skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing

Abstract

Melt processing of multi-phase ceramic waste forms offers potential advantages over traditional solid-state synthesis methods given both the prevalence of melters currently in use and the ability to reduce the possibility of airborne radionuclide contamination. In this work, multi-phase ceramics with a targeted hollandite composition of Ba1.0Cs0.3Cr1.0Al0.3Fe1.0Ti5.7O16 were fabricated by melt processing at 1675 °C and hot isostatic pressing (HIP) at 1250 and 1300 °C. X-ray diffraction analysis (XRD) confirmed hollandite as the major phase in all specimens. Zirconolite/pyrochlore peaks and weaker perovskite reflections were observed after melt processing, while HIP samples displayed prominent perovskite peaks and low-intensity zirconolite reflections. Melt processing produced specimens with large (>50 μm) well-defined hollandite grains, while HIP yielded samples with a more fine-grained morphology. Elemental analysis showed “islands” rich in Cs and Ti across the surface of the 1300 °C HIP sample, suggesting partial melting and partitioning of Cs into multiple phases. Photoemission data revealed multiple Cs 3d spin-orbit pairs for the HIP samples, with the lower binding energy doublets likely corresponding to Cs located in more leachable phases. Among all specimens examined, the melt-processed sample exhibited the lowest fractional release rates for Rb and Cs. However, the retention of Sr and Mo wasmore » greater in the HIP specimens.« less

Authors:
 [1];  [2]; ORCiD logo [2];  [3];  [1]
  1. Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)
  2. Clemson Univ., SC (United States)
  3. Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW (Australia)
Publication Date:
Research Org.:
Savannah River Site (SRS), Aiken, SC (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1427454
Alternate Identifier(s):
OSTI ID: 1548737
Report Number(s):
SRNL-STI-2017-00651
Journal ID: ISSN 0022-3115; PII: S0022311517314241; TRN: US1802593
Grant/Contract Number:  
AC09-08SR22470
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Nuclear Materials
Additional Journal Information:
Journal Volume: 502; Journal Issue: C; Journal ID: ISSN 0022-3115
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Dandeneau, Christopher S., Hong, Tao, Brinkman, Kyle S., Vance, Eric R., and Amoroso, Jake W.. Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing. United States: N. p., 2018. Web. https://doi.org/10.1016/j.jnucmat.2018.02.006.
Dandeneau, Christopher S., Hong, Tao, Brinkman, Kyle S., Vance, Eric R., & Amoroso, Jake W.. Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing. United States. https://doi.org/10.1016/j.jnucmat.2018.02.006
Dandeneau, Christopher S., Hong, Tao, Brinkman, Kyle S., Vance, Eric R., and Amoroso, Jake W.. Thu . "Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing". United States. https://doi.org/10.1016/j.jnucmat.2018.02.006. https://www.osti.gov/servlets/purl/1427454.
@article{osti_1427454,
title = {Comparison of structure, morphology, and leach characteristics of multi-phase ceramics produced via melt processing and hot isostatic pressing},
author = {Dandeneau, Christopher S. and Hong, Tao and Brinkman, Kyle S. and Vance, Eric R. and Amoroso, Jake W.},
abstractNote = {Melt processing of multi-phase ceramic waste forms offers potential advantages over traditional solid-state synthesis methods given both the prevalence of melters currently in use and the ability to reduce the possibility of airborne radionuclide contamination. In this work, multi-phase ceramics with a targeted hollandite composition of Ba1.0Cs0.3Cr1.0Al0.3Fe1.0Ti5.7O16 were fabricated by melt processing at 1675 °C and hot isostatic pressing (HIP) at 1250 and 1300 °C. X-ray diffraction analysis (XRD) confirmed hollandite as the major phase in all specimens. Zirconolite/pyrochlore peaks and weaker perovskite reflections were observed after melt processing, while HIP samples displayed prominent perovskite peaks and low-intensity zirconolite reflections. Melt processing produced specimens with large (>50 μm) well-defined hollandite grains, while HIP yielded samples with a more fine-grained morphology. Elemental analysis showed “islands” rich in Cs and Ti across the surface of the 1300 °C HIP sample, suggesting partial melting and partitioning of Cs into multiple phases. Photoemission data revealed multiple Cs 3d spin-orbit pairs for the HIP samples, with the lower binding energy doublets likely corresponding to Cs located in more leachable phases. Among all specimens examined, the melt-processed sample exhibited the lowest fractional release rates for Rb and Cs. However, the retention of Sr and Mo was greater in the HIP specimens.},
doi = {10.1016/j.jnucmat.2018.02.006},
journal = {Journal of Nuclear Materials},
number = C,
volume = 502,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

