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Modeling Powder X-ray Diffraction Patterns of the Clay Minerals Society Kaolinite Standards: KGa-1, KGa-1b, and KGa-2

Published online by Cambridge University Press:  01 January 2024

B. A. Sakharov ,
V. A. Drits ,
D. K. McCarty  and
G. M. Walker
B. A. Sakharov
Affiliation:
Geological Institute, Russian Academy of Sciences, Pyzevskij per. D.7, 109017 Moscow, Russia
V. A. Drits
Affiliation:
Geological Institute, Russian Academy of Sciences, Pyzevskij per. D.7, 109017 Moscow, Russia
D. K. McCarty*
Affiliation:
Chevron Energy Technology Company (ETC), 3901 Briarpark, Houston, Texas 77042, USA
G. M. Walker
Affiliation:
Chevron Energy Technology Company (ETC), 3901 Briarpark, Houston, Texas 77042, USA
*
*E-mail address of corresponding author: dmccarty@chevron.com
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Abstract

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Three kaolinite reference samples identified as KGa-1, KGa-1b, and KGa-2 from the Source Clays Repository of The Clay Mineral Society (CMS) are used widely in diverse fields, but the defect structures have still not been determined with certainty. To solve this problem, powder diffraction patterns of the KGa-1, KGa-1b, and KGa-2 samples were modeled. In a kaolinite layer among three symmetrically independent octahedral sites named as A, B, and C and separated from each other by b/3 along the b parameter, the A and B sites are occupied by Al cations, whereas, the C sites located along the long diagonal of the oblique kaolinite unit cell are vacant. The layer displacement vectors t1 and t2 are related by a pseudo-mirror plane from defect-free 1Tc kaolinite enantiomorphs, whereas, the random interstratification within individual kaolinite crystallites creates right-hand and left-hand layer sub-sequences producing structural disorder. A third layer displacement vector, t0, located along the long diagonal of the oblique layer unit cell that contains the vacant octahedral site and coincides with the layer pseudo-mirror plane may exist. Thus, a structural model should be defined by the probability of t1, t2, and t0 layer displacement translations Wt1, Wt2, and Wt0, respectively, determined by simulated experimental X-ray diffraction (XRD) patterns. X-ray diffraction patterns were calculated for structures with a given content of randomly interstratified displacement vectors, and other XRD patterns were calculated for a physical mixture of crystallites having contrasting structural order with only C-vacant layers. The samples differ from each other by the content of high- and low-ordered phases referred to as HOK and LOK. The HOK phase has an almost defect-free structure in which 97% of the layer pairs are related by just the layer displacement vector t1 and only 3% of the layer pairs form the enantiomorphic fragments. In contrast, the LOK phases in the KGa-1, KGa-1b, and KGa-2 samples differ from HOK phases by the occurrence probabilities for the t1, t2, and t0 layer displacements. In addition, the LOK phases contain stacking faults that displace adjacent layers in arbitrary lengths and directions. Low XRD profile factors (Rp = 8-11%) support the defect structure models. Additional structural defects and previously published models are discussed.

Keywords

Computer simulationDefect structureKaoliniteX-ray diffraction.
Type
Article
Information
Clays and Clay Minerals , Volume 64 , Issue 3 , June 2016 , pp. 314 - 333
Copyright
Copyright © Clay Minerals Society 2016

