Title: Glass structure and crystallization in boro-alumino-silicate glasses containing rare earth and transition metal cations: a US-UK collaborative program

Abstract

Nuclear wastes generated from reprocessing of used nuclear fuel tend to contain a large fraction of rare earth (RE, e.g., Nd³⁺), transition (TM, e.g., Mo⁶⁺, Zr⁴⁺), alkali (A, e.g., Cs⁺), and alkaline earth cations (AE, e.g., Ba²⁺, Sr²⁺). Various strategies have been considered for immobilizing such waste streams, varying from nominally crystal-free glass to glass-ceramic to multi-phase ceramic waste forms. For glass and glass-ceramic waste forms, the added glass-forming system is generally alkali-alkaline earth-aluminoborosilicate (i.e., Na-Ca-Al-B-Si oxide). In a US-UK collaborative project, summarized here, we investigated the glass structure and crystallization dependence on compositional changes in simulated nuclear waste glasses and glass-ceramics. Compositions ranged in complexity from five – to – eight oxides. Specifically, the roles of Mo and rare earths are investigated, since a proposed glass-ceramic waste form contains crystalline phases such as powellite [(AE,A,RE)MoO₄] and oxyapatite [(RE,AE,A)₁₀Si₆O₂₆], and the precipitation of molybdenum phases is known to be affected by the rare earth concentration in the glass. Additionally, the effects of other chemical additions have been systematically investigated, including Zr, Ru, P, and Ti. A series of studies were also undertaken to ascertain the effect of the RE size on glass structure and on partitioning to crystal phases, investigatingmore » similarities and differences in glasses containing single RE oxides of Sc, Y, La, Ce, Nd, Sm, Er, Yb, or Lu. Finally, the effect of charge compensation was investigated by considering not only the commonly assessed peralkaline glass but also metaluminous and peraluminous compositions. Glass structure and crystallization studies were conducted by spectroscopic methods (i.e., Raman, X-ray absorption, nuclear magnetic resonance (NMR), optical absorption, photoluminescence, photoluminescence excitation, X-ray photoelectron spectroscopy), microscopy (i.e., scanning electron microscopy, transmission electron microscopy, electron probe microanalysis), scattering (i.e., X-ray and neutron diffraction, small angle measurements), and physical characterization (i.e., differential thermal analysis, liquidus, viscosity, density). This paper will give an overview of the research program and some example unpublished results on glass-ceramic crystallization kinetics, microstructure, and Raman spectra, as well as some examples of the effects of rare earths on the absorption, luminescence, and NMR spectra of starting glasses. Finally, the formal collaboration described here has resulted in the generation of a large number of results, some of which are still in the process of being published as separate studies.« less

Authors:

McCloy, John S.  ^[1];

• Search DOE PAGES for author "McCloy, John S."
• Search DOE PAGES for ORCID "0000-0001-7476-7771"

Marcial, José ^[2]; Patil, Deepak ^[2]; Saleh, Muad  ^[2];

• Search DOE PAGES for author "Saleh, Muad"
• Search DOE PAGES for ORCID "0000-0002-1391-2784"

Ahmadzadeh, Mostafa ^[2]; Chen, Hua ^[3]

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+ Show Author Affiliations

1. Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
2. Washington State Univ., Pullman, WA (United States)
3. Washington State Univ., Pullman, WA (United States); Inner Mongolia Univ. of Science and Technology (China)

Publication Date:

Wed Feb 06 00:00:00 EST 2019

Research Org.:

Washington State Univ., Pullman, WA (United States)

Sponsoring Org.:

USDOE Office of Nuclear Energy (NE)

OSTI Identifier:

1558459

Grant/Contract Number:  

NE0008431

Resource Type:

Accepted Manuscript

Journal Name:

MRS Advances

Additional Journal Information:

Journal Volume: 4; Journal Issue: 17-18; Journal ID: ISSN 2059-8521

Publisher:

Materials Research Society (MRS)

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE