Hostname: page-component-76fb5796d-dfsvx Total loading time: 0 Render date: 2024-04-25T09:18:51.976Z Has data issue: false hasContentIssue false

Characterization of modified kaolin from the Ranong deposit Thailand by XRD, XRF, SEM, FTIR and EPR techniques

Published online by Cambridge University Press:  09 July 2018

N. Worasith
Affiliation:
School of Bioresources and Technology, King Mongkut's University of Technology, Thonburi, Bangkhuntien, Bangkok, Thailand
B. A. Goodman
Affiliation:
Health and Environment Department, Environmental Resources & Technologies, Austrian Institute of Technology, A-2444 Seibersdorf, Austria
J. Neampan
Affiliation:
Department of Geology, Chulalongkorn University, Bangkok, Thailand
N. Jeyachoke
Affiliation:
School of Bioresources and Technology, King Mongkut's University of Technology, Thonburi, Bangkhuntien, Bangkok, Thailand
P. Thiravetyan*
Affiliation:
School of Bioresources and Technology, King Mongkut's University of Technology, Thonburi, Bangkhuntien, Bangkok, Thailand

Abstract

Various physical and analytical techniques (XRD, XRF, SEM, FTIR and EPR) have been used to investigate the effects of chemical and/or physical modification of Ranong kaolin, which has been proposed as a potential bleaching clay for vegetable oils. Acid treatment after grinding resulted in major changes compared with acid treatment of the original mineral sample or mechanical treatment alone. Previous work has shown that the combined treatments produce increases in surface area and new porous structures, and the present measurements show reductions in Al:Si ratios. These are accompanied by a major reduction in O–H stretching vibrations as a result of grinding, although acid treatment produced little subsequent effect on the O–H bands in the FTIR spectra. However, acid treatment resulted in a reduction in the Al–OH–Al bending vibrations and the appearance of Si–O bands associated with newly synthesized material; these effects were much greater with samples that had been ground prior to the acid treatment. There were appreciable qualitative differences in the way in which the EPR spectra of Fe and Mn were affected; the Fe signal was sensitive to mechanical treatment, but little subsequent change was induced by acid extraction, whereas the Mn peaks were sensitive to the both the pH and the chemical nature of the acid used. These results therefore indicate that the Fe and Mn are in different types of site in the kaolin structure. Little change was observed in the main oxygen-based free radical centre associated with Si atoms, but that associated with Al was lost as a result of the treatments. Such mineral characterization is of fundamental importance to understanding the modification of kaolins and their uses as adsorbents in the food and environmental sciences.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2011

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

On leave from Department of Chemistry, Faculty of Science and Technology, Rajamangala University of Technology Krungthep, 2 Nang Lin Chi Road, Soi Suan Plu, Sathorn, Bangkok, Thailand 10120.

Current address: State Key Laboratory for Conservation and Utilization of Subtropical Agro-Bioresources, Guangxi University, Nanning, 530004 Guangxi, Peoples' Republic of China. DOI: 10.1180/claymin.2011.046.4.539

