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.

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.

X-ray Absorption Fine Structure Studies of Speciation of Technetium in Borosilicate Glasses

2003 ◽  
Vol 802 ◽  
Author(s):  
Wayne W. Lukens ◽  
David K. Shuh ◽  
Isabelle S. Muller ◽  
David A. McKeown
Keyword(s):  
Fine Structure ◽  
Oxidation State ◽  
Organic Material ◽  
Glass Frit ◽  
High Level Waste ◽  
Borosilicate Glasses ◽  
X Ray ◽  
Synthesis Conditions ◽  
High Level ◽  
X Ray Absorption

ABSTRACTA series of glass samples were prepared analogously to high level waste glass using either glass frit or glass precursors combined with a high level waste surrogate containing NaTcO4. Three different technetium species were observed in these glasses depending upon the synthesis conditions. If the glasses were prepared by reducing NaTcO4 to TcO2•2H2O with hydrazine or if a large amount of organic material was present, inclusions of TcO2 were observed. If no organic material was present, technetium was incorporated as TcO4−. If only a small amount of organic material was present, isolated Tc(IV) sites were observed in the glass. The relative technetium retention of these glasses was estimated from the Tc K-edge height, and had no correlation with the oxidation state of the technetium. Pertechnetate was well retained in these glasses.

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.

scholarly journals Spatially Resolved Forming Mechanisms Detection in Single Point Incremental Forming Using Synchrotron Based Texture Analysis

2021 ◽  
Author(s):  
Mateus Dobecki ◽  
Alexander Poeche ◽  
Walter Reimers
Keyword(s):  
Texture Analysis ◽  
Incremental Forming ◽  
Single Point ◽  
High Energy ◽  
X Ray Diffraction ◽  
X Ray ◽  
Forming Mechanism ◽  
Spatially Resolved ◽  
Step Down ◽  
Stress States

AbstractDespite the ongoing success of understanding the deformation states in sheets manufactured by single-point incremental forming (SPIF), the unawareness of the spatially resolved influence of the forming mechanisms on the residual stress states of incrementally formed sheet metal parts impedes their application-optimized use. In this study, a well-founded experimental proof of the occurring forming mechanisms shear, bending and stretching is presented using spatially resolved, high-energy synchrotron x-ray diffraction-based texture analysis in transmission mode. The measuring method allows even near-surface areas to be examined without any impairment of microstructural influences due to tribological reactions. The depth-resolved texture evolution for different sets of forming parameters offers insights into the forming mechanisms acting in SPIF. Therefore, the forming mechanisms are triggered explicitly by adjusting the vertical step-down increment Δz for groove, plate and truncated cone geometries. The texture analysis reveals that the process parameters and the specimen geometries used lead to characteristic changes in the crystallites’ orientation distribution in the formed parts due to plastic deformation. These forming-induced reorientations of the crystallites could be assigned to the forming mechanisms by means of defined reference states. It was found that for groove, plate and truncated cone geometries, a decreasing magnitude of step-down increments leads to a more pronounced shear deformation, which causes an increasing work hardening especially at the tool contact area of the formed parts. Larger step-down increments, on the other hand, induce a greater bending deformation. The plastic deformation by bending leads to a complex stress field that involves alternating residual tensile stresses on the tool and residual compressive stresses on the tool-averted side incrementally formed sheets. The present study demonstrates the potential of high-energy synchrotron x-ray diffraction for the spatially resolved forming mechanism research in SPIF. Controlling the residual stress states by optimizing the process parameters necessitates knowledge of the fundamental forming mechanism action.

Phase composition depth profiles using spatially resolved energy dispersive X-ray diffraction

2004 ◽  
Vol 37 (6) ◽  
pp. 967-976 ◽  
Author(s):  
Andrew C. Jupe ◽  
Stuart R. Stock ◽  
Peter L. Lee ◽  
Nikhila N. Naik ◽  
Kimberly E. Kurtis ◽  
...  
Keyword(s):  
Phase Composition ◽  
Spatial Resolution ◽  
Zinc Coating ◽  
High Energy ◽  
Sulfate Attack ◽  
Energy Dispersive ◽  
X Ray Diffraction ◽  
X Ray ◽  
Spatially Resolved ◽  
Composition Profiles

Spatially resolved energy dispersive X-ray diffraction, using high-energy synchrotron radiation (∼35–80 keV), was used nondestructively to obtain phase composition profiles along the radii of cylindrical cement paste samples to characterize the progress of the chemical changes associated with sulfate attack on the cement. Phase distributions were acquired to depths of ∼4 mm below the specimen surface with sufficient spatial resolution to discern features less than 200 µm thick. The experimental and data analysis methods employed to obtain quantitative composition profiles are described. The spatial resolution that could be achieved is illustrated using data obtained from copper cylinders with a thin zinc coating. The measurements demonstrate that this approach is useful for nondestructively visualizing the sometimes complex transformations that take place during sulfate attack on cement-based materials. These transformations can be spatially related to microstructure as seen by computed microtomography.

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