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Influence of particle size on the paramagnetic components of kaolins from different origins

Published online by Cambridge University Press:  09 July 2018

N. Worasith
Affiliation:
Department of Science, Faculty of Science and Technology, Rajamangala University of TechnologyKrungthep, 2 Nang Lin Chi Road, Soi Suan Plu, Sathorn, Bangkok, Thailand
B. A. Goodman*
Affiliation:
State Key Laboratory for Conservation and Utilization of Subtropical Agro-Bioresources, Guangxi University, Nanning, 520004 Guangxi, China
*

Abstract

Electron paramagnetic resonance (EPR) spectra of different particle size fractions of four kaolins from diverse sources in North America, Europe and Asia have been investigated in order to characterize their paramagnetic properties and heterogeneity. There were major differences in the sources of the EPR signals from transition metals; V and Mn were structural, Fe was both structural and as associated oxides, and Cu was in the form of an adsorbed ion. The radiation-induced free radical signals commonly known as the A- and B-centres were observed in three of the deposits; however, in addition to the previously reported 27Al hyperfine structure associated with the B-centre, we also observed much smaller 27Al hyperfine structure on the g┴ feature of the A-centre. The other kaolin sample produced four free radical signals that have not previously been reported in kaolins. Each had substantial 1H hyperfine splitting; three are interpreted as corresponding to defect centres associated with Si-OH groups, and the other to a Si hole surrounded by protonated O atoms. The EPR spectra changed progressively with particle size, and measurements on the Asian specimens after grinding showed major differences in the Fe3+ signals from the same particle size fractions separated from the natural samples, thus supporting previous reports that grinding results in major structural changes in the minerals.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2012

