with excess Cu and excess Sn in the system, potentially giving rise to detrimental changes in the mechanical properties of the solder. In order to study such processes in fundamental detail and to get more detailed information about the metastable and stable phase equilibria, model alloys consisting of Cu3Sn + Cu6Sn5 as well as Cu6Sn5 + Sn-rich melt were heat treated. Powder x-ray diffraction and scanning electron microscopy supplemented by electron backscatter diffraction were used to investigate the structural and microstructural changes. It was shown that Sn-poor η can increase its Sn content by Cu3Sn precipitation at grain boundaries or by uptake of Sn from the Sn-rich melt. From the kinetics of the former process at 513 K and the grain size of the η phase, we obtained an interdiffusion coefficient in η of (3 ± 1) × 10−16 m2 s−1. Comparison of this value with literature data implies that this value reflects pure volume (inter)diffusion, while Cu6Sn5 growth at low temperature is typically strongly influenced by grain-boundary diffusion. These investigations also confirm that η′′ forming below a composition-dependent transus temperature gradually enriches in Sn content, confirming that Sn-poor η′′ is metastable against decomposition into Cu3Sn and more Sn-rich η or (at lower temperatures) η′. Graphic Abstract

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