BASELINE STUDIES OF THE CLAY MINERALS SOCIETY SOURCE CLAYS BY X-RAY PHOTOELECTRON SPECTROSCOPY (original) (raw)

Abstract

This paper presents an overview of the chemical analyses of the Clay Mineral Society Source Clays based on X-ray Photoelectron Spectroscopy. This technique does not require any detailed sample preparation and is therefore easy to perform. In contrast to other common chemical analytical techniques fluorine and chlorine can be analysed together with all the major elements. In addition, the high resolution spectra reveal some details about the local environment of different cations in the clay structure, such as the presence of water, distinction between octahedral and tetrahedral aluminium and the presence of two types of Mg in the octahedral sheets.

Figures (9)

Table 1. The Clay Minerals Society Source Clays analysed in this study.

Table 1. The Clay Minerals Society Source Clays analysed in this study.

Fig. 1. Peak identification in XPS survey scan of montmorillonite SWy-2. Baseline studies of the Clay Minerals Society Source Clays by X-ray photoelectron spectroscopy

Fig. 1. Peak identification in XPS survey scan of montmorillonite SWy-2. Baseline studies of the Clay Minerals Society Source Clays by X-ray photoelectron spectroscopy

Table 2a. Chemical compositions (in atom %) based on survey XPS analyses with Si as reference.

Table 2a. Chemical compositions (in atom %) based on survey XPS analyses with Si as reference.

Table 2b. Chemical composition data (in atom %) from Datahandbook for Clay Minerals and Other Non-metallic Minerals (van Olphen and Fripiat, 1979) and Clays and Clay Minerals special issue 49(5) Source Clays (2001). couple of marked differences. Due to the rather low signal strength of iron (Fe 2p) it is difficult to get a very reliable iron analysis and often an over- or under-estimation of the iron content is made. Furthermore, since XPS analyses binding electrons, it is difficult to distinguish between ferric and fer- rous iron in the crystal structure. In a number of clay samples (Swy-2, SAz-l, SCa-3 and VTx-1) fluorine was observed but the signal was too weak to obtain an accurate analysis of the amount of fluorine. Chlorine (2.2 at%) was observed for SapCa-2, which has not been observed before.

Table 2b. Chemical composition data (in atom %) from Datahandbook for Clay Minerals and Other Non-metallic Minerals (van Olphen and Fripiat, 1979) and Clays and Clay Minerals special issue 49(5) Source Clays (2001). couple of marked differences. Due to the rather low signal strength of iron (Fe 2p) it is difficult to get a very reliable iron analysis and often an over- or under-estimation of the iron content is made. Furthermore, since XPS analyses binding electrons, it is difficult to distinguish between ferric and fer- rous iron in the crystal structure. In a number of clay samples (Swy-2, SAz-l, SCa-3 and VTx-1) fluorine was observed but the signal was too weak to obtain an accurate analysis of the amount of fluorine. Chlorine (2.2 at%) was observed for SapCa-2, which has not been observed before.

Fig. 2. High resolution Si 2p spectra.

Fig. 2. High resolution Si 2p spectra.

" trace Mg was observed (Mg 1s 1303.99 eV), but is present in the interlayer and not in the clay sheets 2 vw=very weak Table 3. Binding energies (eV) of the major elements in the clay octahedral and tetrahedral sheets of the Source Clays analysed.

" trace Mg was observed (Mg 1s 1303.99 eV), but is present in the interlayer and not in the clay sheets 2 vw=very weak Table 3. Binding energies (eV) of the major elements in the clay octahedral and tetrahedral sheets of the Source Clays analysed.

Fig. 3. (a) High resolution Al 2p spectrum of beidellite SBCa-1. (b) High resolution Mg |s spectrum of montmorillonite SCa-3.

