Abstract
X-ray diffraction patterns of oriented mounts of clay minerals are often used in clay mineralogy for qualitative and quantitative purposes. Fequently occurring stacking defects, in particular, can be characterized by this technique. Modeling of these diffraction profiles has become an important tool in obtaining structural information about the nature of stacking order. Manual matching of calculated and observed patterns is time consuming and user dependent. Automatic refinement procedures are, therefore, desirable. An improved approach for the treatment of disordered layer structures within a Rietveld refinement is presented here. The recursive calculation of structure factors, similar to that of the simulation program DIFFaX, was introduced in the Rietveld code BGMN. Complete implementation is formulated within the interpreter language of the Rietveld code and is transparent as well as flexible. Such a method has opened the application of Rietveld refinement to patterns of oriented mounts where only basal reflections of stacking disordered structures were recorded. The DIFFaX code was used to simulate basal reflections of illite-smectite mixed layers (I-S) with different ratios of illitic and smectitic layers and with different degrees of long-range ordering (Reichweite). Rietveld refinements with these simulated patterns were used to evaluate the application of this new approach. Several I-S with different degrees of ordering were also chosen as tests for the refinement of basal reflections. The samples were prepared as standard airdried and ethylene glycol-solvated, oriented specimens. Realistic structural parameters were obtained for the composition and ordering of the I-S.
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References
Ahn, J.H. and Buseck, P.R. (1990) Layer-stacking sequences and structural disorder in mixed-layer illite-smectite: image simulations and HRTEM imaging. American Mineralogist, 75, 267–275.
Aplin, A.C., Matenaar, I.F., McCarty, D.K., and van Der Pluijm, B.A. (2006) Influence of mechanical compaction and clay mineral diagenesis on the microfabric and pore-scale properties of deep-water gulf of Mexico mudstones. Clays and Clay Minerals, 54, 500–514.
Bergmann, J., Friedel, P., and Kleeberg, R. (1998) BGMN — a new fundamental parameter based Rietveld program for laboratory X-ray sources, its use in quantitative analysis and structure investigations. CPD Newsletter, Commission of Powder Diffraction, International Union of Crystallography, 20, 5–8.
Bethke, C.M., Vergo, N., and Altaner, S.P. (1986) Pathways of smectite illitization. Clays and Clay Minerals, 34, 125–135.
Casas-Cabanas, M., Rodríguez-Carvajal, J., and Palacín, M.R. (2006) FAULTS, a new program for refinement of powder diffraction patterns from layered structures. Zeitschrift für Kristallographie, Supplement, 23, 243–248.
Cheary, R.W. and Coelho, A. (1992) Fundamental parameters approach to x-ray line-profile fitting. Journal of Applied Crystallography, 25, 109–121.
Dohrmann, R., Rüping, K.B., Kleber, M., Ufer, K., and Jahn, R. (2009) Variation of preferred orientation in oriented clay mounts as a result of sample preparation and composition. Clays and Clay Minerals, 57, 686–694.
Drits, V.A. and Tchoubar, C. (1990) X-ray Diffraction by Disordered Lamellar Structures. Springer-Verlag, Berlin, Heidelberg.
Drits, V.A., McCarty, D.K., and Zviagina, B.B. (2006) Crystal-chemical factors responsible for the distribution of octahedral cations over trans- and cis-sites in dioctahedral 2:1 layer silicates. Clays and Clay Minerals, 54, 131–152.
Ferrage, E., Lanson, B., Sakharov, B.A., and Drits, V.A. (2005a) Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns: Part I. Montmorillonite hydration properties. American Mineralogist, 90, 1358–1374.
Ferrage, E., Lanson, B., Malikova, N., Plançon, A., Sakharov, B.A., and Drits, V.A. (2005b) New Insights on the Distribution of Interlayer Water in Bi-Hydrated Smectite from X-ray Diffraction Profile Modeling of 00l Reflections. Chemistry of Materials, 17, 3499–3512.
Ferrage, E., Lanson, B., Sakharov, B.A., Geoffroy, N., Jacquot, E., and Drits, V.A. (2007) Investigation of dioctahedral smectite hydration properties by modeling of X-ray diffraction profiles: Influence of layer charge and charge location. American Mineralogist, 92, 1731–1743.
Gailhanou, H., van Miltenburg, J.C., Rogez, J., Olives, J., Amouric, M., Gaucher, E.C., and Blanc, P. (2007) Thermodynamic properties of anhydrous smectite MX-80, illite IMt-2 and mixed-layer illite-smectite ISCz-1 as determined by calorimetric methods. Part I: Heat capacities, heat contents and entropies. Geochimica et Cosmochimica Acta, 71, 5463–5473.
Gualtieri, A.F., Ferrari, S., Leoni, M., Grathoff, G., Hugo, R., Shatnawi, M., Paglia, G., and Billinge, S. (2008) Structural characterization of the clay mineral illite-1M. Journal of Applied Crystallography, 41, 402–415.
Howard, S.A. and Preston, K.D. (1989) Profile fitting of powder diffraction patterns. Pp. 217–275 in: Modern Powder Diffraction (D.L. Bish and J.E. Post, editors). Reviews in Mineralogy, 20, Mineralogical Society of America, Washington, D.C.