References

Artioli, G. Bellotto, M. Gualtieri, A. and Pavese, A., 1995 Nature of structural disorder in natural kaolinites: a new model based on computer simulation of powder diffraction data and electrostatic energy calculation Clays and Clay Minerals 43 438–445.CrossRefGoogle Scholar
Bachmaf, S. and Merkel, B.J., 2011 Sorption of uranium (VI) at the clay mineral water interface Environmental Earth Sciences 63 925–934.CrossRefGoogle Scholar
Bailey, S.W., 1963 Polymorphism of the kaolinite minerals American Mineralogist 48 1196–1209.Google Scholar
Bailey, S.W., Bailey, S.W., 1988 Polytypism of 1:1 layer silicates Hydrous Phyllosilicates (Exclusive of Micas) Virginia, USA Mineralogical Society of America, Chantilly 9–27.CrossRefGoogle Scholar
Balan, E. Saitta, A.M. Mauri, F. and Calas, G., 2001 Firstprinciples modeling of the infrared spectrum of kaolinite American Mineralogist 86 1321–1330.CrossRefGoogle Scholar
Balan, E. Delattre, S. Guillaumet, M. and Salje, E.K.H., 2010 Low-temperature infrared spectroscopic study of OH-stretching modes in kaolinite and dickite American Mineralogist 95 1257–1266.CrossRefGoogle Scholar
Bellotto, M. Gualtieri, A. Artioli, G. and Clark, S.M., 1995 Kinetic study of the kaolinite-mullite reaction sequence Part I: Kaolinite dehydroxylation. Physics and Chemistry of Minerals 22 207–214.Google Scholar
Bish, D.L. and Chipera, S.J., 1998.Variation of kaolinite defect structure with particle size Proceedings of the 35th Annual Clay Minerals Society Meeting, Cleveland, OhioGoogle Scholar
Bish, D.L. and von Dreele, R.B., 1989 Rietveld refinement of non-hydrogen atomic positions in kaolinite Clays and Clay Minerals 37 289–296.CrossRefGoogle Scholar
Brindley, G.W., Brindley, G.W. and Brown, G., 1980 Order-disorder in clay mineral structure Crystal Structure of Clay Minerals and their X-ray identification London Mineralogical Society of Great Britain and Ireland 125–196.CrossRefGoogle Scholar
Brindley, G.W. and Nakahira, M., 1958 The kaolinite-mullite reaction Series: II Metakaolinite. Journal of the American Ceramic Society 42 314–318.Google Scholar
Brindley, G.W. and Robinson, K., 1946 The structure of kaolinite Mineralogical Magazine 27 242–253.CrossRefGoogle Scholar
Brindley, G.W. Kao, C.C. Harrison, J.L. Lipsicas, M. and Raythatha, R., 1986 Relation between structural disorder and other characteristics of kaolinites and dickites Clays and Clay Minerals 34 239–249.CrossRefGoogle Scholar
Bookin, A.S. Drits, V.A. Plançon, A. and Tchoubar, C., 1989 Stacking faults in kaolin-group minerals in the light of real structural features Clays and Clay Minerals 37 297–307.CrossRefGoogle Scholar
Chipera, S.J. and Bish, D.L., 2001 Baseline studies of The Clay Mineral Society Source Clays: Powder X-ray diffraction analyses Clays and Clay Minerals 49 398–409.CrossRefGoogle Scholar
Drits, V.A. and Derkowski, A., 2015 Kinetic behavior of partially dehydroxylated kaolinite American Mineralogist 100 883–896.CrossRefGoogle Scholar
Drits, V.A. and Tchoubar, C., 1990 X-ray Diffraction by Disordered Lamellar Structures Berlin, Heidelberg Springer-Verlag..CrossRefGoogle Scholar
Drits, V.A. Sakharov, B.A. Lindgreen, H. and Salyn, A., 1997 Sequential structural transformation of illite-smectite- vermiculite during diagenesis of Upper Jurassic shales from North Sea and Denmark Clay Minerals 32 351–372.CrossRefGoogle Scholar
Drits, V.A. Środoń, J. and Eberl, D.D., 1997 XRD measurements of mean crystallite thickness of illite and illite/smectite: Reappraisal of the Kubler index and the Scherrer equation Clays and Clay Minerals 45 461–475.CrossRefGoogle Scholar
Drits, V.A. Kameneva, M.Y. Sakharov, B.A. Dainyak, L.G. Tsipursky, S.I. Smoliar-Zviagina, B.B. Bookin, A.S. and Salyn, A.L., 1993.The actual structure of glauconites and related mica-like minerals NaukaGoogle Scholar