Table 1 Table 1: Targeted oxide concentrations for the baseline CAF-131 composition.*

Save / Share:

Works referenced in this record:

Materials Science of High-Level Nuclear Waste Immobilization
journal, January 2009

  • Weber, William J.; Navrotsky, Alexandra; Stefanovsky, Sergey
  • MRS Bulletin, Vol. 34, Issue 1
  • DOI: 10.1557/mrs2009.12

Cold crucible induction melter studies for making glass ceramic waste forms: A feasibility assessment
journal, January 2014


The SYNROC process: A geochemical approach to nuclear waste immobilization.
journal, January 1979


Disposal of high-level nuclear wastes: a geological perspective
journal, April 1985


Immobilisation of high level nuclear reactor wastes in SYNROC
journal, March 1979

  • Ringwood, A. E.; Kesson, S. E.; Ware, N. G.
  • Nature, Vol. 278, Issue 5701
  • DOI: 10.1038/278219a0

Comparative Study of Synroc-C Ceramics Produced by Hot-Pressing and Inductive Melting
journal, January 1996

  • Sobolev, I. A.; Stefanovsky, S. V.; Omelianenko, B. I.
  • MRS Proceedings, Vol. 465
  • DOI: 10.1557/PROC-465-371

The crystal structure of hollandite.
journal, January 1986


Preparation and characterization of (Ba,Cs)(M,Ti)8O16 (M=Al3+, Fe3+, Ga3+, Cr3+, Sc3+, Mg2+) hollandite ceramics developed for radioactive cesium immobilization
journal, June 2007


Synthesis and characterization of hollandite-type material intended for the specific containment of radioactive cesium
journal, October 2006

  • Leinekugel-le-Cocq, A. Y.; Deniard, P.; Jobic, S.
  • Journal of Solid State Chemistry, Vol. 179, Issue 10
  • DOI: 10.1016/j.jssc.2006.05.047

Thermochemistry of Barium Hollandites
journal, March 2013

  • Costa, Gustavo C. C.; Xu, Hongwu; Navrotsky, Alexandra
  • Journal of the American Ceramic Society, Vol. 96, Issue 5
  • DOI: 10.1111/jace.12224

Nuclear waste disposal—pyrochlore (A2B2O7): Nuclear waste form for the immobilization of plutonium and “minor” actinides
journal, June 2004

  • Ewing, Rodney C.; Weber, William J.; Lian, Jie
  • Journal of Applied Physics, Vol. 95, Issue 11
  • DOI: 10.1063/1.1707213

Ceramic Waste Forms for Actinides
journal, December 2006


Structural Transformations and Disordering in Zirconolite (CaZrTi 2 O 7 ) at High Pressure
journal, January 2013

  • Salamat, Ashkan; McMillan, Paul F.; Firth, Steven
  • Inorganic Chemistry, Vol. 52, Issue 3
  • DOI: 10.1021/ic302346g

Crystal Chemistry and Cation Ordering in Zirconolite 2M
journal, January 2006


Structural characterization of Nd-doped Hf-zirconolite Ca1−xNdxHfTi2−xAlxO7 ceramics
journal, December 2010


Analysis and Structural Determination of Nd-Substituted Zirconolite-4M
journal, March 1997

  • Coelho, A. A.; Cheary, R. W.; Smith, K. L.
  • Journal of Solid State Chemistry, Vol. 129, Issue 2
  • DOI: 10.1006/jssc.1996.7263

