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Journal of Sol-Gel Science and Technology

, Volume 86, Issue 2, pp 329–342 | Cite as

Production of monodisperse cerium oxide microspheres with diameters near 100 µm by internal-gelation sol–gel methods

  • Jeffrey A. Katalenich
  • Brian B. Kitchen
  • Bruce D. Pierson
Original Paper: Fundamentals of sol-gel and hybrid materials processing
  • 90 Downloads

Abstract

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 them on glass slides 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 the fastest silicone oil flow rate to 211 ± 4.7 µm for the largest needle and the slowest silicone oil flow rate. Standard deviations for measured diameters were less than 8% for all samples and most of them 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 the 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.

Keywords

Internal gelation Cerium oxide Microsphere Monodisperse Two-fluid nozzle Nuclear fuel 

Notes

Acknowledgements

The authors would like to acknowledge and thank Pilar Herrera-Fierro of the University of Michigan’s Lurie Nanofabrication Facility for her instruction and assistance with optical microscopy. The authors would also like to thank Dr. Gary Was of the University of Michigan Department of Nuclear Engineering and Radiological Sciences for his input on this work. This research was conducted with government support under and awarded by DoD, Air Force Office of Scientific Research, and National Defense Science and Engineering Graduate (NDSEG) Fellowship, 32 CFR 168a. This material is based upon work supported by the National Science Foundation Graduate Student Research Fellowship under Grant No. DGE 1256260. Any opinion, findings, and conclusions or recommendations expressed in this material are that of the author and do not necessarily reflect the views of the National Science Foundation. This material is based upon work supported by the Center for Space Nuclear Research (CSNR) under the Universities Space Research Association (USRA) Subcontract 06711-003. The USRA operates the CSNR for the Idaho National Laboratory.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. 1.
    Brugghen FW vd, Noothout AJ, Hermans MEA et al. (1970) A U(VI)-process for microsphere production. In: Wymer RG, Lotts AL (eds) Sol-gel processes and reactor fuel cycles. Oak Ridge National Laboratory, Gatlinburg, TennesseeGoogle Scholar
  2. 2.
    Kanij JBW, Noothout AJ, Votocek O (1973) The KEMA U(VI)-process for the production of UO2 microspheres. In: Hermans MEA (ed) Proceedings of a panel on sol-gel process for fuel fabrication. International Atomic Energy Agency, ViennaGoogle Scholar
  3. 3.
    Collins JL, Lloyd MH, Fellows RL (1987) The basic chemistry involved in the internal-gelation method of precipitating uranium as determined by pH measurements. Radiochim Acta 42:121–134CrossRefGoogle Scholar
  4. 4.
    Collins JL, Lloyd MH, Fellows RL (1984) Effects of process variables on reaction mechanisms responsible for ADUN hydrolysis, precipitation, and gelation in the internal gelation gel-sphere process. Oak Ridge National Laboratory, Oak Ridge, TennesseeGoogle Scholar
  5. 5.
    King CM, King RB, Garber RA et al. (1990) Magnetic resonance as a structural probe of a uranium (VI) sol-gel process. MRS Online Proceedings Library, San Francisco, CAGoogle Scholar
  6. 6.
    Cordfunke EHP (1972) The system UO2(NO3)2-UO3-H2O. J Inorg Nucl Chem 34:531–534CrossRefGoogle Scholar
