clay mineral

any of a group of hydrous aluminum silicate minerals, as kaolinite, illite, and montmorillonite, that constitute the major portion of most clays.

[1945-50]

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Any of a group of important hydrous aluminum silicates with a layered structure and very small (less than 0.005 mm or microscopic) particle size.

They are usually the products of weathering. Clay minerals occur widely in such sedimentary rocks as mudstones and shales, in marine sediments, and in soils. Different geologic environments produce different clay minerals from the same parent rock. They are used in the petroleum industry (as drilling muds and as catalysts in refining) and in the processing of vegetable and mineral oils (as decolorizing agents).

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▪ rock

Introduction

      any of a group of important hydrous aluminum silicates with a layer (sheetlike) structure and very small particle size. They may contain significant amounts of iron, alkali metals, or alkaline earths.

General considerations

      The term clay is generally applied to (1) a natural material with plastic properties, (2) particles of very fine size, customarily those defined as particles smaller than two micrometres (7.9 × 10⁻⁵ inch), and (3) very fine mineral fragments or particles composed mostly of hydrous-layer silicates of aluminum, though occasionally containing magnesium and iron. Although, in a broader sense, clay minerals can include virtually any mineral of the above-cited particle size, the definition adapted here is restricted to represent hydrous-layer silicates and some related short-range ordered aluminosilicates, both of which occur either exclusively or frequently in very fine-size grades.

      The development of X-ray diffraction techniques in the 1920s and the subsequent improvement of microscopic and thermal procedures enabled investigators to establish that clays are composed of a few groups of crystalline minerals. The introduction of electron microscopic methods proved very useful in determining the characteristic shape and size of clay minerals. More recent analytical techniques such as infrared spectroscopy, neutron diffraction analysis, Mössbauer spectroscopy, and nuclear magnetic resonance spectroscopy have helped advance scientific knowledge of the crystal chemistry of these minerals.

      Clay minerals are composed essentially of silica, alumina or magnesia or both, and water, but iron substitutes for aluminum and magnesium in varying degrees, and appreciable quantities of potassium, sodium, and calcium are frequently present as well. Some clay minerals may be expressed using ideal chemical formulas as the following: 2SiO₂ · Al₂O₃ · 2H₂O (kaolinite), 4SiO₂ · Al₂O₃ · H₂O ( pyrophyllite), 4SiO₂ · 3MgO · H₂O ( talc), and 3SiO₂ · Al₂O₃ · 5FeO · 4H₂O ( chamosite). The SiO₂ ratio in a formula is the key factor determining clay mineral types. These minerals can be classified on the basis of variations of chemical composition and atomic structure into nine groups: (1) kaolin-serpentine (kaolinite, halloysite, lizardite, chrysotile), (2) pyrophyllite-talc, (3) mica (illite, glauconite, celadonite), (4) vermiculite, (5) smectite (montmorillonite, nontronite, saponite), (6) chlorite (sudoite, clinochlore, chamosite), (7) sepiolite-palygorskite, (8) interstratified clay minerals (e.g., rectorite, corrensite, tosudite), and (9) allophane-imogolite. Information and structural diagrams for these groups are given below.

      Kaolinite is derived from the commonly used name kaolin, which is a corruption of the Chinese Gaoling (Pinyin; Wade-Giles: Kao-ling) meaning “high ridge,” the name of a hill near Ching-te-chen where the occurrence of the mineral is known as early as the 2nd century BC. Montmorillonite and nontronite are named after the localities Montmorillon and Nontron, respectively, in France, where these minerals were first reported. Celadonite is from the French céladon (meaning grayish yellow-green) in allusion to its colour. Because sepiolite is a light and porous material, its name is based on the Greek word for cuttlefish, the bone of which is similar in nature. The name saponite is derived from the Latin sapon (meaning soap), owing to its appearance and cleaning ability. Vermiculite is from the Latin vermiculari (“to breed worms”), because of its physical characteristic of exfoliation upon heating, which causes the mineral to exhibit a spectacular volume change from small grains to long wormlike threads. Baileychlore, brindleyite, corrensite, sudoite, and tosudite are examples of clay minerals that were named after distinguished clay mineralogists—Sturges W. Bailey, George W. Brindley, Carl W. Correns, and Toshio Sudō, respectively.