References

Angel, B.R., Jones, J.P.E. & Hall, P.L. (1974) Studies of doped synthetic kaolinite I. Clay Minerals, 10, 247256.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 fitting at X- and Q-band frequencies. Clays and Clay Minerals, 47, 605616.Google Scholar
Balan, E., Lazzeri, M., Saitta, A.M., Allard, T., Fuchs, Y. & Mauri, F. (2005) First-principles study of OH-stretching modes in kaolinite, dickite, and nacrite. American Mineralogist, 90, 5060.Google Scholar
Belver, C., Munoz, M.A.B. & Vicente, M.A. (2002) Chemical activation of kaolinite under acid and alkaline conditions. Chemistry of Materials, 14, 20332043.Google Scholar
Bhattacharyya, K.G. & Sen Gupta, S. (2007) Influence of activation of kaolinite and montmorillonite on adsorptive removal of Cd(II) from water. Industrial & Engineering Chemistry Research, 46, 37343742.Google Scholar
Brindley, G.W. & Brown, G. (1980) Crystal Structures of Clay Minerals and their Identification. Mineralogical Society Monograph no. 5. Mineralogical Society, London.Google Scholar
Brindley, G.W., Cao, C.C., Harrison, J.L., Lipsicas, M. & Raythatha, R. (1986) Relation between structural disorder and other characteristics of kaolinites and dickites. Clays and Clay Minerals, 34, 239249.Google Scholar
Calas, G. (1988) Electron paramagnetic resonance. Pp. 513571 in: Spectroscopic Methods in Mineralogy and Geology, (Hawthorne, F.C., editor). Reviews in Mineralogy, Vol. 18, Mineralogical Society of America, Washington, DC.Google Scholar
Christidis, G.E., Scott, P.W. & Dunham, A.C. (1997) Acid activation and bleaching capacity of bentonites from the islands of Milos and Chios, Aegean, Greece. Applied Clay Science, 12, 329347.Google Scholar
Clozel, B., Calas, G., Muller, J.-P., Dran, J.-C. & Herve, A. (1990) Kaolinites as dosimeters: a new possibility of tracing radionuclides migration. Chemical Geology, 84, 259260.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, 657666.Google Scholar
Clozel, B., Gaite, J.-M. & Muller, J.-P. (1995) Al-O-Al paramagnetic defects in kaolinite. Physics and Chemistry of Minerals, 22, 351356.Google Scholar
Coyne, L.M., Blake, D.F., McKeever, S.W. & McKeever, S.W.S., editors (1998) Spectroscopic Characterization of Minerals and their Surfaces. ACS Symposium Series no. 415, American Chemical Society, Washington D.C. Google Scholar
Cuttler, A.H. (1981) Further studies of a ferrous iron doped synthetic kaolin: dosimetry of X-ray induced defects. Clay Minerals, 16, 6980.Google Scholar
Duzgoren-Aydin, N.S., Aydin, A. & Malpas, J. (2002) Distribution of clay minerals along a weathered pyroclastic profile, Hong Kong. Catena, 50, 1741.Google Scholar
Ekosse, G.-I. (2005) Fourier transform infrared spectrophotometry and X-ray powder diffractometry as complementary techniques in characterizing clay size fraction of kaolin. Journal of Applied Science & Environmental Management, 9, 4348.Google Scholar
Farmer, V.C. (1974) The Infrared Spectra of Minerals. Mineralogical Society, London.Google Scholar
Farmer, V.C. (1998) Differing effects of particle size and shape in the infrared and Raman spectra of kaolinite. Clay Minerals, 33, 601604.Google Scholar
Farmer, V.C. & Russell, J.D. (1964) The infrared spectra of layered silicates. Spectrochimica Ada, 20, 11491173.Google Scholar
Fialips, C.-L., Petit, S., Decarreau, A. & Beaufort, D.I (2000) Influence of synthesis pH on kaolinite crystallinity and surface properties. Clays and Clay Minerals, 48, 173184.Google Scholar
Frost, R.L., Makó, É., Kristóf, J., Horváth, E. & Kloprogge, J.T. (2001a) Mechanochemical treatment of kaolinite. Journal of Colloid and Interface Science, 239, 458466.Google Scholar