  7. 7.
    Borland M, Frank S, Lessing P et al. (2008) Evaluation of aqueous and powder processing techniques for production of Pu-238 fueled general purpose heat sources. Idaho National Laboratory, Idaho Falls, IdahoGoogle Scholar
  8. 8.
    Katalenich JA (2014) Production of monodisperse, crack-free cerium oxide microspheres by internal gelation sol-gel methods. University of Michigan, Ann Arbor, MichiganGoogle Scholar
  9. 9.
    Katalenich JA (2017) Production of cerium dioxide microspheres by an internal gelation sol–gel method. J Sol Gel Sci Technol 1–10.  https://doi.org/10.1007/s10971-017-4345-8
  10. 10.
    Kent RA (1979) LASL fabrication flowsheet for GPHS fuel pellets. Los Alamos Scientific Laboratory, Los Alamos, New MexicoGoogle Scholar
  11. 11.
    Duncan A, Kane M (2009) Properties and behavior of Pu-238 relevant to decontamination of building 235-F. Savannah River Nuclear Solutions, Aiken, South CarolinaGoogle Scholar
  12. 12.
    Congdon JW (1996) Physical behavior of Pu-238 oxide. Westinghouse Savannah River Company, Aiken, South CarolinaGoogle Scholar
  13. 13.
    Icenhour AS (2005) Transport of radioactive material by alpha recoil. Oak Ridge National Laboratory, Oak Ridge, TennesseeGoogle Scholar
  14. 14.
    Office of Oversight, Rollow T (2000) Type A accident investigation of the March 16, 2000 Plutonium-238 multiple intake event at the plutonium facility Los Alamos National Laboratory. U.S. Department of Energy, Office of Environment, Safety, and Health, Los Alamos, New MexicoGoogle Scholar
  15. 15.
    Department of Energy, Germantown, MD. National Nuclear Security Administration (2003) Type B accident investigation of the August 5, 2003 Plutonium-238 multiple uptake event at the plutonium facility. Los Alamos National Laboratory, New Mexico, Technical Information Center Oak Ridge TennesseeGoogle Scholar
  16. 16.
    Serandour AL, Tsapis N, Gervelas C et al. (2007) Decorporation of plutonium by pulmonary administration of Ca-DTPA dry powder: a study in rat after lung contamination with different plutonium forms. Radiat Prot Dosim 127:472–476.  https://doi.org/10.1093/rpd/ncm300 CrossRefGoogle Scholar
  17. 17.
    Bickford DF, Rankin DT (1975) Fabrication of granule and pellet heat sources from oxalate-based 238PuO2. Savannah River Laboratory, Aiken, South CarolinaGoogle Scholar
  18. 18.
    Folger RL (1980) 238Pu fuel form processes bimonthly report—May/June 1979. Savannah River Laboratory, Aiken, South CarolinaGoogle Scholar
  19. 19.
    Wymer RG (1968) Laboratory and engineering studies of sol-gel processes at Oak Ridge National Laboratory. Oak Ridge National Laboratory, Oak Ridge, TennesseeGoogle Scholar
  20. 20.
    Ferguson DE (1968) Chemical technology division annual progress report for period ending 31 May. Oak Ridge National Laboratory, Oak Ridge, TennesseeGoogle Scholar
  21. 21.
    Haas PA, Bond WD, Lloyd MH, McBride JP (1966) Sol-gel process development and microsphere preparation. In: Wymer RG (ed) Second international thorium fuel cycle symposium. U.S. Atomic Energy Commission, Gatlinburg, TennesseeGoogle Scholar
  22. 22.
    Haas PA, Haws CC, Kitts FG, Ryon AD (1967) Engineering development of sol-gel processes at the Oak Ridge National Laboratory. Oak Ridge National Laboratory, Turin, ItalyGoogle Scholar
  23. 23.
    Wymer RG (1965) Preliminary studies of the preparation of UO2 microspheres by a sol-gel technique. Oak Ridge National Laboratory, Oak Ridge, TennesseeGoogle Scholar