Ralph E. Grim Hideomi Kodama

Structure

General features

     The structure of clay minerals has been determined largely by X-ray diffraction methods. The essential features of hydrous-layer silicates (phyllosilicate) were revealed by various scientists including Charles Mauguin, Linus C. Pauling, W.W. Jackson, J. West, and John W. Gruner through the late 1920s to mid-1930s. These features are continuous two-dimensional tetrahedral sheets of composition Si₂O₅, with SiO₄ tetrahedrons (Figure 1—>) linked by the sharing of three corners of each tetrahedron to form a hexagonal mesh pattern (Figure 2A—>). Frequently, silicon atoms of the tetrahedrons are partially substituted for by aluminum and, to a lesser extent, ferric iron. The apical oxygen at the fourth corner of the tetrahedrons, which is usually directed normal to the sheet, forms part of an adjacent octahedral sheet in which octahedrons are linked by sharing edges (Figure 3—>). The junction plane between tetrahedral and octahedral sheets consists of the shared apical oxygen atoms of the tetrahedrons and unshared hydroxyls that lie at the centre of each hexagonal ring of tetrahedrons and at the same level as the shared apical oxygen atoms (Figure 4—>). Common cations that coordinate the octahedral sheets are Al, Mg, Fe³⁺, and Fe²⁺; but occasionally Li, V, Cr, Mn, Ni, Cu, and Zn substitute in considerable amounts. If divalent cations (M²⁺) are in the octahedral sheets, the composition is M²⁺/₃ (OH)₂O₄ and all the octahedrons are occupied. If there are trivalent cations (M³⁺), the composition is M³⁺/₂ (OH)₂O₄ and two-thirds of the octahedrons are occupied, with the absence of the third octahedron. The former type of octahedral sheet is called trioctahedral, and the latter dioctahedral. If all the anion groups are hydroxyl ions in the compositions of octahedral sheets, the resulting sheets may be expressed by M²⁺(OH)₂ and M³⁺(OH)₃, respectively. Such sheets, called hydroxide sheets, occur singly, alternating with silicate layers in some clay minerals. brucite, Mg(OH)₂, and gibbsite, Al(OH)₃, are typical examples of minerals having similar structures. There are two major types for the structural “backbones” of clay minerals called silicate layers. The unit silicate layer formed by aligning one octahedral sheet to one tetrahedral sheet is referred to as a 1:1 silicate layer, and the exposed surface of the octahedral sheet consists of hydroxyls. In another type, the unit silicate layer consists of one octahedral sheet sandwiched by two tetrahedral sheets that are oriented in opposite directions and is termed a 2:1 silicate layer (Figure 5—>). These structural features, however, are limited to idealized geometric arrangements.

 Real structures of clay minerals contain substantial crystal strains and distortions, which produce irregularities such as deformed octahedrons and tetrahedrons rather than polyhedrons with equilateral triangle faces, ditrigonal symmetry modified from the ideal hexagonal surface symmetry, and puckered surfaces instead of the flat planes made up by the basal oxygen atoms of the tetrahedral sheet. One of the major causes of such distortions is dimensional “misfits” between the tetrahedral and octahedral sheets. If the tetrahedral sheet contains only silicon in the cationic site and has an ideal hexagonal symmetry, the longer unit dimension within the basal plane is 9.15 Å, which lies between the corresponding dimensions 8.6 Å of gibbsite and 9.4 Å of brucite. To fit the tetrahedral sheet into the dimension of the octahedral sheet, alternate SiO₄ tetrahedrons rotate (up to a theoretical maximum of 30°) in opposite directions to distort the ideal hexagonal array into a doubly triangular (ditrigonal) array (Figure 2B—>). By this distortion mechanism, tetrahedral and octahedral sheets of a wide range of compositions resulting from ionic substitutions can link together and maintain silicate layers. Among ionic substitutions, those between ions of distinctly different sizes most significantly affect geometric configurations of silicate layers.

