Phyllosilicates, and among them clay minerals, are of great interest not only for the scientific community but also for their potential applications in many novel and advanced areas. However, the correct application of these minerals requires a thorough knowledge of their crystal chemical properties. This chapter provides crystal chemical and structural details related to phyllosilicates and describes the fundamental features leading to their different behaviour in different natural or technical processes, as also detailed in other chapters of this book. Phyllosilicates, described in this chapter, are minerals of the (i) kaolin-serpentine group (e.g. kaolinite, dickite, nacrite, halloysite, hisingerite, lizardite, antigorite, chrysotile, amesite, carlosturanite, greenalite); (ii) talc and pyrophyllite group (e.g. pyrophyllite, ferripyrophyllite); (iii) mica group, with particular focus to illite; (iv) smectite group (e.g. montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite); (v) vermiculite group; (vi) chlorite group; (vii) some 2:1 layer silicates involving a discontinuous octahedral sheet and a modulated tetrahedral sheet such as kalifersite, palygorskite and sepiolite; (viii) allophane and imogolite and (ix) mixed layer structures with particular focus on illite-smectite.

Structure and Mineralogy of Clay Minerals

Hydration of the <1 μm size fraction of SWy-1 source clay (low-charge montmorillonite) was studied by modeling of X-ray diffraction (XRD) patterns recorded under controlled relative humidity (RH) conditions on Li-, Na-, K-, Mg-, Ca-, and Sr-saturated specimens. The quantitative description of smectite hydration, based on the relative proportions of different layer types derived from the fitting of experimental XRD patterns, was consistent with previous reports of smectite hydration. However, the coexistence of smectite layer types exhibiting contrasting hydration states was systematically observed, and heterogeneity rather than homogeneity seems to be the rule for smectite hydration. This heterogeneity can be characterized qualitatively using the standard deviation of the departure from rationality of the 00 l reflection series (ξ), which is systematically larger than 0.4 A when the prevailing layer type accounts for ~70% or less of the total layers (~25% of XRD patterns examined). In addition, hydration heterogeneities are not distributed randomly within smectite crystallites, and models describing these complex structures involve two distinct contributions, each containing different layer types that are interstratifed randomly. As a result, the different layer types are partially segregated in the sample. However, these two contributions do not imply the actual presence of two populations of particles in the sample.

XRD profile modeling also has allowed the refinement of structural parameters, such as the location of interlayer species and the layer thickness corresponding to the different layer types, for all interlayer cations and RH values. From the observed dependence of the latter parameter on the cation ionic potential ( v / r; v = cation valency and r = ionic radius) and on RH, the following equations were derived:

\batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \[Layer\ thickness\ (1W)\ =\ 12.556\ +\ 0.3525\ {\times}\ ({\nu}/\mathit{r}\ {-}\ 0.241)\ {\times}\ ({\nu}\ {\times}\ RH\ {-}\ 0.979)\] \end{document} 

\batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \[Layer\ thickness\ (2W)\ =\ 15.592\ +\ 0.6472\ {\times}\ ({\nu}/\mathit{r}\ {-}\ 0.839)\ {\times}\ ({\nu}\ {\times}\ RH\ {-}\ 1.412)\] \end{document} 

which allow the quantification of the increase of layer thickness with increasing RH for both 1W (one water) and 2W (two water) layers. In addition, for 2W layers, interlayer H2O molecules are probably distributed as a unique plane on each side of the central interlayer cation. This plane of H2O molecules is located at ~1.20 A from the central interlayer cation along the c* axis.

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Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns: Part I. Montmorillonite hydration properties

Publisher Summary This chapter describes structures and mineralogy of clay minerals. Phyllosilicates considered in this chapter ideally contain a continuous tetrahedral sheet. Each tetrahedron consists of a cation, T, coordinated to four oxygen atoms and linked to adjacent tetrahedra by sharing three corners (the basal oxygen atoms, Ob) to form an infinite two-dimensional hexagonal mesh pattern along the a, b crystallographic directions. The free corners (the tetrahedral apical oxygen atoms, Oa) of all tetrahedra point to the same side of the sheet and connect the tetrahedral and octahedral sheets to form a common plane with octahedral anionic position Ooct. Ooct anions lie near to the center of each tetrahedral 6-fold ring, but are not shared with tetrahedra. The 1:1 layer structure consists of the repetition of one tetrahedral and one octahedral sheet, while in the 2:1 layer structure one octahedral sheet is sandwiched between two tetrahedral sheets. In the 1:1 layer structure, the unit cell includes six octahedral sites (i.e., four cis and two trans-oriented octahedral) and four tetrahedral sites. Six octahedral sites and eight tetrahedral sites characterize the 2:1 layer unit cell. Structures with all the six octahedral sites occupied are known as “trioctahedral.” If only four of the six octahedra are occupied, the structure is referred to as “dioctahedral.” The structural formula is often reported based on the half unit-cell content—that is, it is based on three octahedral sites.