  24. 24.
    Haas PA (1969) Sol-gel preparation of spheres: design and operation of fluidized bed columns. Oak Ridge National Laboratory, Oak Ridge, TennesseeGoogle Scholar
  25. 25.
    Haas PA, Clinton SD, Kleinsteuber AT (1966) Preparation of urania and urania-zirconia microspheres by a sol-gel process. Can J Chem Eng December: 348–353Google Scholar
  26. 26.
    Dewell EH (1969) Gel-addition process chemical studies—Quarterly Progress Report No. 9. Babcock & Wilcox, Lynchburg, VirginiaGoogle Scholar
  27. 27.
    Finney BC, Haas PA (1972) Sol-gel process—engineering-scale demonstration of the preparation of high-density UO2 microspheres. Oak Ridge National Laboratory, Oak Ridge, TennesseeGoogle Scholar
  28. 28.
    Grove GR, Kelly DP, Vallee RE, Lonadier, FD, Brown WB (1967) Mound Laboratory Isotopic Power Fuels Programs: January–March, 1967. Mound LaboratoryGoogle Scholar
  29. 29.
    Bradley JE, Grove GR, Gnagey LB, Sheidler WC, Huddleston FM, Lonadier FD, Wittenberg LJ, Kershner CJ, Kelly DP (1967) Mound Laboratory Isotopic Power Fuels Programs: October–December 1966. Mound LaboratoryGoogle Scholar
  30. 30.
    Grove GR, Kelly DP, Vallee RE, Lonadier, FD, Brown WB (1967) Mound Laboratory Isotopic Power Fuels Programs: April–June 1967. Mound LaboratoryGoogle Scholar
  31. 31.
    Plymale DL, Smith WH (1968) The preparation of plutonium-238 dioxide microspheres by the sol-gel process. Mound Laboratory, Miamisburg, OhioGoogle Scholar
  32. 32.
    Wymer RG (1973) Sol-gel processes at Oak Ridge National Laboratory: development, demonstration, and irradiation tests. Oak Ridge National Laboratory, Oak Ridge, TennesseeGoogle Scholar
  33. 33.
    Haas PA, Lackey WJ (1973) Improved size uniformity of sol-gel spheres by imposing a vibration on the sol in dispersion nozzles. Oak Ridge National Laboratory, Oak Ridge, TennesseeGoogle Scholar
  34. 34.
    Haas PA (1975) Formation of liquid drops with uniform and controlled diameters at rates of 10^3 to 10^5 drops per minute. Am Inst Chem Eng 21:383–385CrossRefGoogle Scholar
  35. 35.
    Collins JL (2004) Production of depleted UO2 kernels for the advanced gas-cooled reactor program for use in TRISO coating development. Oak Ridge National Laboratory, Oak Ridge, TennesseeGoogle Scholar
  36. 36.
    Hunt RD, Collins JL (2004) Uranium kernel formation via internal gelation. Radiochim Acta 92:909–915.  https://doi.org/10.1524/ract.92.12.909.55110 CrossRefGoogle Scholar
  37. 37.
    Barnes CM, Richardson WC, Husser D, Ebner M (2008) Fabrication process and product quality improvements in advanced gas reactor UCO kernels. In: Fourth international topical meeting on high temperature reactor technology, American Society of Mechanical Engineers, 177–188Google Scholar
  38. 38.
    Haas PA (1992) Formation of uniform liquid drops by application of vibration to laminar jets. Ind Eng Chem Res 31:959–967CrossRefGoogle Scholar
  39. 39.
    Kumar N, Sharma RK, Ganatra VR et al. (1991) Studies of the preparation of thoria and thoria-urania microspheres using an internal gelation process. Nucl Technol 96:169–177CrossRefGoogle Scholar
  40. 40.
    Ganatra VR, Kumar N, Suryanarayana S et al. (2008) Process and equipment development for the preparation of small size UO2 microspheres by jet entrainment technique. J Radioanal Nucl Chem 275:515–522.  https://doi.org/10.1007/s10967-007-6998-1 CrossRefGoogle Scholar