      Another significant feature of layer silicates, owing to their similarity in sheet structures and hexagonal or near-hexagonal symmetry, is that the structures allow various ways to stack up atomic planes, sheets, and layers, which may be explained by crystallographic operations such as translation or shifting and rotation, thereby distinguishing them from polymorphs (polymorphism) (e.g., diamond-graphite and calcite-aragonite). The former involves one-dimensional variations, but the latter generally three-dimensional ones. The variety of structures resulting from different stacking sequences of a fixed chemical composition are termed polytypes. If such a variety is caused by ionic substitutions that are minor but consistent, they are called polytypoids.

kaolin- serpentine group

 Minerals of this groups are 1:1 layer silicates. Their basic unit of structure consists of tetrahedral and octahedral sheets in which the anions at the exposed surface of the octahedral sheet are hydroxyls (see Figure 4—>). The general structural formula may be expressed by Y_{2 - 3}Z₂O₅(OH)₄, where Y are cations in the octahedral sheet such as Al³⁺ and Fe³⁺ for dioctahedral species and Mg²⁺, Fe²⁺, Mn²⁺, and Ni²⁺ for trioctahedral species, and Z are cations in the tetrahedral sheet, largely Si and, to a lesser extent, Al and Fe³⁺. A typical dioctahedral species of this group is kaolinite, with an ideal structural formula of Al₂Si₂O₅(OH)₄. Kaolinite is electrostatically neutral and has triclinic (triclinic system) symmetry. Oxygen atoms and hydroxyl ions between the layers are paired with hydrogen bonding. Because of this weak bonding, random displacements between the layers are quite common and result in kaolinite minerals of lower crystallinity than that of the triclinic kaolinite. dickite and nacrite are polytypic varieties of kaolinite. Both of them consist of a double 1:1 layer and have monoclinic symmetry, but they distinguish themselves by different stacking sequences of the two 1:1 silicate layers.

       halloysite also has a composition close to that of kaolinite and is characterized by its tubular nature in contrast to the platy nature of kaolinite particles. Although tubular forms are the most common, other morphological varieties are also known: prismatic, rolled, pseudospherical, and platy forms. The structure of halloysite is believed to be similar to that of kaolinite, but no precise structure has been revealed yet. Halloysite has a hydrated form with a composition of Al₂Si₂O₅(OH)₄ · 2H₂O. This hydrated form irreversibly changes to a dehydrated variety at relatively low temperatures (60° C) or upon being exposed to conditions of low relative humidity. The dehydrated form has a basal spacing about the thickness of a kaolinite layer (approximately 7.2 Å), and the hydrated form has a basal spacing of about 10.1 Å. The difference of 2.9 Å is approximately the thickness of a sheet of water one molecule thick. Consequently, the layers of halloysite in the hydrated form are separated by monomolecular water layers that are lost during dehydration.

      In trioctahedral magnesium species, chrysotile, antigorite, and lizardite are commonly known; the formula of these three clay minerals is Mg₃Si₂O₅(OH)₄. Chrysotile crystals have a cylindrical roll morphology, while antigorite crystals exhibit an alternating wave structure. These morphological characteristics may be attributed to the degree of fit between the lateral dimensions of the tetrahedral and octahedral sheets. On the other hand, lizardite crystals are platy and often have a small amount of substitution of aluminum or ferric iron for both silicon and magnesium. This substitution appears to be the main reason for the platy nature of lizardite. Planar polytypes of the trioctahedral species are far more complicated than those of dioctahedral ones, owing to the fact that the trioctahedral silicate layer has a higher symmetry because all octahedral cationic sites are occupied. In addition, recent detailed structural investigations have shown that there are considerable numbers of hydrous-layer silicates whose structures are periodically perturbed by inversion or revision of SiO₄ tetrahedrons. Modulated structures therefore produce two characteristic linkage configurations: strips and islands. Antigorite is an example of the strip configuration in the modulated 1:1 layer silicates. Greenalite, a species rich in ferrous iron, also has a modulated layer structure containing an island configuration.

