Structural, Spectroscopic, and Kinetic Insight into the Heating Rate Dependence of Studtite and Metastudtite Dehydration
Abstract
Uranyl peroxide minerals studtite (UO2O2·4H2O) and metastudtite (UO2O2·2H2O) are important materials in the nuclear fuel cycle. When heated, they dehydrate and transform to amorphous uranium oxides (UOx), yet phase stability and heating rate dependence of these transformations are poorly understood. This information is critical to proper management of fuel cycle materials. In this work, we use in situ powder X-ray diffraction (PXRD), Raman spectroscopy, and thermogravimetric analysis (TGA) to monitor the dehydration of studtite and metastudtite. Strong linear correlation between the heating rate and phase transition temperature is observed. Geometric contraction and diffusion-related kinetic models describe studtite dehydration at slow heating rates, whereas Avrami–Erofeev or reaction order models become more accurate for faster thermal treatments. A second order model describes the transition from metastudtite to UOx regardless of the heating rate. Water retention during studtite dehydration is indicated by PXRD, Raman spectroscopy, and TGA. Here, we observe mixed-phase UOx dehydration products of metastudtite with a likely formation mechanism involving conversion of some uranyl centers from hexagonal to pentagonal bipyramidal coordination units via peroxide liberation. Our observations clarify over 100 years of measurements on these materials and represent an advancement in understanding the chemical behavior of nuclear fuel cycle materials.
- Authors:
-
[1];
[1];
[1];
[1];
[1];
[1];
[1]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1735445
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 124; Journal Issue: 49; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Spano, Tyler, Niedziela, Jennifer L., Shields, Ashley E., McFarlane, Joanna, Zirakparvar, Alex, Brubaker, Zachary, Kapsimalis, Roger J., and Miskowiec, Andrew J. Structural, Spectroscopic, and Kinetic Insight into the Heating Rate Dependence of Studtite and Metastudtite Dehydration. United States: N. p., 2020.
Web. doi:10.1021/acs.jpcc.0c09082.
Spano, Tyler, Niedziela, Jennifer L., Shields, Ashley E., McFarlane, Joanna, Zirakparvar, Alex, Brubaker, Zachary, Kapsimalis, Roger J., & Miskowiec, Andrew J. Structural, Spectroscopic, and Kinetic Insight into the Heating Rate Dependence of Studtite and Metastudtite Dehydration. United States. https://doi.org/10.1021/acs.jpcc.0c09082
Spano, Tyler, Niedziela, Jennifer L., Shields, Ashley E., McFarlane, Joanna, Zirakparvar, Alex, Brubaker, Zachary, Kapsimalis, Roger J., and Miskowiec, Andrew J. Mon .
"Structural, Spectroscopic, and Kinetic Insight into the Heating Rate Dependence of Studtite and Metastudtite Dehydration". United States. https://doi.org/10.1021/acs.jpcc.0c09082. https://www.osti.gov/servlets/purl/1735445.
@article{osti_1735445,
title = {Structural, Spectroscopic, and Kinetic Insight into the Heating Rate Dependence of Studtite and Metastudtite Dehydration},
author = {Spano, Tyler and Niedziela, Jennifer L. and Shields, Ashley E. and McFarlane, Joanna and Zirakparvar, Alex and Brubaker, Zachary and Kapsimalis, Roger J. and Miskowiec, Andrew J.},
abstractNote = {Uranyl peroxide minerals studtite (UO2O2·4H2O) and metastudtite (UO2O2·2H2O) are important materials in the nuclear fuel cycle. When heated, they dehydrate and transform to amorphous uranium oxides (UOx), yet phase stability and heating rate dependence of these transformations are poorly understood. This information is critical to proper management of fuel cycle materials. In this work, we use in situ powder X-ray diffraction (PXRD), Raman spectroscopy, and thermogravimetric analysis (TGA) to monitor the dehydration of studtite and metastudtite. Strong linear correlation between the heating rate and phase transition temperature is observed. Geometric contraction and diffusion-related kinetic models describe studtite dehydration at slow heating rates, whereas Avrami–Erofeev or reaction order models become more accurate for faster thermal treatments. A second order model describes the transition from metastudtite to UOx regardless of the heating rate. Water retention during studtite dehydration is indicated by PXRD, Raman spectroscopy, and TGA. Here, we observe mixed-phase UOx dehydration products of metastudtite with a likely formation mechanism involving conversion of some uranyl centers from hexagonal to pentagonal bipyramidal coordination units via peroxide liberation. Our observations clarify over 100 years of measurements on these materials and represent an advancement in understanding the chemical behavior of nuclear fuel cycle materials.},
doi = {10.1021/acs.jpcc.0c09082},
journal = {Journal of Physical Chemistry. C},
number = 49,
volume = 124,
place = {United States},
year = {Mon Nov 23 00:00:00 EST 2020},
month = {Mon Nov 23 00:00:00 EST 2020}
}
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