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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. 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:
 [1];  [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [2];  [3];  [3];  [3];  [4];  [4];  [5];  [6];  [5];  [5]
  1. Washington State University
  2. BATTELLE (PACIFIC NW LAB)
  3. Rutgers University
  4. University of Warwick
  5. University of Sheffield
  6. The University of Sheffield
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1557239
Report Number(s):
PNNL-SA-141110
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
MRS Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 17-18
Country of Publication:
United States
Language:
English

Citation Formats

McCloy, John S., Marcial, Jose, Patil, Deepak, Saleh, Muad, Ahmadzadeh, Mostafa, Chen, Hua, Crum, Jarrod, Riley, Brian J., Kamat, Hrishikesh, Brehault, Antoine, Goel, Ashutosh, Barnsley, Kristian, Hanna, John, Rajbhandari, Prashant, Corkhill, Claire L., Hand, Russell J., and Hyatt, Neil. Glass structure and crystallization in boro-alumino-silicate glasses containing rare earth and transition metal cations: a US-UK collaborative program. United States: N. p., 2019. Web. doi:10.1557/adv.2019.99.
McCloy, John S., Marcial, Jose, Patil, Deepak, Saleh, Muad, Ahmadzadeh, Mostafa, Chen, Hua, Crum, Jarrod, Riley, Brian J., Kamat, Hrishikesh, Brehault, Antoine, Goel, Ashutosh, Barnsley, Kristian, Hanna, John, Rajbhandari, Prashant, Corkhill, Claire L., Hand, Russell J., & Hyatt, Neil. Glass structure and crystallization in boro-alumino-silicate glasses containing rare earth and transition metal cations: a US-UK collaborative program. United States. doi:10.1557/adv.2019.99.
McCloy, John S., Marcial, Jose, Patil, Deepak, Saleh, Muad, Ahmadzadeh, Mostafa, Chen, Hua, Crum, Jarrod, Riley, Brian J., Kamat, Hrishikesh, Brehault, Antoine, Goel, Ashutosh, Barnsley, Kristian, Hanna, John, Rajbhandari, Prashant, Corkhill, Claire L., Hand, Russell J., and Hyatt, Neil. Thu . "Glass structure and crystallization in boro-alumino-silicate glasses containing rare earth and transition metal cations: a US-UK collaborative program". United States. doi:10.1557/adv.2019.99.
@article{osti_1557239,
title = {Glass structure and crystallization in boro-alumino-silicate glasses containing rare earth and transition metal cations: a US-UK collaborative program},
author = {McCloy, John S. and Marcial, Jose and Patil, Deepak and Saleh, Muad and Ahmadzadeh, Mostafa and Chen, Hua and Crum, Jarrod and Riley, Brian J. and Kamat, Hrishikesh and Brehault, Antoine and Goel, Ashutosh and Barnsley, Kristian and Hanna, John and Rajbhandari, Prashant and Corkhill, Claire L. and Hand, Russell J. and Hyatt, Neil},
abstractNote = {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, investigating 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. 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.},
doi = {10.1557/adv.2019.99},
journal = {MRS Advances},
number = 17-18,
volume = 4,
place = {United States},
year = {2019},
month = {2}
}

Works referenced in this record:

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976