Polymorphic Transitions in Cerium-Substituted Zirconolite (CaZrTi2O7)
journal, July 2017


Chemical Structures and Performance of Perovskite Oxides
journal, July 2001

  • Pena, M.; Fierro, J.
  • Chemical Reviews, Vol. 101, Issue 7, p. 1981-2018
  • DOI: 10.1021/cr980129f

HIPed Tailored Hollandite Waste Forms for the Immobilization of Radioactive Cs and Sr
journal, May 2009


Melt processed multiphase ceramic waste forms for nuclear waste immobilization
journal, November 2014


Immobilisation of radioactive waste in glasses, glass composite materials and ceramics
journal, February 2006

  • Lee, W. E.; Ojovan, M. I.; Stennett, M. C.
  • Advances in Applied Ceramics, Vol. 105, Issue 1
  • DOI: 10.1179/174367606X81669

Melt processed single phase hollandite waste forms for nuclear waste immobilization: Ba1.0Cs0.3A2.3Ti5.7O16; A=Cr, Fe, Al
journal, January 2014


Wasteforms for waste from advanced reprocessing
journal, December 2016

  • Hsieh, Y-H; Horlait, D.; Humphry-Baker, S.
  • MRS Advances, Vol. 1, Issue 63-64
  • DOI: 10.1557/adv.2017.217

Structural Evolution in Hollandite Solid Solutions Across the A‐Site Compositional Range from Ba 1.33 Ga 2.66 Ti 5.34 O 16 to Cs 1.33 Ga 1.33 Ti 6.67 O 16
journal, August 2016

  • Xu, Yun; Feygenson, Mikhail; Page, Katharine
  • Journal of the American Ceramic Society, Vol. 99, Issue 12
  • DOI: 10.1111/jace.14443

Cold crucible induction melter test for crystalline ceramic waste form fabrication: A feasibility assessment
journal, April 2017


Crystal field effects in chromium and its partitioning in the mantle
journal, June 1975


Crystallization behavior during melt-processing of ceramic waste forms
journal, May 2016


Influence of Lubricants and Attrition Milling Parameters on the Quality of Zirconolite Ceramics, Consolidated by Hot Isostatic Pressing, for Immobilization of Plutonium
journal, February 2014

  • Squire, Jonathan; Maddrell, Ewan R.; Hyatt, Neil C.
  • International Journal of Applied Ceramic Technology, Vol. 12, Issue S2
  • DOI: 10.1111/ijac.12239

Zirconolite-rich titanate ceramics for immobilisation of actinides – Waste form/HIP can interactions and chemical durability
journal, December 2009


Hot isostatically pressed wasteforms for future nuclear fuel cycles
journal, April 2013


The evolution of ‘sol–gel’ chemistry as a technique for materials synthesis
journal, January 2016

  • Danks, A. E.; Hall, S. R.; Schnepp, Z.
  • Materials Horizons, Vol. 3, Issue 2
  • DOI: 10.1039/C5MH00260E

Structure of CsAlTiO4 – a compound with TiO4 tetrahedra
journal, November 1989

  • Gatehouse, B. M.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 45, Issue 11
  • DOI: 10.1107/S010827018900418X

    Works referencing / citing this record:

    Thermodynamic assessment of the hollandite high‐level radioactive waste form
    journal, April 2019

    • Utlak, Stephen A.; Besmann, Theodore M.; Brinkman, Kyle S.
    • Journal of the American Ceramic Society, Vol. 102, Issue 10
    • DOI: 10.1111/jace.16438

    Synthesis and phase structure of (Cs0.8−xBa0.4+x)(Al3+1.6+ xTi4+6.4− x)O16 ceramics using sol-spray pyrolysis route for immobilizing radioactive cesium
    journal, May 2019

    • Yang, Yushan; Xie, Xiaodong; Yang, Xiaoyong
    • Journal of Radioanalytical and Nuclear Chemistry, Vol. 320, Issue 3
    • DOI: 10.1007/s10967-019-06545-2