Jagodzinski, H. (1949) Eindimensionale Fehlordnung in Kristallen und ihr Einfluss auf die Röntgeninterferenzen. I. Berechnung des Fehlordnungsgrades aus den Röntgenintensitäten. Acta Crystallographica, 2, 201–207.
Leoni, M., Gualtieri, A.F., and Roveri, N. (2004) Simultaneous refinement of structure and microstructure of layered materials. Journal of Applied Crystallography, 37, 166–173.
Maegdefrau, E. and Hofmann, U. (1937) Glimmerartige Mineralien als Tonsubstanzen. Zeitschrift für Kristallographie, 98, 31–59.
Marshall, C.E. (1935) Layer lattices and the base exchange clays. Zeitschrift für Kristallographie. 91, 443–449.
Marshall, C.E. (1949) The Colloid Chemistry of the Silicate Minerals. Academic Press, New York.
Oie, T., Topol, I.A., and Burt, S.K. (1994) Ab initio and density functional calculations on ethylene glycol. Journal of Physical Chemistry, 98, 1121–1128.
Plançon, A. (2004) Consistent modeling of the XRD patterns of mixed-layer phyllosilicates. Clays and Clay Minerals, 52, 47–54.
Plançon, A. and Drits, V.A. (2000) Phase analysis of clays using an expert system and calculation programs for X-ray diffraction by two-and three-component mixed-layer minerals. Clays and Clay Minerals, 48, 57–62.
Plançon, A. and Roux, J. (2010) Software for the assisted determination of the structural parameters of mixed-layer phyllosilicates. European Journal of Mineralogy, 22, 733–740.
Reynolds, R.C., Jr. (1980) Interstratified clay minerals: Pp. 249–303 in: Crystal Structures of Clay Minerals and their X-ray Identification (G.W. Brindley and G. Brown, editors). Mineralogical Society, London.
Reynolds, R.C., Jr. (1985) NEWMOD: a computer program for calculation of one-dimensional diffraction patterns of mixed-layer clays. R.C. Reynolds, 9 Brook Rd., New Hampshire 03755, USA.
Ross, C.S. and Hendricks, S.B. (1945) Minerals of the montmorillonite group, their origin and relation to soils and clays. U.S. Geological Survey, Professional Paper 205-B, pp. 23–79.
Sakharov, B.A., Besson, G., Drits, V.A., Kameneva, M.Y., Salyn, A.L., and Smoliar, B.B. (1990) X-ray study of the nature of stacking faults in the structure of glauconites. Clay Minerals, 25, 419–435.
Sakharov, B.A., Lindgreen, H., Salyn, A.L., and Drits, V.A. (1999) Determination of illite-smectite structures using multispecimen X-ray diffraction profile fitting. Clays and Clay Minerals, 47, 555–566.
Środoń, J., Elsass, F., McHardy, W.J., and Morgan, D.J. (1992) Chemistry of illite-smectite inferred from TEM measurements of fundamental particles. Clay Minerals, 27, 137–158.
Taylor, R.M. and Norrish, K. (1966) The measurement of orientation distribution and its application to quantitative Xray diffraction analysis. Clay Minerals, 6, 127–142.
Treacy, M.M., Newsam, J.M., and Deem, M.W. (1991) A General Recursion Method for Calculating Diffracted Intensities From Crystals Containing Planar Faults. Proceedings of the Royal Society of London, A433, 499–520.
Treacy, M.M., Newsam, J.M., and Deem, M.W. (1993) Simulation of electron diffraction patterns from partially ordered layer lattices. Ultramicroscopy, 52, 512–522.
Ufer, K., Roth, G., Kleeberg, R., Stanjek, H., and Dohrmann, R. (2004) Description of X-ray powder pattern of turbostratically disordered layer structures with a Rietveld compatible approach. Zeitschrift für Kristallographie, 219, 519–527.
Ufer, K., Kleeberg, R., Bergmann, J., Curtius, H., and Dohrmann, R. (2008) Refining real structure parameters of disordered layer structures within the Rietveld method. Zeitschrift für Kristallographie Supplements, 27, 151–158.
Ufer, K., Kleeberg, R., Bergmann, J., and Dohrmann, R. (2012) Rietveld refinement of disordered illite-smectite mixed layer structures by a recursive algorithm. Part II: Powder pattern refinement and quantitative phase analysis. Clays and Clay Minerals, 60, 536–553.
Yuan, H. and Bish, D.L. (2010a) NEWMOD+, a new version of the NEWMOD program for interpreting X-ray powder diffraction patterns from interstratified clay minerals. Clays and Clay Minerals, 58, 318–326.
Yuan, H. and Bish, D.L. (2010b) Automated fitting of X-ray powder diffraction patterns from interstratified phyllosilicates. Clays and Clay Minerals, 58, 727–742.
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Ufer, K., Kleeberg, R., Bergmann, J. et al. Rietveld Refinement of Disordered Illite-Smectite Mixed-Layer Structures by a Recursive Algorithm. I: One-Dimensional Patterns. Clays Clay Miner. 60, 507–534 (2012). https://doi.org/10.1346/CCMN.2012.0600507
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DOI: https://doi.org/10.1346/CCMN.2012.0600507