Drits, V.A. Sakharov, B.A. Dainyak, L.G. Salyn, A.L. and Lindgreen, H., 2002 Structural and chemical heterogeneity of illite-smectites from Upper Jurassic mudstones of East Greenland related to volcanic and weathered parent rocks American Mineralogist 87 1590–1607.CrossRefGoogle Scholar
Drits, V.A. Lindgreen, H. Sakharov, B.A. Jakobsen, H.J. Salyn, A.L. and Dainyak, L.G., 2002 Tobelitization of smectite during oil generation in oil-source shales Application to North Sea illite-tobelite-smectite-vermiculite. Clays and Clay Minerals 50 82–98.CrossRefGoogle Scholar
Drits, V.A. Derkowski, A. and McCarty, D.K., 2011 New insight into the structural transformation of partially dehydroxylated pyrophyllite American Mineralogist 96 153–171.CrossRefGoogle Scholar
Drits, V.A. Derkowski, A. and McCarty, D.K., 2011 Kinetics of thermal transformation of partially dehydroxylated pyrophyllite American Mineralogist 96 1504–1069.Google Scholar
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.CrossRefGoogle Scholar
Franco, F. Pérez-Maqueda, L.A. and Perez-Rodriguez, J., 2004 The effect of ultrasound on the particle size and structural disorder of a well ordered kaolinite Journal of Colloid and Interface Science 274 107–117.CrossRefGoogle ScholarPubMed
Frost, R.L. and Vassallo, A.M., 1996 The dihydroxylation of the kaolinite clay minerals using infrared emission spectroscopy Clays and Clay Minerals 44 635–651.CrossRefGoogle Scholar
Giese, R.F., 1982 Theoretical studies of the kaolinite minerals: Electrost atic calculations Bul letin de Minéralogie 105 417–424.CrossRefGoogle Scholar
Hinckley, D.N., 1963 Variability in "crystallinity" values among the kaolin deposits of the coastal plain of Georgia and South Carolina Clays and Clay Minerals 11 229–235.CrossRefGoogle Scholar
Johnston, C.T. Agnew, S.F. and Bish, D.L., 1990 Polarized single-crystal Fourier-transform infrared microscopy of Ouray dickite and Keokuk kaolinite Clays and Clay Minerals 38 573–583.CrossRefGoogle Scholar
Johnston, C.T. Kogel, J.E. Bish, D.L. Kogure, T. and Murray, H.H., 2008 Low-temperature FTIR study of kaolin-group minerals Clays and Clay Minerals 56 470–485.CrossRefGoogle Scholar
Kogure, T., 2011 Stacking disorder in kaolinite revealed by HRTEM: a review Clay Science 15 3–11.Google Scholar
Kogure, T. and Inoue, A., 2005 Determination of defect structures in kaolin minerals by high-resolution transmission electron microscopy (HRTEM) American Mineralogist 90 85–89.CrossRefGoogle Scholar
Kogure, T. Johnston, C.T. Kogel, J.E. and Bish, D., 2010 Stacking disorder in a sedimentary kaolinite Clays and Clay Minerals 58 63–72.CrossRefGoogle Scholar
Lanson, B. Sakharov, B.A. Claret, F. and Drits, V.A., 2009 Diagenetic smectite-to-illite transition in clay-rich sediments: a reappraisal of X-ray diffraction results using the multi-specimen method American Journal of Science 309 476–516.CrossRefGoogle Scholar
Lindgreen, H. Drits, V.A. Sakharov, B.A. Jakobsen, H.J. Salyn, A.L. Dainyak, L.G. and Krøyer, H., 2002 The structure and diagenetic transformation of illite-smectite and chlorite-smectite from North Sea Cretaceous-Tertiary chalk Clay Minerals 37 429–450.CrossRefGoogle Scholar
Madejová, J. and Komadel, P., 2001 Baseline studies of The Clay Mineral Society Source Clays: Infrared methods Clays and Clay Minerals 49 410–432.CrossRefGoogle Scholar
McCarty, D.K. Sakharov, B.A. and Drits, V.A., 2009 New insights into smectite illitization: A zoned K-bentonite revisited American Mineralogist 94 1653–1671.CrossRefGoogle Scholar
Mermut, A.R. and Cano, A.F., 2001 Baseline studies of The Clay Mineral Society Source Clays: Chemical analyses of major elements Clays and Clay Minerals 49 381–386.CrossRefGoogle Scholar
Moll, W.F. Jr., 2001 Baseline studies of The Clay Mineral Society Source Clays: Geological origin Clays and Clay Minerals 49 374–380.CrossRefGoogle Scholar