pyrophyllite- talc group

 Minerals of this group have the simplest form of the 2:1 layer with a unit thickness of approximately 9.2 to 9.6 Å—i.e., the structure consists of an octahedral sheet sandwiched by two tetrahedral sheets (Figure 5B—>). Pyrophyllite and talc represent the dioctahedral and trioctahedral members, respectively, of the group. In the ideal case, the structural formula is expressed by Al₂Si₄O₁₀(OH)₂ for pyrophyllite and by Mg₃Si₄O₁₀(OH)₂ for talc. Therefore, the 2:1 layers of these minerals are electrostatically neutral and are held together with van der Waals bonding. One-layer triclinic and two-layer monoclinic forms are known for polytypes of pyrophyllite and talc. The ferric iron analogue of pyrophyllite is called ferripyrophyllite.

mica mineral group

      Mica minerals have a basic structural unit of the 2:1 layer type like pyrophyllite and talc, but some of the silicon atoms (ideally one-fourth) are always replaced by those of aluminum. This results in a charge deficiency that is balanced by potassium ions between the unit layers. The sheet thickness (basal spacing or dimension along the direction normal to the basal plane) is fixed at about 10 Å. Typical examples are muscovite, KAl₂(Si₃Al)O₁₀(OH)₂, for dioctahedral species, and phlogopite, KMg₃(Si₃Al)O₁₀(OH)₂, and biotite, K(Mg, Fe)₃(Si₃Al)O₁₀(OH)₂, for trioctahedral species. (Formulas rendered may vary slightly due to possible substitution within certain structural sites.) Various polytypes of the micas are known to occur. Among them, one-layer monoclinic (1M), two-layer monoclinic (2M, including 2M₁ and 2M₂), and three-layer trigonal (3T) polytypes are most common. The majority of clay-size micas are dioctahedral aluminous species; those similar to muscovite are called illite and generally occur in sediments. The illites are different from muscovite in that the amount of substitution of aluminum for silicon is less; sometimes only one-sixth of the silicon ions are replaced. This reduces a net unbalanced-charge deficiency from 1 to about 0.65 per unit chemical formula. As a result, the illites have a lower potassium content than the muscovites. To some extent, octahedral aluminum ions are replaced by magnesium (Mg²⁺) and iron ions (Fe²⁺, Fe³⁺). In the illites, stacking disorders of the layers are common, but their polytypes are often unidentifiable.

      Celadonite and glauconite are ferric iron-rich species of dioctahedral micas. The ideal composition of celadonite may be expressed by K(Mg, Fe³⁺)(Si_{4 - x}Al_x)O₁₀(OH)₂, where x = 0–0.2. Glauconite is a dioctahedral mica species with tetrahedral Al substitution greater than 0.2 and octahedral Fe³⁺ or R³⁺ (total trivalent cations) greater than 1.2. Unlike illite, a layer charge deficiency of celadonite and glauconite arises largely from the unbalanced charge due to ionic substitution in the octahedral sheets.

vermiculite

      The vermiculite unit structure consists of sheets of trioctahedral mica or talc separated by layers of water molecules; these layers occupy a space about two water molecules thick (approximately 4.8 Å). Substitutions of aluminum cations (Al³⁺) for silicon cations (Si⁴⁺) constitute the chief imbalance, but the net charge deficiency may be partially balanced by other substitutions within the mica layer; there is always a residual net charge deficiency commonly in the range from 0.6 to 0.8 per O₁₀(OH)₂. This charge deficiency is satisfied with interlayer cations that are closely associated with the water molecules between the mica layers. In the natural mineral, the balancing cation is magnesium (Mg²⁺). The interlayer cation, however, is readily replaced by other inorganic and organic cations. A number of water molecules are related to the hydration state of cations located at the interlayer sites. Therefore, the basal spacing of vermiculite changes from about 10.5 to 15.7 Å, depending on relative humidity and the kind of interlayer cation. Heating vermiculite to temperatures (depending on its crystal size) as high as 500° C drives the water out from between the mica layers, but the mineral quickly rehydrates at room temperature to maintain its normal basal spacing of approximately 14 to 15 Å if potassium or ammonium ions are not present in the interlayer sites. It has been reported that some dioctahedral analogues of vermiculite occur in soils.

