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Title: The structure and ordering of zirconium and hafnium containing garnets studied by electron channelling, neutron diffraction and Moessbauer spectroscopy

Abstract

Garnets, A {sub 3} B {sub 2}C{sub 3}O{sub 12}, are an important group of minerals and have potential uses in the safe immobilisation of high-level nuclear waste. They have been found naturally to incorporate Zr, Ti and Fe, three elements of interest in the safe storage of nuclear waste. Kimzeyite, Ca{sub 3}(Zr,Ti){sub 2}(Si,Al,Fe){sub 3}O{sub 12}, is a naturally occurring garnet that contains Zr in a high percentage{approx}30 wt%. For such a material to be of potential immobilisation for nuclear waste the structure needs to be completely understood. Electron channelling studies have shown that the Zr/Ti cations are located on the Y-site, with the Al/Fe cations located on the Z-site. This work has investigated synthetic analogues of kimzeyite, Ca{sub 3}(Zr,Hf){sub 2}(Al,Fe,Si){sub 3}O{sub 12}, by neutron powder diffraction, using the C2 spectrometer at the Chalk River nuclear facility, coupled with {sup 57}Fe Moessbauer spectroscopy. Such work has allowed the structure of the synthetic material to be determined along with the distribution of cations across the X (CN=8), Y (CN=6), and Z (CN=4) sites. Results have shown that it is possible to synthesise Ca{sub 3}(Zr,Hf){sub 2}(Al,Fe,Si){sub 3}O{sub 12} with a range of Al/Fe ratios containing Zr and Hf. The Moessbauer data has indicatedmore » the Fe is located on the Z site. The structural analyses show that the unit cell changes linearly as a function of composition, and analysis of the disorder indicates that the Zr, Hf reside on the Y site and the Al, Fe, and Si reside on the Z site. - Graphical abstract: Dynamical diffraction pattern for kimzeyite along the 3 1 1 direction, used in the electron channelling analysis, and a bright field image of the sample investigated, the magnification is 25 000.« less

Authors:
 [1];  [2];  [1];  [3];  [4];  [4];  [5];  [6];  [7]
  1. Department of Earth Sciences, Downing Street, Cambridge, CB2 3EQ (United Kingdom)
  2. (United Kingdom), E-mail: k.r.whittle@shef.ac.uk
  3. (Australia)
  4. Department of Chemistry, The Open University, Walton Hall, Milton Keynes, MK7 6AA (United Kingdom)
  5. Materials Division, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234 (Australia)
  6. Institute of Geology of Ore Deposits, Russian Academy of Sciences (RAS), Staromonetnii Pereulok 35, Moscow 109017 (Russian Federation)
  7. Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States)
Publication Date:
OSTI Identifier:
21015711
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 2; Other Information: DOI: 10.1016/j.jssc.2006.12.006; PII: S0022-4596(06)00644-X; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALUMINIUM COMPOUNDS; CYANIDES; GARNETS; HAFNIUM COMPOUNDS; HIGH-LEVEL RADIOACTIVE WASTES; IRON COMPOUNDS; MOESSBAUER EFFECT; NEUTRON DIFFRACTION; OXIDES; SILICON COMPOUNDS; SYNTHETIC MATERIALS; TITANIUM COMPOUNDS; ZIRCONIUM COMPOUNDS

Citation Formats

Whittle, Karl R., Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield, S1 3JD, Lumpkin, Gregory R., Materials Division, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Berry, Frank J., Oates, Gordon, Smith, Katherine L., Yudintsev, Sergey, and Zaluzec, Nestor J. The structure and ordering of zirconium and hafnium containing garnets studied by electron channelling, neutron diffraction and Moessbauer spectroscopy. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.12.006.
Whittle, Karl R., Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield, S1 3JD, Lumpkin, Gregory R., Materials Division, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Berry, Frank J., Oates, Gordon, Smith, Katherine L., Yudintsev, Sergey, & Zaluzec, Nestor J. The structure and ordering of zirconium and hafnium containing garnets studied by electron channelling, neutron diffraction and Moessbauer spectroscopy. United States. doi:10.1016/j.jssc.2006.12.006.
Whittle, Karl R., Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield, S1 3JD, Lumpkin, Gregory R., Materials Division, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Berry, Frank J., Oates, Gordon, Smith, Katherine L., Yudintsev, Sergey, and Zaluzec, Nestor J. Thu . "The structure and ordering of zirconium and hafnium containing garnets studied by electron channelling, neutron diffraction and Moessbauer spectroscopy". United States. doi:10.1016/j.jssc.2006.12.006.
@article{osti_21015711,
title = {The structure and ordering of zirconium and hafnium containing garnets studied by electron channelling, neutron diffraction and Moessbauer spectroscopy},
author = {Whittle, Karl R. and Department of Engineering Materials, University of Sheffield, Sir Robert Hadfield Building, Mappin Street, Sheffield, S1 3JD and Lumpkin, Gregory R. and Materials Division, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234 and Berry, Frank J. and Oates, Gordon and Smith, Katherine L. and Yudintsev, Sergey and Zaluzec, Nestor J.},
abstractNote = {Garnets, A {sub 3} B {sub 2}C{sub 3}O{sub 12}, are an important group of minerals and have potential uses in the safe immobilisation of high-level nuclear waste. They have been found naturally to incorporate Zr, Ti and Fe, three elements of interest in the safe storage of nuclear waste. Kimzeyite, Ca{sub 3}(Zr,Ti){sub 2}(Si,Al,Fe){sub 3}O{sub 12}, is a naturally occurring garnet that contains Zr in a high percentage{approx}30 wt%. For such a material to be of potential immobilisation for nuclear waste the structure needs to be completely understood. Electron channelling studies have shown that the Zr/Ti cations are located on the Y-site, with the Al/Fe cations located on the Z-site. This work has investigated synthetic analogues of kimzeyite, Ca{sub 3}(Zr,Hf){sub 2}(Al,Fe,Si){sub 3}O{sub 12}, by neutron powder diffraction, using the C2 spectrometer at the Chalk River nuclear facility, coupled with {sup 57}Fe Moessbauer spectroscopy. Such work has allowed the structure of the synthetic material to be determined along with the distribution of cations across the X (CN=8), Y (CN=6), and Z (CN=4) sites. Results have shown that it is possible to synthesise Ca{sub 3}(Zr,Hf){sub 2}(Al,Fe,Si){sub 3}O{sub 12} with a range of Al/Fe ratios containing Zr and Hf. The Moessbauer data has indicated the Fe is located on the Z site. The structural analyses show that the unit cell changes linearly as a function of composition, and analysis of the disorder indicates that the Zr, Hf reside on the Y site and the Al, Fe, and Si reside on the Z site. - Graphical abstract: Dynamical diffraction pattern for kimzeyite along the 3 1 1 direction, used in the electron channelling analysis, and a bright field image of the sample investigated, the magnification is 25 000.},
doi = {10.1016/j.jssc.2006.12.006},
journal = {Journal of Solid State Chemistry},
number = 2,
volume = 180,
place = {United States},
year = {Thu Feb 15 00:00:00 EST 2007},
month = {Thu Feb 15 00:00:00 EST 2007}
}