Clay minerals are hydrous aluminium phyllosilicates, sometimes with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations. Clays form flat hexagonal sheets similar to the micas. Clay minerals are common weathering products (including weathering of feldspar) and low temperature hydrothermal alteration products. Clay minerals are very common in fine grained sedimentary rocks such as shale, mudstone, and siltstone and in fine grained metamorphic slate and phyllite.
Clay minerals are usually (but not necessarily) ultrafine-grained (normally considered to be less than 2 micrometres in size on standard particle size classifications) and so may require special analytical techniques for their identification/study. These include x-ray diffraction, electron diffraction methods, various spectroscopic methods such as Mössbauer spectroscopy, infrared spectroscopy, and SEM-EDS or automated mineralogy solutions. These methods can be augmented by polarized light microscopy, a traditional technique establishing fundamental occurrences or petrologic relationships.
Clay minerals can be classified as 1:1 or 2:1, this originates from the fact that they are fundamentally built of tetrahedral silicate sheets and octahedral hydroxide sheets, as described in the structure section below. A 1:1 clay would consist of one tetrahedral sheet and one octahedral sheet, and examples would be kaolinite and serpentine. A 2:1 clay consists of an octahedral sheet sandwiched between two tetrahedral sheets, and examples are talc, vermiculite and montmorillonite.
Clay minerals include the following groups:
- Kaolin group which includes the minerals kaolinite, dickite, halloysite, and nacrite (polymorphs of Al2Si2O5(OH)4).
- Some sources include the kaolinite-serpentine group due to structural similarities (Bailey 1980).
- Smectite group which includes dioctahedral smectites such as montmorillonite and nontronite and trioctahedral smectites for example saponite. In 2013, analytical tests by the Curiosity rover found results consistent with the presence of smectite clay minerals on the planet Mars.
- Illite group which includes the clay-micas. Illite is the only common mineral.
- Chlorite group includes a wide variety of similar minerals with considerable chemical variation.
- Other 2:1 clay types exist such as sepiolite or attapulgite, clays with long water channels internal to their structure.
Mixed layer clay variations exist for most of the above groups. Ordering is described as random or regular ordering, and is further described by the term reichweite, which is German for range or reach. Literature articles will refer to a R1 ordered illite-smectite, for example. This type would be ordered in an ISISIS fashion. R0 on the other hand describes random ordering, and other advanced ordering types are also found (R3, etc.). Mixed layer clay minerals which are perfect R1 types often get their own names. R1 ordered chlorite-smectite is known as corrensite, R1 illite-smectite is rectorite.
Knowledge of the nature of clay became better understood in the 1930s with advancements in x-ray diffraction technology necessary to analyze the molecular nature of clay particles. Standardization in terminology arose during this period as well with special attention given to similar words that resulted in confusion such as sheet and plane.
Like all phyllosilicates, clay minerals are characterised by two-dimensional sheets of corner sharing SiO4 tetrahedra and/or AlO4 octahedra. The sheet units have the chemical composition (Al,Si)3O4. Each silica tetrahedron shares 3 of its vertex oxygen atoms with other tetrahedra forming a hexagonal array in two-dimensions. The fourth vertex is not shared with another tetrahedron and all of the tetrahedra "point" in the same direction; i.e. all of the unshared vertices are on the same side of the sheet.
In clays, the tetrahedral sheets are always bonded to octahedral sheets formed from small cations, such as aluminium or magnesium, and coordinated by six oxygen atoms. The unshared vertex from the tetrahedral sheet also forms part of one side of the octahedral sheet, but an additional oxygen atom is located above the gap in the tetrahedral sheet at the center of the six tetrahedral. This oxygen atom is bonded to a hydrogen atom forming an OH group in the clay structure. Clays can be categorized depending on the way that tetrahedral and octahedral sheets are packaged into layers. If there is only one tetrahedral and one octahedral group in each layer the clay is known as a 1:1 clay. The alternative, known as a 2:1 clay, has two tetrahedral sheets with the unshared vertex of each sheet pointing towards each other and forming each side of the octahedral sheet.
Bonding between the tetrahedral and octahedral sheets requires that the tetrahedral sheet becomes corrugated or twisted, causing ditrigonal distortion to the hexagonal array, and the octahedral sheet is flattened. This minimizes the overall bond-valence distortions of the crystallite.
Depending on the composition of the tetrahedral and octahedral sheets, the layer will have no charge, or will have a net negative charge. If the layers are charged this charge is balanced by interlayer cations such as Na+ or K+. In each case the interlayer can also contain water. The crystal structure is formed from a stack of layers interspaced with the interlayers.
- Amethyst Galleries. "The Clay Mineral Group." 2006. February 22, 2007
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- Moore, D. and R.C. Reynolds, Jr., 1997, X-Ray Diffraction and the Identification and Analysis of Clay Minerals, 2nd ed.: Oxford University Press, New York
- Bailey, S. W., 1980, Summary of recommendations of AIPEA nomenclature committee on clay minerals, American Mineralogist Volume 65, pages 1-7.