Smectite

      The structural units of smectite can be derived from the structures of pyrophyllite and talc. Unlike pyrophyllite and talc, the 2:1 silicate layers of smectite have a slight negative charge owing to ionic substitutions in the octahedral and tetrahedral sheets. The net charge deficiency is normally smaller than that of vermiculite—from 0.2 to 0.6 per O₁₀(OH)₂—and is balanced by the interlayer cations as in vermiculite. This weak bond offers excellent cleavage between the layers. The distinguishing feature of the smectite structure is that water and other polar molecules (in the form of certain organic substances) can, by entering between the unit layers, cause the structure to expand in the direction normal to the basal plane. Thus this dimension may vary from about 9.6 Å, when there are no polar molecules between the unit layers, to nearly complete separation of the individual layers.

      The structural formula of smectites of the dioctahedral aluminous species may be represented by (Al_{2 - y}Mg²⁺/_y)(Si_{4 - x}Al_x)O₁₀(OH)₂M⁺/_{x + y} · nH₂O, where M⁺ is the interlayer exchangeable cation expressed as a monovalent cation and where x and y are the amounts of tetrahedral and octahedral substitutions, respectively (0.2 ≤ x + y ≤ 0.6). The smectites with y > x are called montmorillonite and those with x > y are known as beidellite. In the latter type of smectites, those in which ferric iron is a dominant cation in the octahedral sheet instead of aluminum and magnesium, are called nontronite. Although less frequent, chromium (Cr³⁺) and vanadium (V³⁺) also are found as dominant cations in the octahedral sheets of the beidellite structure, and chromium species are called volkonskoite. The ideal structural formula of trioctahedral ferromagnesian smectites, the series saponite through iron saponite, is given by (Mg, Fe²⁺)₃(Si_{4 - x}Al_x)O₁₀(OH)₂M⁺/_x · nH₂O. The tetrahedral substitution is responsible for the net charge deficiency in the smectite minerals of this series. Besides magnesium and ferrous iron, zinc, cobalt, and manganese are known to be dominant cations in the octahedral sheet. Zinc dominant species are called sauconite. There are other types of trioctahedral smectites in which the net charge deficiency arises largely from the imbalanced charge due to ionic substitution or a small number of cation vacancies in the octahedral sheets or both conditions. Ideally x is zero, but most often it is less than 0.15. Thus, the octahedral composition varies to maintain similar amounts of the net charge deficiency as those of other smectites. Typical examples are (Mg_{3 - y}□_y) and (Mg_{3 - y} Li_y) for stevensite and hectorite, respectively. [The □ denotes a vacant site in the structure. (Mg_{3 - y}□_y) indicates, therefore, that y sites out of three are vacant.]

chlorite

      The structure of the chlorite minerals consists of alternate micalike layers and brucitelike hydroxide sheets about 14 Å thick. Structural formulas of most trioctahedral chlorites may be expressed by four end-member compositions:

(Mg₅Al)(Si₃Al)O₁₀(OH)₈ (clinochlore)

(Fe₅²⁺ Al)(Si₃Al)O₁₀(OH)₈ (chamosite)

(Mn₅Al)(Si₃Al)O₁₀(OH)₈ (pennantite)

(Ni₅Al)(Si₃Al)O₁₀(OH)₈ (nimite)

See as table:

      The unbalanced charge of the micalike layer is compensated by an excess charge of the hydroxide sheet that is caused by the substitution of trivalent cations (Al³⁺, Fe³⁺, etc.) for divalent cations (Mg²⁺, Fe²⁺, etc.). Chlorites with a muscovite-like silicate layer and an aluminum hydroxide sheet are called donbassite and have the ideal formula of Al_4.33(Si₃Al)O₁₀(OH)₈ as an end-member for the dioctahedral chlorite. In many cases, the octahedral aluminum ions are partially replaced by magnesium, as in magnesium-rich aluminum dioctahedral chlorites called sudoite. Cookeite is another type of dioctahedral chlorite, in which lithium substitutes for aluminum in the octahedral sheets.