Fig. 3. (a) High resolution Al 2p spectrum of beidellite SBCa-1. (b) High resolution Mg |s spectrum of montmorillonite SCa-3.

x. 4. (a) High resolution O 1s spectrum of kaolinite KGa-1. (b) O 1s spectrum of beidellite SBCa-1. (c) O 1s spectrum of ripidolite CCa-1. (d) O 1s spectrum of attapulgite PFI-1. (e) O 1s spectrum of sepiolite SepNev-1. (f) O 1 spectrum of corrensite CorWa-1. Baseline studies of the Clay Minerals Society Source Clays by X-ray photoelectron spectroscopy

x. 4. (a) High resolution O 1s spectrum of kaolinite KGa-1. (b) O 1s spectrum of beidellite SBCa-1. (c) O 1s spectrum of ripidolite CCa-1. (d) O 1s spectrum of attapulgite PFI-1. (e) O 1s spectrum of sepiolite SepNev-1. (f) O 1 spectrum of corrensite CorWa-1. Baseline studies of the Clay Minerals Society Source Clays by X-ray photoelectron spectroscopy

‘ig. 5. (a) Na 1s spectrum of hectorite SHCa-1. (b) Ca 2p spec- Fig. 6. (a) F 1s spectra of Barasym Syn-l, sepiolite SepNev-1 and trum of nontronite NG-1. hectorite SHCa-1. (b) Cl 2p spectrum of saponite SapCa-2. The Ca 2p transitions for exchangeable Ca are split in two Gaussian shaped bands Ca 2pl and Ca 2p3 bands around 350.7 eV and 347.2 eV (e.g., nontronite NG-1, Figure 5b). Simi- ar to the exchangeable Ca, K is observed as the K 2p transi- ions K 2pl around 297.2 eV and K 2p3 around 294.3 eV but with very low intensity to noise ratio the bands are difficult to accurately fit. Though Adams and Evans (1979) used XPS o determine the cation exchange capacity (CEC) of beidellite using a variety of cations including Ca”* and K*, they did not report the binding energies for these atoms in the interlayer of he beidellite making comparison impossible. A similar type study on micas and illite-smectite clays by Johns and Gier 2001) also used XPS to determine interlayer cation ratios without providing binding energy details for these cations. In contrast K 2p binding energy values similar to those observed in this study have been reported for micas. Bhattacharyya Despite the fact that corrensite consists of a regular |: 1 in- terstratification of a trioctahedral chlorite and a trioctahedral smectite, this is not reflected in the O 1s spectrum that only shows a single transition at 532.01 eV for oxygen atoms in the structure and a single transition at 533.29 eV for the hydroxyl groups (Figure 4f). The ratio between oxygen and hydroxyls is about 1:2.5 which is slightly on the low side compared to the theoretical ratio of 1 :2. However the peak fit is rather poor and introduces a relatively large error in the determination of the ratio.

‘ig. 5. (a) Na 1s spectrum of hectorite SHCa-1. (b) Ca 2p spec- Fig. 6. (a) F 1s spectra of Barasym Syn-l, sepiolite SepNev-1 and trum of nontronite NG-1. hectorite SHCa-1. (b) Cl 2p spectrum of saponite SapCa-2. The Ca 2p transitions for exchangeable Ca are split in two Gaussian shaped bands Ca 2pl and Ca 2p3 bands around 350.7 eV and 347.2 eV (e.g., nontronite NG-1, Figure 5b). Simi- ar to the exchangeable Ca, K is observed as the K 2p transi- ions K 2pl around 297.2 eV and K 2p3 around 294.3 eV but with very low intensity to noise ratio the bands are difficult to accurately fit. Though Adams and Evans (1979) used XPS o determine the cation exchange capacity (CEC) of beidellite using a variety of cations including Ca”* and K*, they did not report the binding energies for these atoms in the interlayer of he beidellite making comparison impossible. A similar type study on micas and illite-smectite clays by Johns and Gier 2001) also used XPS to determine interlayer cation ratios without providing binding energy details for these cations. In contrast K 2p binding energy values similar to those observed in this study have been reported for micas. Bhattacharyya Despite the fact that corrensite consists of a regular |: 1 in- terstratification of a trioctahedral chlorite and a trioctahedral smectite, this is not reflected in the O 1s spectrum that only shows a single transition at 532.01 eV for oxygen atoms in the structure and a single transition at 533.29 eV for the hydroxyl groups (Figure 4f). The ratio between oxygen and hydroxyls is about 1:2.5 which is slightly on the low side compared to the theoretical ratio of 1 :2. However the peak fit is rather poor and introduces a relatively large error in the determination of the ratio.