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References

Abragam, A. & and Bleaney, B. (1970) Electron Paramagnetic Resonance of Transition Ions. Oxford University Press, Oxford, UK.Google Scholar
Allard, T., Muller, J.-P., Dran, J.-C. & Ménager, M.-T. (1994) Radiation-induced paramagnetic defects in natural kaolinites: Alpha dosimetry with ion beam irradiation. Physics and Chemistry of Minerals, 21, 85–96.Google Scholar
Angel, B.R. & Vincent, W.E.J. (1978) Electron spin resonance studies of iron oxides associated with the surface of kaolins. Clays and Clay Minerals, 26, 263–272.Google Scholar
Angel, B.R., Jones, J.P.E. & Hall, P.L. (1974) Electron spin resonance studies of doped synthetic kaolinite, I. Clay Minerals, 10, 247–255.Google Scholar
Bader, L.W. & Gesser, H.D. (1972) Hydrogen atom recombination on glass surfaces. Canadian Journal of Chemistry, 50, 2305–2312.CrossRefGoogle Scholar
Bailey, S.W. (1984) Structures of layer silicates. Pp. 1–124 in: Crystal Structures of Clay Minerals and their X-ray Identification (Brindley, G.W. & Brown, G., editors). Monograph 5, Mineralogical Society, London.Google Scholar
Balan, E., Allard, T., Boizot, B., Morin, G. & Muller, J.-P. (1999) Structural Fe3+ in natural kaolinites: new insights from electron paramagnetic resonance spectra fitting at X and Q-band frequencies. Clays and Clay Minerals, 47, 605–616.Google Scholar
Brindley, G.W., Chih-Chun Kao, T, Harrison, J.L., Lipsicas, M. & Raythatha, R. (1986) Relation between structural disorder and other characteristics of kaolinites and dickites. Clays and Clay Minerals, 34, 239–249.Google Scholar
Clozel, B., Allard, T. & Muller, J.-P. (1994) Nature and stability of radiation-induced defects in natural kaolinites: new results and a reappraisal of published works. Clays and Clay Minerals, 42, 657–666.Google Scholar
Clozel, B., Gaite, J.-M. & Muller, J.-P. (1995) Al-O-Al paramagnetic defects in kaolinite. Physics and Chemistry of Minerals, 22, 351–356.Google Scholar
Cuttler, A.H. (1980) The behaviour of a synthetic 57Fedoped kaolin: Mössbauer and electron paramagnetic resonance studies. Clay Minerals, 15, 429–444.CrossRefGoogle Scholar
Cuttler, A.H. (1981) Further studies of a ferrous iron doped synthetic kaolin: dosimetry of X-ray induced defects. Clay Minerals, 16, 69–80.Google Scholar
Delineau, T., Allard, T., Muller, J.-P., Barges, O., Yvon, J. & Cases, J.-M. (1994) FTIR reflectance vs. EPR studies of structural iron in kaolinites. Clays and Clay Minerals, 42, 308–320.Google Scholar
Frost, R.L., Makó, É., Kristóf, J., Horváth, E. & Kloprogge, J.T. (2001) Mechanochemical treatment of kaolinite. Journal of Colloid and Interface Science, 239, 458–466.CrossRefGoogle ScholarPubMed
Frost, R.L., Makó, É., Kristóf, J. & Kloprogge, J.T. (2002) Modification of kaolinite surfaces through mechanochemical treatment – a mid-R and near-IR spectroscopic study. Spectrochimica Acta A, 58, 2849–2859.Google Scholar
Fysh, S.A., Cashion, J.D. & Clark, P.E. (1983) Mössbauer effect studies of iron in kaolin. I. Structural iron. Clays and Clay Minerals, 31, 285–292.Google Scholar
Gaite, J.-M., Ermakoff, P. & Muller, J.-P. (1993) Characterization and origin of two Fe3+ EPR spectra in kaolinite. Physics and Chemistry of Minerals, 20, 242–247.CrossRefGoogle Scholar
Gaite, J.-M., Ermakoff, P., Allard, T. & Muller, J.-P. (1997) Paramagnetic Fe3+: a sensitive probe for disorder in kaolinite. Clays and Clay Minerals, 45, 496–505.Google Scholar
Gehring, A.U., Fry, I.V., Luster, J. & Sposito, G. (1993) The chemical form of vanadium (IV) in kaolinite. Clays and Clay Minerals, 41, 662–667.Google Scholar
Goodman, B.A. & Hall, P.L. (1994) Electron paramagnetic resonance spectroscopy. Pp. 173–225 in: Clay Mineralogy: Physical Determinative Methods (Wilson, M.J., editor). Chapman & Hall, London.Google Scholar
Goodman, B.A. & Raynor, J.B. (1970) Electron spin resonance of transition metal complexes. Advances in Inorganic Chemistry and Radiochemistry, 13, 135–362.Google Scholar
Herbillon, A.J., Mestdagh, M.M., Vielvoye, L. & Derouane, E. (1976) Iron in kaolinite with special reference to kaolinite from tropical soils. Clay Minerals, 11, 201–220.Google Scholar
Hyun, S.P. & Hayes, K.K. (2004) Copper(II) sorption mechanism on kaolinite: an EPR and EXAFS study. Journal of the Mineralogical Society of Korea 17, 1–9.Google Scholar
Hyun, S.P., Cho, Y.H. & Hahn, P.S. (2005) An electron paramagnetic resonance study of Cu(II) sorbed on kaolinite. Applied Clay Science, 30, 69–78.Google Scholar
