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Title: Use of boiled hexamethylenetetramine and urea to increase the porosity of cerium dioxide microspheres formed in the internal gelation process

Abstract

Cerium dioxide (CeO 2) is a commonly used simulant for plutonium dioxide and for plutonium (Pu) in a mixed uranium (U) and Pu oxide [(U, Pu)O 2] in nuclear fuel development. This effort developed CeO 2 microspheres with different porosities and diameters for use in a crush-strength study. The internal gelation technique has produced CeO 2 microspheres with limited initial porosity. When an equal molar solution of urea and hexamethylenetetramine (HMTA) is gently boiling for 1 hr and used in the gelation process, the crystallite size and porosity of mixed U and thorium oxide microspheres and the (U, Pu)O 2 microspheres increased significantly. In this study with cerium, the combination of ammonium cerium nitrate and 1-h boiled HMTA-urea failed to produce a stable feed broth. However, when the 1-h heated HMTA-urea was combined with unheated HMTA-urea in 1 to 3 volume ratio or the boiling time of the HMTA-urea was reduced to 15-20 min, a stable solution of HMTA, urea, and Ce was formed at 273 K. This new Ce solution produced CeO 2 microspheres with much higher initial porosities. Intermediate porosities were possible when the heated HMTA/urea was aged prior to use.

Authors:
 [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
OSTI Identifier:
1408648
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Nuclear Materials
Additional Journal Information:
Journal Volume: 492; Journal Issue: C; Journal ID: ISSN 0022-3115
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; Cerium oxide spheres; Internal gelation

Citation Formats

Hunt, R. D., Collins, J. L., and Cowell, B. S. Use of boiled hexamethylenetetramine and urea to increase the porosity of cerium dioxide microspheres formed in the internal gelation process. United States: N. p., 2017. Web. doi:10.1016/j.jnucmat.2017.04.061.
Hunt, R. D., Collins, J. L., & Cowell, B. S. Use of boiled hexamethylenetetramine and urea to increase the porosity of cerium dioxide microspheres formed in the internal gelation process. United States. doi:10.1016/j.jnucmat.2017.04.061.
Hunt, R. D., Collins, J. L., and Cowell, B. S. 2017. "Use of boiled hexamethylenetetramine and urea to increase the porosity of cerium dioxide microspheres formed in the internal gelation process". United States. doi:10.1016/j.jnucmat.2017.04.061.
@article{osti_1408648,
title = {Use of boiled hexamethylenetetramine and urea to increase the porosity of cerium dioxide microspheres formed in the internal gelation process},
author = {Hunt, R. D. and Collins, J. L. and Cowell, B. S.},
abstractNote = {Cerium dioxide (CeO2) is a commonly used simulant for plutonium dioxide and for plutonium (Pu) in a mixed uranium (U) and Pu oxide [(U, Pu)O2] in nuclear fuel development. This effort developed CeO2 microspheres with different porosities and diameters for use in a crush-strength study. The internal gelation technique has produced CeO2 microspheres with limited initial porosity. When an equal molar solution of urea and hexamethylenetetramine (HMTA) is gently boiling for 1 hr and used in the gelation process, the crystallite size and porosity of mixed U and thorium oxide microspheres and the (U, Pu)O2 microspheres increased significantly. In this study with cerium, the combination of ammonium cerium nitrate and 1-h boiled HMTA-urea failed to produce a stable feed broth. However, when the 1-h heated HMTA-urea was combined with unheated HMTA-urea in 1 to 3 volume ratio or the boiling time of the HMTA-urea was reduced to 15-20 min, a stable solution of HMTA, urea, and Ce was formed at 273 K. This new Ce solution produced CeO2 microspheres with much higher initial porosities. Intermediate porosities were possible when the heated HMTA/urea was aged prior to use.},
doi = {10.1016/j.jnucmat.2017.04.061},
journal = {Journal of Nuclear Materials},
number = C,
volume = 492,
place = {United States},
year = 2017,
month = 5
}

Journal Article:
Free Publicly Available Full Text
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  • Hundreds of grams of calcined cerium dioxide (CeO 2) microspheres were produced in this paper using the internal gelation process with a focus on 75–150 µm and <75 µm diameter sizes. To achieve these small sizes, a modified internal gelation system was employed, which utilized a two-fluid nozzle, two static mixers for turbulent flow, and 2-ethyl-1-hexanol as the medium for gel formation at 333–338 K. This effort generated over 400 g of 75–150 µm and 300 g of <75 µm CeO 2 microspheres. The typical product yields for the 75–150 µm and <75 µm microspheres that were collected and processedmore » were 72 and 99%, respectively, with a typical throughput of 66–73 g of CeO 2 microspheres per test, which could generate a maximum of 78.6 g of CeO 2. The higher yield of very small cerium spheres led to challenges and modifications, which are discussed in detail. Finally, as expected, when the <75 µm microspheres were targeted, losses to the system increased significantly.« less
  • An internal gelation sol-gel technique was used to prepare cerium dioxide microspheres with uniform diameters near 100 µm. In this process, chilled aqueous solutions containing cerium, hexamethylenetetramine (HMTA), and urea are transformed into a solid gel by heat addition and are subsequently washed, dried, and sintered to produce pure cerium dioxide. Cerous nitrate and ceric ammonium nitrate solutions were compared for their usefulness in microsphere production. Gelation experiments were performed with both cerous nitrate and ceric ammonium nitrate to determine desirable concentrations of cerium, HMTA, and urea in feed solutions as well as the necessary quantity of ammonium hydroxide addedmore » to cerium solutions. Analysis of the pH before and after sample gelation was found to provide a quantitative metric for optimal parameter selection along with subjective evaluations of gel qualities. The time necessary for chilled solutions to gel upon inserting into a hot water bath was determined for samples with a variety of parameters and also used to determine desirable formulations for microsphere production. A technique for choosing the optimal mixture of ceric ammonium nitrate, HMTA, and urea was determined using gelation experiments and used to produce microspheres by dispersion of the feed solution into heated silicone oil. Gelled spheres were washed to remove excess reactants and reaction products before being dried and sintered. X-ray diffraction of air-dried microspheres, sintered microspheres, and commercial CeO 2 powders indicated that air-dried and sintered spheres were pure CeO 2.« less
  • The U.S. National Aeronautics and Space Administration (NASA) is developing a uranium dioxide (UO2)/tungsten cermet fuel for potential use as the nuclear cryogenic propulsion stage (NCPS). The first generation NCPS is expected to be made from dense UO2 microspheres with diameters between 75 and 150 m. Previously, the internal gelation process and a hood-scale apparatus with a vibrating nozzle were used to form gel spheres, which became UO2 kernels with diameters between 350 and 850 m. For the NASA spheres, the vibrating nozzle was replaced with a custom designed, two-fluid nozzle to produce gel spheres in the desired smaller sizemore » range. This paper describes the operational methodology used to make 3 kg of uranium oxide microspheres.« less