Chapter 2 Structures and Mineralogy of Clay Minerals

Terra rossa samples were taken from the B horizons of soil profiles and from cracks within limestone in Italy. The average annual temperature (AAT) of the sites ranged from 8.4 to 20.3°C and the average annual precipitation (AAP) from 511 to 3113 mm, with either a 5–6 month water deficit or a large water surplus. Goethite and hematite were identified in all the samples. Under a moist (> 1700 mm AAP) and cool (13°C AAT) climate, a xeric, hematitic pedoenvironment was preserved by the well-litified carbonate rock. Hematite occurred in trace amounts, even with an AAT of 8.4°C and an AAP of 3300 mm, confirming the specific role of the hard limestone on the pedoclimate of terra rossa. The lowest mean crystallite dimension of goethite and hematite was found in the samples from the wettest sites, and in these samples hematite was nearly free of Al substitution. Rubification in terra rossa appeared to be due to the specific pedoenvironment. The hematite cannot be considered a relict phase formed under another climate. Illite and kaolinite were the main clay minerals in samples from xeric sites whereas more weathered clays, such as Al-interlayered vermiculite, occurred in cool, moist sites. We postulate that the processes of rubification and vermiculitization could have taken place at the same time. The effects of layer charge magnitude and location on expansion were represented by an energy change (expansion energy: ΔEr) during the hydration and solvation processes. Plots of basal spacings versus ΔEr show a reasonable relationship; the spacings generally decrease stepwise as the value of ΔEr increases. The basal spacings of K-samples with glycerol solvation, Na-saturated and K-saturated samples at 100% RH are apt to contract stepwise with increasing value of ΔEr. For these samples, the figures showing the relationship between each expanded phase and the charge characteristics are obtained from the isoquants of ΔEr, given the boundary of the expanded phases. A behavior test using these figures may be combined with the Greene-Kelly test to estimate the amount and the location of the layer charge of common smectites.

Effects of Layer Charge, Charge Location, and Energy Change on Expansion Properties of Dioctahedral Smectites

The diagenetic evolution of kaolin and illitic minerals in sandstones is described here. The structural characterization of these minerals, the possible reaction pathways leading to their crystallization, and the origin of the fluids involved are discussed specifically.

While early precipitation of kaolinite is in general related to flushing by meteoric waters, subsequent diagenetic kaolinite-to-dickite transformation probably results from invasion by acidic fluids of organic origin. Dickite is the stable polytype in most sandstone formations and the kaolinite-to-dickite conversion is kinetically controlled.

The conventional model of kaolin illitization, assuming a thermodynamic control in a closed system, is discussed and compared to an alternative model in which illitization of kaolin is not coupled to dissolution of K-feldspar (Berger et al. , 1997). In the latter model, illite crystallization at the expense of kaolin implies that an energy barrier is overcome either by an increased K+/H+ activity ratio in solution or by a considerable temperature increase.

Authigenic kaolin and illitic minerals during burial diagenesis of sandstones: a review

The basal spacings of the homoionic (Na+, K+ and Ca2+) montmorillonite (T1) and saponite (SapCa-1) were examined by X-ray powder diffraction (XRD) analysis under the atmospheres of relative humidity (RH). RH was controlled by ReCX (Relative humidity Control system for X-ray diffractometer) precisely in the range of 0 to 100% RH. The variations of basal spacing were almost similar in both minerals at the range of 0 to 80% RH. However, noticeable differences between the hydration state of T1 and SapCa-1 were observed at 100% RH. It was explained that the differences were caused by charge localization and hydroxyl orientation in silicate layer because of these specimens having similar layer charge. In the region between 2 hydration states, irrational and asymmetrical reflections were observed. These reflections indicated interstratified structure of 2 hydration states. Especially at 60% RH, that the segregation structure was recognized. The existence of 2 phases indicates that there is heterogeneity in its charge density of layer.

https://www.jstage.jst.go.jp/article/jcssjclayscience1960/7/3/7_3_129/_pdf

Expansion characteristics of montmorillonite and saponite under various relative humidity conditions.

The structural model of illite/smectite interstratified mineral and the diagram for its identification

Infrared spectra of interstratified illite/smectite from hydrothermally altered tuffs (shinzan, japan) and diagenetic bentonites (kinnekulle, sweden)

X-ray diffraction experiment of a granular glauconitic clay and the computer simulation of the X-ray diffraction line profile of the clays from the Minamishiraoi Kuroko-type deposit, southwestern Hokkaido, Japan, were carried out to elucidate its mixed layer structure The mixed layer structure which shows an intermediate property of glauconite and smectite were evaluated to be of a random-type interstratification somewhat deviated from random interstratification towards the direction of segregation structure of glauconite and smectite, through comparison of the measured and the calculated X-ray diffraction line profiles

https://www.jstage.jst.go.jp/article/jcssjclayscience1960/9/2/9_2_53/_pdf

Takashi Watanabe

Papers

Expansion characteristics of montmorillonite and saponite under various relative humidity conditions.

The structural model of illite/smectite interstratified mineral and the diagram for its identification

Infrared spectra of interstratified illite/smectite from hydrothermally altered tuffs (shinzan, japan) and diagenetic bentonites (kinnekulle, sweden)

X-ray diffraction line profile of glauconitic clay from the minamishiraoi deposit and evaluation of its mixed-layer structure