Jen, C.K., Foner, S.N., Cochran, E.L. & Bowers, V.A. (1958) Electron spin resonance of atomic and molecular free radicals trapped at liquid helium temperature. Physical Review, 112, 1169–1182.Google Scholar
Jones, J.P.E., Angel, B.R. & Hall, P.L. (1974) Electron spin resonance studies of doped synthetic kaolinite II. Clay Minerals, 10, 257–269.Google Scholar
Kodama, H., Kotlyar, L.S. & Ripmeester, J.A. (1989) Quantification of crystalline and non-crystalline material in ground kaolinite by X-ray powder diffraction, infrared, solid-state nuclear magnetic resonance, and chemical dissolution analyses. Clays and Clay Minerals, 37, 364–370.Google Scholar
Kuentag, C. & Wasuwanich, P. (1978) Clay. Economic Geology Bulletin, no. 19. Economic Geology Division, Department of Mineral Resources, Thailand (in Thai).Google Scholar
Lombardi, G., Russell, J.D. & Keller, W.D. (1987) Compositional and structural variations in the size fractions of a sedimentary and a hydrothermal kaolin. Clays and Clay Minerals, 35, 321–335.Google Scholar
Lombardi, K., Guimarães, J.L., Mangrich, A.S., Mattoso, N., Abbate, M., Schreiner, W.H. & Wypych, F. (2002) Structural and morphological characterization of the PP-0559 kaolinite from the Brazilian Amazon region. Journal of the Brazilian Chemical Society, 13, 270–275.CrossRefGoogle Scholar
Ma, C. & Eggleton, R.A. (1999) Cation exchange capacity of kaolinite. Clays and Clay Minerals, 47, 174–180.Google Scholar
McBride, M.B. (1990) Electron spin resonance spectroscopy. Pp. 233–281 in: Instrumental Surface Analysis of Geological Materials (Perry, D.L., editor). VCH Publishers, New York.Google Scholar
McBride, M. B. (1995) On the natural Mn(II) EPR signal of SWy-1 montmorillonite. Clays and Clay Minerals, 43, 383–384.Google Scholar
McBride, M.B., Pinnavaia, T.J. & Mortland, M.M. (1975) Electron spin relaxation and the mobility of manganese(II) exchange sites in smectites. American Mineralogist, 60, 66–72.Google Scholar
McPhail, D.B. & Goodman, B.A. (1985) An electron paramagnetic resonance (EPR) study of copper(II)- diglycine complexes, Journal of Chemical Research, M2901–M2923, S276–S277.Google Scholar
Makó, É., Frost, R.L., Kristóf, J. & Horváth, E. (2001) The effect of quartz content on the mechanochemical activation of kaolinite. Journal of Colloid and Interface Science, 244, 359–364.Google Scholar
Malengreau, N., Muller, J.-P. & Calas, G. (1994) Fespeciation in kaolins: a diffuse reflectance study. Clays and Clay Minerals, 42, 137–147.Google Scholar
Meads, R.E. and Malden, P.J. (1975). Electron spin resonance in natural kaolinites containing Fe3+ and other transition metal ions. Clay Minerals, 10, 313–345.Google Scholar
Mestagh, M.M., Vielvoye, L. & Herbillon, A.J. (1980) Iron in kaolinite: II. The relationship between kaolinite crystallinity and iron content. Clay Minerals, 15, 1–13.Google Scholar
Miller, J.G. & Oulton, T.D. (1970) Prototrophy in kaolinite during percussive grinding. Clays and Clay Minerals, 18, 313–323.Google Scholar
Miranda-Trevino, J.C. & Coles, C.A. (2003) Kaolinite properties, structure and influence of metal retention on pH. Applied Clay Science, 23, 133–139.Google Scholar
Mosser, C., Boudeulle, M., Weber, F. & Pacquet, A. (1996) Ferriferous and vanadiferous kaolinites from the hydrothermal alteration halo of the Cigar Lake uranium deposit (Canada). Clay Minerals, 31, 291–299.Google Scholar
Muller, J.-P., Clozel, B., Ildefonse, P. & Calas, G. (1992) Radiation-induced defects in kaolinites: indirect assessment of radionuclide migration in the geosphere. Applied Geochemistry, 7, 205–216.Google Scholar
Petit, S., Decarreau, A., Mosser, S. M., Ehret, G. & Grauby, O. (1995) Hydrothermal synthesis (250ºC) of copper-substituted kaolinites. Clays and Clay Minererals, 43, 482–494.Google Scholar
Schossleler, P. M., Weidler, P. G. & Gehring, A. U. (1998) Octahedral sites in talc revisited; an EPR study. Clay Minerals, 33, 661–664.Google Scholar
Sengupta, P., Saikia, N.J., Bharali, D.J., Saikia, P.C. & Borthakur, P.C. (2006) ESR investigation of deferration treatment of iron-rich kaolinite clay from Deopani, Assam, India. Current Science, 91, 86–90.Google Scholar
Tanner, C.B. & Jackson, M.L. (1947) Nomographs of sedimentation times for soil particles under gravity or centrifugal acceleration. Soil Science Society of America Proceedings, 12, 60–65.Google Scholar
Velde, B. (1995) Origin and Mineralogy of Clays: Clay and the Environment. Springer-Verlag, New York.Google Scholar
Worasith, N., Goodman, B.A., Nempean, J., Jeyachoke, N. & Thiravetyan, P. (2011) Characterization of modified kaolin from the Ranong deposit Thailand studied by XRD, XRF, SEM, FTIR and EPR techniques. Clay Minerals, 46, 539–559.Google Scholar