Loading...

Loading Preview

Sorry, preview is currently unavailable. You can download the paper by clicking the button above.

References (45)

  1. Abdel-SAmAd, H. and WAtSon, P.R. (1997) An XPS study of the adsorp- tion of chromate on goethite (α-FeOOH). Applied Surface Science, 108, 371-377.
  2. AdAmS, J.M. and evAnS, S. (1979) Exchange and selective surface uptake of cations by layered silicates using X-ray photoelectron spectroscopy (XPS). Clays and Clay Minerals, 27, 248-252.
  3. Allen, G.C., eAStmAn, J.R., HAllAm, K.R., grAveling, G.J., rAgnArSdot- tir, K.V., and SKuSe, D.R. (1999) Mineral/reagent interactions: An X-ray photoelectron spectroscopic study of adsorption of reagents onto mix- tures of minerals. Clay Minerals, 34, 51-56.
  4. bArr, T.L., SeAl, S., He, H., and KlinoWSKi, J. (1995) X-ray photoelectron spectroscopic studies of kaolinite and montmorillonite. Vacuum, 46, 1391-1395.
  5. bHAttAcHAryyA, K.G. (1993) XPS study of mica surfaces. Journal of Elec- tron Spectroscopy and Related Phenomena, 63, 289-306.
  6. cAneSSon, P. (1982) ESCA studies of clay minerals. Developments in Sedi- mentology, 34, 211-226.
  7. dAlton, J.S., Allen, G.C., HAllAm, K.R., elton, N.J., Hooper, J.J., and SKuSe, D.R. (2002) An AFM and XPS investigation of the selective floc- culation of kaolinite from a mineral mixture. Special Publication-Royal Society of Chemistry, 282, 71-80.
  8. defoSSe, C. and rouxHet, P.G. (1980) Advanced chemical methods for soil and clay minerals research. Introduction to X-ray photoelectron spec- troscopy. NATO Advanced Study Institutes Series, Series C. Mathemati- cal and Physical Sciences, 63, 169-203.
  9. dillArd, J.G., emerSon, A.B., KoppelmAn, M.H., croWtHer, D.L., and ScHencK, C.V. (1982) Adsorption of metal ions and metal complexes on clay minerals: a study on the nature of bonding by X-ray photoelectron spectroscopy. Dep. Chem., Virginia Polytech. Inst. and State Univ., Blacksburg, VA, USA. 217 pp.
  10. dillArd, J.G., KoppelmAn, M.H., croWtHer, D.L., ScHencK, C.V., murrAy, J.W., and bAliStrieri, L. (1981) X-ray photoelectron spectroscopic (XPS) studies on the chemical nature of metal ions adsorbed on clays and min- erals. Adsorpt Aqueous Solutions, 227-240.
  11. dove, M.T., tHAyApArAm, S., Heine, V., and HAmmondS, K.D. (1996) The phenomenon of low Al-Si ordering temperatures in aluminosilicate framework structures. The American Mineralogist, 81, 349-362.
  12. du, J., Wu, D., xiAo, H., and li, P. (2011) Adsorption of fluoride on clay minerals and their mechanisms using X-ray photoelectron spectros- copy. Frontiers of Environmental Science & Engineering in China, 5, 212-226.
  13. ebinA, T., iWASAKi, T., cHAtterjee, A., KAtAgiri, M., and StucKy, G.D. (1997) Comparative study of XPS and DFT with reference to the distri- bution of Al in tetrahedral and octahedral sheets of phyllosilicates. The Journal of Physical Chemistry B, 101, 1125-1129.
  14. gier, S. and joHnS, W.D. (2000) Heavy metal-adsorption on micas and clay minerals studied by X-ray photoelectron spectroscopy. Applied Clay Science, 16, 289-299.