      Chlorite structures are relatively thermally stable compared to kaolinite, vermiculite, and smectite minerals and are thus resistant to high temperatures. Because of this, after heat treatment at 500°–700° C, the presence of a characteristic X-ray diffraction peak at 14 Å is widely used to identify chlorite minerals.

Interstratified clay minerals

      Many clay materials are mixtures of more than one clay mineral. One such mixture involves the interstratification of the layer clay minerals where the individual component layers of two or more kinds are stacked in various ways to make up a new structure different from those of its constituents. These interstratified structures result from the strong similarity that exists between the layers of the different clay minerals, all of which are composed of tetrahedral and octahedral sheets of hexagonal arrays of atoms, and from the distinct difference in the heights (thicknesses) of clay mineral layers.

      The most striking examples of interstratified structures are those having a regular ABAB . . . -type structure, where A and B represent two component layers. There are several minerals that are known to have structures of this type—i.e., rectorite (dioctahedral mica/montmorillonite), tosudite (dioctahedral chlorite/smectite), corrensite (trioctahedral vermiculite/chlorite), hydrobiotite (trioctahedral mica/vermiculite), aliettite (talc/saponite), and kulkeite (talc/chlorite). Other than the ABAB . . . type with equal numbers of the two component layers in a structure, many modes of layer-stacking sequences ranging from nearly regular to completely random are possible. The following interstratifications of two components are found in these modes in addition to those given above: illite/smectite, glauconite/smectite, dioctahedral mica/chlorite, dioctahedral mica/vermiculite, and kaolinite/smectite.

      As the mixing ratio (proportion of the numbers of layers) for the two component layers varies, the number of possible layer-stacking modes increases greatly. For interstratified structures of three component layers, structures consisting of illite/chlorite/smectite and illite/vermiculite/smectite have been reported. Because certain interstratified structures are known to be stable under relatively limited conditions, their occurrence may be used as a geothermometer or other geoindicator.

sepiolite and palygorskite

      Sepiolite and palygorskite are papyrus-like or fibrous hydrated magnesium silicate minerals and are included in the phyllosilicate group because they contain a continuous two-dimensional tetrahedral sheet of composition Si₂O₅. They differ, however, from the other layer silicates because they lack continuous octahedral sheets. The structures of sepiolite and palygorskite are alike and can be regarded as consisting of narrow strips or ribbons of 2:1 layers that are linked stepwise at the corners. One ribbon is linked to the next by inversion of the direction of the apical oxygen atoms of SiO₄ tetrahedrons; in other words, an elongated rectangular box consisting of continuous 2:1 layers is attached to the nearest boxes at their elongated corner edges. Therefore, channels or tunnels due to the absence of the silicate layers occur on the elongated sides of the boxes. The elongation of the structural element is related to the fibrous morphology of the minerals and is parallel to the a axis. Since the octahedral sheet is discontinuous, some octahedral magnesium ions are exposed at the edges and hold bound water molecules (OH₂). In addition to the bound water, variable amounts of zeolitic (i.e., free) water (H₂O) are contained in the rectangular channels. The major difference between the structures of sepiolite and palygorskite is the width of the ribbons, which is greater in sepiolite than in palygorskite. The width determines the number of octahedral cation positions per formula unit. Thus, sepiolite and palygorskite have the ideal compositions Mg₈Si₁₂O₃₀(OH)₄(OH₂)₄(H₂O)₈ and (Mg, Al, □)₅Si₈O₂₀(OH)₂(OH₂)₄(H₂O)₄, respectively.

Imogolite and allophane

      Imogolite is an aluminosilicate with an approximate composition of SiO₂ · Al₂O₃ · 2.5H₂O. This mineral was discovered in 1962 in a soil derived from glassy volcanic ash known as “imogo.” Electron-optical observations indicate that imogolite has a unique morphological feature of smooth and curved threadlike tubes varying in diameter from 10 to 30 nanometres (3.9 × 10⁻⁷ to 1.2 × 10⁻⁶ inches) and extending several micrometres in length. The structure of imogolite is cylindrical and consists of a modified gibbsite sheet in which the hydroxyls of one side of a gibbsite octahedral sheet lose protons and bond to silicon atoms that are located at vacant octahedral cation sites of gibbsite. Thus, three oxygen atoms and one hydroxyl as the fourth anion around one silicon atom make up an isolated SiO₄ tetrahedron as in orthosilicates, and such tetrahedrons make a planar array on the side of a gibbsite sheet. Because silicon-oxygen bonds are shorter than aluminum-oxygen bonds, this effect causes that sheet to curve. As a result, the curved sheet ideally forms a tubelike structure with inner and outer diameters of about 6.4 Å and 21.4 Å, respectively, and with all hydroxyls exposed at the surface. The number of modified gibbsite units therefore determines the diameter of the threadlike tubes.