Murray, H.H., 1954 Structural variation of some kaolinites in relat ion to dehydroxylated hal loysite American Mineralogist 39 97–108.Google Scholar
Newnham, R.E., 1961 A refinement of the dickite structure and some remarks on polymorphism in kaolinite minerals Mineralogical Magazine 32 683–704.CrossRefGoogle Scholar
Paris, M., 2014 The two aluminum sites in the 27Al MAS NMR spectrum of kaolinite: Accurate determination of isotopic chemical shifts and quadrupolar interaction parameters American Mineralogist 99 393–400.CrossRefGoogle Scholar
Plançon, A. and Tchoubar, C., 1977 Determination of structural defects in phyllosilicates by X-ray powder diffraction- II Nature and proportion of defects in natural kaolinites. Clays and Clay Minerals 25 436–450.CrossRefGoogle Scholar
Plançon, A. and Zakharie, C., 1990 An expert system for the structural characterization of kaolinites Clay Minerals 25 249–260.CrossRefGoogle Scholar
Plançon, A. Giese, R.F. Snyder, R. Drits, V.A. and Bookin, A.S., 1989 Stacking faults in the kaolin-group mineraldefect structures of kaolinite Clays and Clay Minerals 37 203–210.CrossRefGoogle Scholar
Pruett, R.J. and Webb, H.L., 1993 Sampling and analysis of KGa-1b well crystallized kaolin source clay Clays and Clay Minerals 41 514–519.CrossRefGoogle Scholar
Reynolds, R.C. Jr., 1986 The Lorentz-polarization factor and preferred orientation in oriented clay aggregates Clays and Clay Minerals 34 359–367.CrossRefGoogle Scholar
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.CrossRefGoogle Scholar
Sakharov, B.A. Plançon, A. Lanson, B. and Drits, V.A., 2004 Influence of the outer surface layers of crystals on the X-ray diffraction intensity of basal reflections Clays and Clay Minerals 52 680–692.CrossRefGoogle Scholar
Schroth, B.K. and Sposito, G., 1997 Surface charge properties of kaolinite Clays and Clay Minerals 45 85–91.CrossRefGoogle Scholar
Sperinck, S. Raiteri, P. Marks, N. and Wright, K., 2011 Dehydroxylation of kaolinite to metakaolin — a molecular dynamics study Journal of Materials Chemistry 21 2118–2125.CrossRefGoogle Scholar
Suitch, P.R. and Young, R.A., 1983 Atom position in highly ordered kaolinite Clays and Clay Minerals 31 357–366.CrossRefGoogle Scholar
Sutheimer, S. Maurice, P.A. and Zhou, Q., 1999 Dissolution of well and poorly crystallized kaolinites: Al speciation and effects of surface characteristics American Mineralogist 84 620–628.CrossRefGoogle Scholar
Ufer, K. Kleeberg, R. and Monecke, T., 2015 Quantification of stacking disordered Si-Al layer silicates by the Rietveld method: application to exploration for high-sulphidation epithermal gold deposits Powder Diffraction 30 111–118.CrossRefGoogle Scholar
Van Olphen, H. and Fripiat, J.J., 1979 Data Handbook for Clay Minerals and Other Non-metallic Minerals Oxford, UK Pergamon Press.Google Scholar
White, C.E. Provis, J.L. Riley, D.P. Kearley, G.J. and van Deventer, J.S.J., 2009 What is the structure of kaolinite? Reconciling theory and experiment Journal Physical Chemistry 113 6756–6765.CrossRefGoogle ScholarPubMed
White, C.E. Provis, J.L. Proffen, T. Riley, D.P. and van Deventer, J.S.J., 2010 Density functional modeling of the local structure of kaolinite subjected to thermal dehydroxylation Journal of Physical Chemistry A 114 4988–4996.CrossRefGoogle ScholarPubMed
White, C.E. Kearley, G.J. Provis, J.L. and Riley, D.P., 2013 Inelastic neutron scattering analysis of the thermal decomposition of kaolinite to metakaolin Chemical Physics 427 82–86.CrossRefGoogle Scholar
White, C.E. Kearley, G.J. Provis, J.L. and Riley, D.P., 2013 Structure of kaolinite and influence of stacking faults: reconciling theory and experiment using inelastic neutron scattering analysis The Journal of Chemical Physics 138 194501–194507.CrossRefGoogle ScholarPubMed
Wu, W., 2001 Baseline studies of The Clay Mineral Society Source Clays: Colloid and surface phenomena Clays and Clay Minerals 49 446–452.CrossRefGoogle Scholar