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Title: Production of cerium dioxide microspheres by an internal gelation sol–gel method

Abstract

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 added 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 spheresmore » 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

Authors:
ORCiD logo
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1361970
Report Number(s):
PNNL-SA-123942
Journal ID: ISSN 0928-0707
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Sol-Gel Science and Technology; Journal Volume: 82; Journal Issue: 3
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; sol-gel; internal gelation; cerium oxide; microsphere; nuclear fuel

Citation Formats

Katalenich, Jeffrey A. Production of cerium dioxide microspheres by an internal gelation sol–gel method. United States: N. p., 2017. Web. doi:10.1007/s10971-017-4345-8.
Katalenich, Jeffrey A. Production of cerium dioxide microspheres by an internal gelation sol–gel method. United States. doi:10.1007/s10971-017-4345-8.
Katalenich, Jeffrey A. Mon . "Production of cerium dioxide microspheres by an internal gelation sol–gel method". United States. doi:10.1007/s10971-017-4345-8.
@article{osti_1361970,
title = {Production of cerium dioxide microspheres by an internal gelation sol–gel method},
author = {Katalenich, Jeffrey A.},
abstractNote = {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 added 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 CeO2 powders indicated that air-dried and sintered spheres were pure CeO2.},
doi = {10.1007/s10971-017-4345-8},
journal = {Journal of Sol-Gel Science and Technology},
number = 3,
volume = 82,
place = {United States},
year = {Mon Mar 27 00:00:00 EDT 2017},
month = {Mon Mar 27 00:00:00 EDT 2017}
}
  • Internal gelation sol-gel methods have used a variety of sphere forming methods in the past to produce metal oxide microspheres, but typically with poor control over the size uniformity at diameters near 100 µm. This work describes efforts to make and measure internal gelation, sol-gel microspheres with very uniform diameters in the 100 – 200 µm size range using a two-fluid nozzle. A custom apparatus was used to form aqueous droplets of sol-gel feed solutions in silicone oil and heat them to cause gelation of the spheres. Gelled spheres were washed, dried, and sintered prior to mounting on glass slidesmore » for optical imaging and analysis. Microsphere diameters and shape factors were determined as a function of silicone oil flow rate in a two-fluid nozzle and the size of a needle dispensing the aqueous sol-gel solution. Nine batches of microspheres were analyzed and had diameters ranging from 65.5 ± 2.4 µm for the smallest needle and fastest silicone oil flow rate to 211 ± 4.7 µm for the largest needle and slowest silicone oil flow rate. Standard deviations for measured diameters were less than 8% for all samples and most were less than 4%. Microspheres had excellent circularity with measured shape factors of 0.9 – 1. However, processing of optical images was complicated by shadow effects in the photoresist layer on glass slides and by overlapping microspheres. Based on calculated flow parameters, microspheres were produced in a simple dripping mode in the two-fluid nozzle. Using flow rates consistent with a simple dripping mode in a two-fluid nozzle configuration allows for very uniform oxide microspheres to be produced using the internal-gelation sol-gel method.« less
  • 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
  • Recently, an internal gelation study demonstrated that the use of heated urea and hexamethylenetetramine can have a pronounced impact on the porosity and sintering characteristics of cerium dioxide (CeO 2) microspheres. This effort has identified process variables that can significantly change the initial porosity of the CeO 2 microspheres with slight modifications. A relatively small difference in the sample preparation of cerium ammonium nitrate and ammonium hydroxide solution had a large reproducible impact on the porosity and slow pour density of the produced microspheres. Increases in the gelation temperature as small as 0.5 K also produced a noticeable increase inmore » the slow pour density. If the gelation temperature was increased too high, the use of the heated hexamethylenetetramine and urea was no longer observed to be effective in increasing the porosity of the CeO 2 microspheres. In conclusion, the final process variable was the amount of dispersing agent, Span™ 80, which can increase the slow pour density and produce significantly smaller microspheres.« less