Frost, R.L., Makó, É., Kristóf, J., Horváth, E. & J.T., Kloprogge, E. (2001b) Modification of kaolinite surfaces by mechanochemical treatment. Langmuir, 17, 47314738.Google Scholar
Frost, R.L., Makó, É., Kristóf, J. & Kloprogge, J.T. (2002) Modification of kaolinite surfaces through mechanichemical treatment — a mid-IR and near-IR spectroscopic study. Spectrochimica Acta, 58A, 28492859.Google Scholar
Frost, R.L., Horváth, E., Makó, É., Kristóf, J. & Rédey, Á. (2003) Slow transformation of mechanically dehydroxylated kaolinite to kaolinite — an aged mechanochemically activated formamide-intercalated kaolinite study. Thermochimica Acta, 408, 103113.Google Scholar
Frost, R.L., Horváth, E., Makó, É. & Kristóf, J. (2004) Modification of low and high defect kaolinite surfaces: implications for kaolinite mineral processing. Journal of Colloid and Interface Science, 270, 337346.Google 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, 496505.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, 662667.Google Scholar
Gogoi, P.K. & Baruah, R. (2008) Fluoride removal from water by adsorption on acid activated kaolinite clay. Indian Journal of Chemical Technology, 15, 500503.Google Scholar
Golding, R.M., Singhasuwich, T. & Tennant, W.C. (1977) An analysis of the conditions for an isotropic gtensor in high-spin d5 systems. Molecular Physics, 34, 13431350.Google Scholar
Goodman, B.A. & Hall, P.L. (1994) Electron paramagnetic resonance spectroscopy. Pp. 173225 in: Clay Mineralogy: Physical Determinative Methods (Wilson, M.J., editor), Chapman & Hall, London.Google Scholar
Goodman, B.A., Russell, J.D., Fraser, A.R. & Woodhams, F.W.D. (1976) A Mossbauer and infra-red spectroscopic study of the structure of nontronite. Clays and Clay Minerals, 24, 5359.Google Scholar
Hawthorne, F.C., editor (1988) Spectroscopic Methods in Mineralogy and Geology. Reviews in Mineralogy, 18, Mineralogical Society of America. Washington D.C.Google Scholar
Hinckley, D.N. (1963) Variability in “crystallinity” values among the kaolin deposits of the coastal plain of Georgia and South Carolina. Proceedings of the 11* National Conference on Clays and Clay Minerals, 229-235.Google Scholar
Huertas, F.I., Chou, L. & Wollast, R. (1998) Mechanism of kaolinite dissolution at room temperature and pressure: Part 1. Surface speciation. Geochimica et Cosmochimica Acta, 62, 417431.Google Scholar
Jahn, H. & Teller, E. (1937). Stability of polyatomic molecules in degenerate electronic states. I. Orbital degeneracy. Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences, 161, 220235.Google Scholar
Joussein, E., Petit, S., Churchman, J., Theng, B., Righi, D. & Delvaux, B. (2005) Halloysite clay minerals — a review. Clay Minerals, 40, 383426.Google Scholar
Karaoğlu, M.H., Doğan, M. & Alkan, M. (2010) Removal of reactive blue 221 by kaolinite from aqueous solutions. Industrial & Engineering Chemistry Research, 49, 15341540.Google Scholar
Kuentag, C. (2001) Clay deposits in Thailand. Pp. 2843 in: The 2nd Workshop on Clays and their Applications, Department of Mineral Resources, Thailand.Google Scholar
Kuentag, C. & Wasuwanich, P. (1978) Clay. Economic Geology Bulletin No. 19, Economic Geology Division, Department of Mineral Resources, Thailand.Google Scholar
Langford, J.I. & Wilson, A.J.C. (1978). Scherrer after sixty years. A survey and some new results in the determination of crystallite size. Journal of Applied Crystallography, 11, 102113.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, 321335.Google Scholar
Mabbs, F.E. & Collison, D. (1992) Electron paramagnetic resonance of d- transition metal compounds. Elsevier, Amsterdam.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, 6672.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, 359364 Google Scholar