  15. gonzAleS-elipe, A.R., eSpinoS, J.P., munuerA, G., SAnz, J., and SerrAtoSA, J.M. (1988) Bonding-state characterization of constituent elements in phyllosilicate minerals by XPS and NMR. Journal of Physical Chemis- try, 92, 3471-3476.
  16. He, H., bArr, T.L., and KlinoWSKi, J. (1995) ESCA and Solid-State NMR studies of allophane. Clay Minerals, 30, 201-209.
  17. He, H., zHou, Q., froSt, R.L., Wood, B.J., duong, L.V., and Kloprogge, J.T. (2007) A X-ray photoelectron spectroscopy study of HDTMAB dis- tribution within organoclays. Spectrochimica Acta. Part A: Molecular Spectroscopy, 66, 1180-1188.
  18. joHnS, W.D. and gier, S. (2001) X-ray photoelectron spectroscopic study of layer-charge magnitude in micas and illite-smectite clays. Clay Miner- als, 36, 355-367.
  19. Kim, Y., cygAn, R.T., and KirKpAtricK, R.J. (1996) 133 Cs NMR and XPS investigation of cesium adsorbed on clay minerals and related phases. Geochimica et Cosmochimica Acta, 60, 1041-1052.
  20. Kloprogge, J.T. (2006) Spectroscopic studies of synthetic and natural beidellites: A review. Applied Clay Science, 31, 165-179.
  21. Kloprogge, J.T., duong, L.V., Wood, B.J., and froSt, R.L. (2006) XPS study of the major minerals in bauxite: Gibbsite, bayerite and (pseudo-)boehm- ite. Journal of Colloid and Interface Science, 296, 572-576.
  22. Kloprogge, J.T. and Wood, B.J. (2015) Chemical bonding and electronic structures of the Al 2 Si 2 O 5 (OH) 4 polymorphs kaolinite, dickite, nacrite, and halloysite by X-ray Photoelectron Spectroscopy. Clay Science, 19, 39-44.
  23. Kogel, J.E. and leWiS, S.A. (2001) Baseline studies of the clay minerals so- ciety Source Clays: Chemical analysis by Inductively Coupled Plasma- Mass Spectroscopy (ICP-MS). Clays and Clay Minerals, 49, 387-392.
  24. KOPPELMAN, M.H. (1976) An X-ray photoelectron spectroscopic study of the adsorption of metal ions on marine clay minerals.
  25. KoppelmAn, M.H. and dillArd, J.G. (1978) An X-ray photoelectron spec- troscopic (XPS) study of cobalt adsorbed on the clay mineral chlorite. Journal of Colloid and Interface Science, 66, 345-351.
  26. liu, Z.H. and broWn, N.M.D. (1998) XPS characterization of mica surfaces processed using a radio-frequency (rf) argon plasma. Journal of Physics. D, Applied Physics, 31, 1771-1781.
  27. mermut, A.R. and cAno, A.F. (2001) Baseline studies of the Clay Minerals Society Source Clays: Chemical analysis of major elements. Clays and Clay Minerals, 49, 381-386.
  28. moSSer, C., moSSer, A., romeo, M., petit, S., and decArreAu, A. (1992) Natural and synthetic copper phyllosilicates studied by XPS. Clays and Clay Minerals, 40, 593-599.
  29. nylund, A. and olefjord, I. (1994) Surface analysis of oxidized aluminium.
  30. Hydration of Al 2 O 3 and decomposition of Al(OH) 3 in a vacuum as studied by ESCA. Surface and Interface Analysis, 21, 283-289.
  31. oKAdA, K., KAmeSHimA, Y., and yASumori, A. (1998) Chemical shifts of silicon X-ray photoelectron spectra by polymerization structures of sili- cates. Journal of the American Ceramic Society, 81, 1970-1972.
