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Nature and Stability of Radiation-Induced Defects in Natural Kaolinites: New Results and a Reappraisal of Published Works

Published online by Cambridge University Press:  28 February 2024

Blandine Clozel ,
Thierry Allard  and
Jean-Pierre Muller
Blandine Clozel*
Affiliation:
Laboratoire de Minéralogie-Cristallographie, UA CNRS 09 Universités Paris 6 et 7, 4 Place Jussieu, 75252 Paris Cedex 05, France
Thierry Allard
Affiliation:
Laboratoire de Minéralogie-Cristallographie, UA CNRS 09 Universités Paris 6 et 7, 4 Place Jussieu, 75252 Paris Cedex 05, France
Jean-Pierre Muller
Affiliation:
Laboratoire de Minéralogie-Cristallographie, UA CNRS 09 Universités Paris 6 et 7, 4 Place Jussieu, 75252 Paris Cedex 05, France O.R.S.T.O.M., Département T.O.A., 75480 Paris Cedex 10, France
*
*Present address: BRGM, DRIGGP, Research Division, Geotechnical Engineering and Mineral Technology, Avenue de Concyr. B.P. 6009, 45060 Orleans Cedex 2, France
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Abstract

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A new appraisal of radiation-induced defects (RID) in natural kaolinite, i.e., positive trapped holes on oxygen atoms, has been undertaken using Q-band EPR spectra, recorded at 93 K, of irradiated annealed and oriented kaolinite samples originating from various environments. Three different centers were identified. Two of the centers, A- and A’-centers, are trapped holes on oxygen from Si-O bonds. They have a distinct signature and orthogonal orientation, i.e., perpendicular and parallel to the (ab) plane, respectively. The third center, the B-center, is a hole trapped on the oxygen bonding Al in adjacent octahedral positions (AlVI-O−-AlVI bridge). This confirmed some previous assignments from the literature, some others are no longer considered as valid.

A least squares fitting procedure is proposed to assess the RID concentration in any kaolinite. It allows a quantitative approach of the thermal stability of RID. Isochronal annealing shows that the thermal stability of the centers decreases in the order A, A′, B over the temperature range 0–450°C: (1) B-center is completely annealed above 300°C; (2) A′-center can be annealed by heating at 400°C for more than two hours; (3) A-center is stable up to 450°C. The activation energy and the magnitude of the mean half-life for A-center is evaluated through isothermal annealing at 350, 375 and 400°C, with Ea = 2.0 eV ± 0.2, and t½ > 1012 years at 300 K. The stability of A-center seems to decrease with increasing crystalline disorder. Nevertheless, it is high enough for radiation dosimetry using kaolinites from any environment on the Earth's surface.

Keywords

EPRKaoliniteRadiation induced defectsRID
Type
Research Article
Information
Clays and Clay Minerals , Volume 42 , Issue 6 , December 1994 , pp. 657 - 666
Copyright
Copyright © 1994, Clay Minerals Society

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