Martin, F., Micoud, P., Delmotte, L., Marichal, C., Le Dred, R., De Parseval, P., Mari, A., Fortune, J.-P., Salvi, S., Béziat, D., Grauby, O. & Ferret, J. (1999) The structural formula of talc from the Trimouns deposit, Pyrenees, France. The Canadian Mineralogist, 37, 9971006.Google Scholar
Meenakshi, S., Sairam Sundaram, C. & Sukumar, R. (2008) Enhanced fluoride sorption by mechanochemically- activated kaolinites. Journal of Hazardous Materials, 153, 164172.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, 113.Google Scholar
Miller, J.G. & Oulton, T.D. (1970) Prototrophy in kaolinite during percussive grinding. Clays and Clay Minerals, 18, 313323.Google Scholar
Murray, H.H. (2007) Applied Clay Mineralogy: Occurrences, Processing, and Application of Kaolins, Bentonites, Palygorskite-Sepiolite, and Common Clays. Elsevier, Amsterdam.Google Scholar
Nuntiya, A. & Prasanphan, S. (2006) The rheological behavior of kaolin suspensions. Chiang Mai Journal of Science, 33, 271281.Google Scholar
Panda, A.K., Mishra, B.G., Mishra, D.K. & Singh, R.K. (2010) Effect of sulphuric acid treatment on physicochemical characteristics of kaolin clay. Colloids and Surfaces A, 363, 98104.Google Scholar
Rancourt, D.G., Christie, I.A.D., Royer, M., Kodama, H., Robert, J.-L., Lalonde, A.E. & Murad, E. (1994) Determination of accurate [4]Fe3+, [6]Fe3+ and [6]Fe2+ site populations in synthetic annite by Mossbauer spectroscopy. American Mineralogist, 79, 5162.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, 8690.Google Scholar
Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Ada Crystallogriphica A, 32, 751767.Google Scholar
Steudel, A., Batenburg, L.F., Fischer, H.R., Weidler, P.G. & Emmerich, K. (2009) Alteration of non-swelling clay minerals and magadiite by acid activation. Applied Clay Science, 44, 95104.Google Scholar
Temuujin, J., Okada, K., MacKenzie, K.J.D. & Jadambaa, Ts. (2001) Characterization of porous silica prepared from mechanically amorphized kaolinite by selective leaching. Powder Technology, 121, 259262.Google Scholar
Title, R.S. (1963) Electron paramagnetic resonance spectra of Cr+, Mn++, and Fe3+ in cubic ZnS. Physical Review, 131, 623627.Google Scholar
Vágvölgyi, V., Kovacs, J., Horváth, E., Kristóf, J. & Makó, É. (2008) Investigation of mechanochemically modified kaolinite surfaces by thermoanalytical and spectroscopic methods. Journal of Colloid and Interfile Science, 317, 523529.Google Scholar
Vallyathan, V., Shi, X., Dalai, N.S., Irr, W. & Castranova, V. (1988) Generation of free radicals from freshly fractured silica dust. American Review of Respiration Disease, 138, 12131219.Google Scholar
van der Marel, H.W. & Krohmer, P. (1969) O-H stretching vibrations in kaolinite and related minerals. Contributions to Mineralogy and Petrology, 22, 7382.Google Scholar
Weeks, R.A. (1956) Paramagnetic resonance of lattice defects in quartz. Journal of Applied Physics, 27, 13761381.Google Scholar
Worasith, N., Goodman, B.A., Jeyashoke, N. & Thiravetyan, P. (2011) Decolorization of rice bran oil using modified kaolin. Journal of the American Oil Chemists’ Society. <doi: 10.1007/sl 1746-011-1872-2>>Google Scholar
Woumfo, D., Kamga, R., Figueras, F. & Njopwouo, D. (2007) Acid activation and bleaching capacity of some Cameroonian smectite soil clays. Applied Clay Science, 37, 149156.Google Scholar
Wu, Z., Li, C., Sun, X., Xu, X., Dai, B., Li, J. & Zhao, H. (2006) Characterization, acid activation and bleaching performance of bentonite from Xinjiang. Chinese Journal of Chemical Engineering, 14, 253258.Google Scholar