Impurity Ions Mn2+ and Fe3+ as Paired Spin Labels for the Study of Structural Transformations in Phyllosilicates by the ESR Method

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Abstract

Impurity paramagnetic ions Mn2+ and high spin Fe3+ (S = 5/2) are shown to be very informative “paired spin labels” to investigate structural transformations in natural aluminosilicate clay minerals by ESR spectroscopy. Second derivative ESR (SD ESR) enables to detect minor narrow lines of the ions against the background of intense broad lines of other paramagnetic impurities. Complex SD ESR spectra of the ions are explained by the Jahn-Teller effect and hyperfine interactions with OH-groups. SD ESR spectra before and after heating (620°C and 900°C) proved transformations of octahedral crystal cells accompanied by the loss of the OH-groups, displacement of the ions to equivalent positions.

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About the authors

A. G. Chetverikova

Orenburg State University

Author for correspondence.
Email: kr-727@mail.ru
Russian Federation, Orenburg

V. L. Berdinsky

Orenburg State University

Email: kr-727@mail.ru
Russian Federation, Orenburg

O. N. Kanygina

Orenburg State University

Email: kr-727@mail.ru
Russian Federation, Orenburg

E. K. Alidzhanov

Orenburg State University

Email: kr-727@mail.ru
Russian Federation, Orenburg

A. N. Nikiyan

Orenburg State University

Email: kr-727@mail.ru
Russian Federation, Orenburg

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Supplementary files

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2. Fig. 1. Atomic three-layer (T-O-T) structure of chlorite and elementary ideal octahedral lattice. The data are taken from [8].

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3. Fig. 2. Scattering of particles and their microaggregates (optical microscopy, reflection) in polymineral clay (a), individual particle with distinguishable layers (AFM scanning) (b).

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4. Fig. 3. X-ray fluorescence spectrum of the polymineral sample.

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5. Fig. 4. Diffractogram of polymineral clay, λCo = 0.17902 nm.

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6. Fig. 5. Overview EPR spectra of the clay sample in the initial state (a), after firing at temperatures 620 (b) and 900С (c): the g-factor values of the paramagnetic centers of iron and manganese are presented.

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7. Fig. 6. Second derivative EPR spectra of natural clay and diagrams of superfine interactions of Mn2+ ions. The values of the g-factor and the hyperfine interaction constant a are presented for three positions of ions inside the octahedral lattice of phyllosilicates.

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8. Fig. 7. Three positions of Mn2+ ions in the unit cell octahedron in the initial lattice (a); equilibrium position of Mn2+ ions in the unit cell octahedron after heating for 1 h at 900C (b).

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9. Fig. 8. EP EPR spectrum of clay after firing for 1 h at 900C and diagram of Mn2+ ions superfine interactions. The lower part of the figure shows the values of g-factor and STV constant, a.

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