  41. 41.
    Ganguly C (1993) Sol-gel microsphere pelletization: a powder-free advanced process for fabrication of ceramic nuclear fuel pellets. Bull Mater Sci 16:509–522CrossRefGoogle Scholar
  42. 42.
    Pai RV, Mukerjee S, Vaidya V (2004) Fabrication of (Th,U)O2 pellets containing 3 mol% of uranium by gel pelletisation technique. J Nucl Mater 325:159–168.  https://doi.org/10.1016/j.jnucmat.2003.11.010 CrossRefGoogle Scholar
  43. 43.
    Sood DD (1988) Fuel chemistry division progress report for 1988. Bhabha Atomic Research Institute, Mumbai, Maharashtra, IndiaGoogle Scholar
  44. 44.
    Vaidya VN, Mukherjee SK, Joshi JK et al. (1987) A study of chemical parameters of the internal gelation based sol-gel process for uranium dioxide. J Nucl Mater 148:324–331CrossRefGoogle Scholar
  45. 45.
    Suryanarayana S, Kumar N, Bamankar YR et al. (1996) Fabrication of UO2 pellets by gel pelletization technique without addition of carbon as pore former. J Nucl Mater 230:140–147CrossRefGoogle Scholar
  46. 46.
    Pai RV, Dehadraya JV, Bhattacharya S et al. (2008) Fabrication of dense (Th,U)O2 pellets through microspheres impregnation technique. J Nucl Mater 381:249–258.  https://doi.org/10.1016/j.jnucmat.2008.07.044 CrossRefGoogle Scholar
  47. 47.
    Sood DD (2011) The role of sol–gel process for nuclear fuels—an overview. J Sol Gel Sci Technol 59:404–416.  https://doi.org/10.1007/s10971-010-2273-y CrossRefGoogle Scholar
  48. 48.
    Merrington AC, Richardson EG (1947) The break-up of liquid jets. Proceeedings Phys Soc 59:1–13CrossRefGoogle Scholar
  49. 49.
    Hunt RD, Collins JL, Johnson JA, Cowell BS (2017) Production of 75–150 µm and 75 µm of cerium dioxide microspheres in high yield and throughput using the internal gelation process. Ann Nucl Energy 105:116–120.  https://doi.org/10.1016/j.anucene.2017.03.010 CrossRefGoogle Scholar
  50. 50.
    Umbanhowar PB, Prasad V, Weitz DA (2000) Monodisperse emulsion generation via drop break off in a coflowing stream. Langmuir 16:347–351.  https://doi.org/10.1021/la990101e CrossRefGoogle Scholar
  51. 51.
    Than P, Preziosi L, Joseph D, Arney M (1988) Measurement of interfacial tension between immiscible liquids with the spinning rod tensiometer. J Colloid Interface Sci 124:552–559CrossRefGoogle Scholar
  52. 52.
    Utada AS, Chu L-Y, Fernandez-Nieves A et al. (2007) Dripping, jetting, drops, and wetting: the magic of microfluidics. MRS Bull 32:702–708CrossRefGoogle Scholar
  53. 53.
    Clanet C, Lasheras JC (1999) Transition from dripping to jetting. J Fluid Mech 383:307–326CrossRefGoogle Scholar
  54. 54.
    Ambravaneswaran B, Phillips SD, Basaran OA (2000) Theoretical analysis of a dripping faucet. Phys Rev Lett 85:5332–5335CrossRefGoogle Scholar
  55. 55.
    Ambravaneswaran B, Subramani H, Phillips S, Basaran O (2004) Dripping-jetting transitions in a dripping faucet. Phys Rev Lett 93.  https://doi.org/10.1103/PhysRevLett.93.034501
  56. 56.
    Cramer C, Fischer P, Windhab EJ (2004) Drop formation in a co-flowing ambient fluid. Chem Eng Sci 59:3045–3058.  https://doi.org/10.1016/j.ces.2004.04.006 CrossRefGoogle Scholar

Copyright information

© This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply 2018

Authors and Affiliations

  1. 1.Department of Nuclear Engineering and Radiological SciencesUniversity of MichiganAnn ArborUSA
  2. 2.Pacific Northwest National LaboratoryRichlandUSA

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