  32. pAlin, E.J., dove, M.T., redfern, S.A.T., boSenicK, A., SAinz-diAz, C.I., and WArren, M.C. (2001) Computational study of tetrahedral Al-Si ordering in muscovite. Physics and Chemistry of Minerals, 28, 534-544.
  33. rAeburn, S.P., ilton, E.S., and veblen, D.R. (1997a) Quantitative determi- nation of the oxidation state of iron in biotite using X-ray photoelectron spectroscopy: I. Calibration. Geochimica et Cosmochimica Acta, 61, 4519-4530.
  34. rAeburn, S.P., ilton, E.S., and veblen, D.R. (1997b) Quantitative determi- nation of the oxidation state of iron in biotite using X-ray photoelectron spectroscopy: II. In situ analysis. Geochimica et Cosmochimica Acta, 61, 4531-4537.
  35. reynoldS, R.C.J. (1988) Mixed layer chlorite minerals. Pp. 601-630 in: Hydrous Phyllosilicates (Exclusive of Micas) (S.W. Bailey, (editor). Reviews in Mineralogy, vol. 19, Mineralogical Society of America, Chelsea.
  36. StrAHlin, A. and Hjertberg, T. (1994) Influence of surface composition on initial hydration of aluminium in boiling water. Applied Surface Science, 74, 263-275.
  37. StroHmeier, B.R. (1990) An ESCA method for determining the oxide thick- ness on aluminum alloys. Surface and Interface Analysis, 15, 51-56.
  38. StucKi, J.W., rotH, C.B., and bAitinger, W.E. (1976) Analysis of iron- bearing clay minerals by electron spectroscopy for chemical analysis (ESCA). Clays and Clay Minerals, 24, 289-292.
  39. Sun, D., li, B., li, Y., yu, C., zHAng, B., and fei, H. (2011) Characterization of exfoliated/delaminated kaolinite. Materials Research Bulletin, 46, 101-104.
  40. torreS SAncHez, R.M., bASAldellA, E.I., and mArco, J.F. (1999) The effect of thermal and mechanical treatments on kaolinite: Characterization by XPS and IEP measurements. Journal of Colloid and Interface Science, 215, 339-344.
  41. tSucHidA, T. and tAKAHASHi, T. (1994) X-ray photoelectron spectroscopic study of hydrated aluminas and aluminas. Journal of Materials Re- search, 9, 29219-22224.
  42. vAn olpHen, H. and fripiAt, J.J. (1979) Data handbook for Clay Minerals and Other Non-Metallic Materials. Pergamon Press, 346 pp. vAntelon, D., belKHou, R., biHAnnic, I., micHot, L.J., montArgeS-pelle- tier, E., and robert, J.-L. (2009) An XPEEM study of structural cation distribution in swelling clays. I. Synthetic trioctahedral smectites. Phys- ics and Chemistry of Minerals, 36, 593-602.
  43. vieirA coelHo, A.C., lAdriere, J., and poncelet, G. (2000) Nickel, iron- bearing clay minerals from Niquelandia deposit, Brazil 2. Behaviour under reducing conditions. Applied Clay Science, 17, 183-204.
  44. yAno, Y., nAKAno, M., and tAKAKurA, D. (1997) The X-ray photoelectron spectroscopy of copper complexes in the interlayer space of clay miner- als. Analytical Sciences, 13(Supplement), 355-358.
  45. yeongKyoo, K., cygAn, R.T., and KirKpAtricK, R.J. (1996) 133Cs NMR and XPS investigation of cesium adsorbed on clay minerals and related phases. Geochimica et Cosmochimica Acta, 60, 1041-1052.