      Allophane can be regarded as a group of naturally occurring hydrous aluminosilicate minerals that are not totally amorphous but are short-range (partially) ordered. Allophane structures are characterized by the dominance of Si-O-Al bonds—i.e., the majority of aluminum atoms are tetrahedrally coordinated. Unlike imogolite, the morphology of allophane varies from fine, rounded particles through ring-shaped particles to irregular aggregates. There is a good indication that the ring-shaped particles may be hollow spherules or polyhedrons. Sizes of the small individual allophane particles are on the order of 30–50 Å in diameter. In spite of their indefinable structure, their chemical compositions surprisingly fall in a relatively narrow range, as the SiO₂:Al₂O₃ ratios are mostly between 1.0 and 2.0. In general, the SiO₂:Al₂O₃ ratio of allophane is higher than that of imogolite.

Hideomi Kodama

Chemical and physical properties

Ion exchange (ion-exchange reaction)

       Cation-exchange capacities and specific surface areas of clay mineralsDepending on deficiency in the positive or negative charge balance (locally or overall) of mineral structures, clay minerals are able to adsorb certain cations and anions and retain them around the outside of the structural unit in an exchangeable state, generally without affecting the basic silicate structure. These adsorbed ions are easily exchanged by other ions. The exchange reaction differs from simple sorption because it has a quantitative relationship between reacting ions. The range of the cation-exchange capacities of the clay minerals is given in the Table (Cation-exchange capacities and specific surface areas of clay minerals).

      Exchange capacities vary with particle size, perfection of crystallinity, and nature of the adsorbed ion; hence, a range of values exists for a given mineral rather than a single specific capacity. With certain clay minerals—such as imogolite, allophane, and to some extent kaolinite—that have hydroxyls at the surfaces of their structures, exchange capacities also vary with the pH (index of acidity or alkalinity) of the medium, which greatly affects dissociation of the hydroxyls.

      Under a given set of conditions, the various cations are not equally replaceable and do not have the same replacing power. Calcium, for example, will replace sodium more easily than sodium will replace calcium. Sizes of potassium and ammonium ions are similar, and the ions are fitted in the hexagonal cavities of the silicate layer. Vermiculite and vermiculitic minerals preferably and irreversibly adsorb these cations and fix them between the layers. Heavy metal ions such as copper, zinc, and lead are strongly attracted to the negatively charged sites on the surfaces of the 1:1 layer minerals, allophane and imogolite, which are caused by the dissociation of surface hydroxyls of these minerals.

      The ion-exchange properties of the clay minerals are extremely important because they determine the physical characteristics and economic use of the minerals.

Clay- water relations

      Clay materials contain water in several forms. The water may be held in pores and may be removed by drying under ambient conditions. Water also may be adsorbed on the surface of clay mineral structures and in smectites, vermiculites, hydrated halloysite, sepiolite, and palygorskite; this water may occur in interlayer positions or within structural channels. Finally, the clay mineral structures contain hydroxyls that are lost as water at elevated temperatures.

      The water adsorbed between layers or in structural channels may further be divided into zeolitic and bound waters. The latter is bound to exchangeable cations or directly to the clay mineral surfaces. Both forms of water may be removed by heating to temperatures on the order of 100°–200° C and in most cases, except for hydrated halloysite, are regained readily at ordinary temperatures. It is generally agreed that the bound water has a structure other than that of liquid water; its structure is most likely that of ice. As the thickness of the adsorbed water increases outward from the surface and extends beyond the bound water, the nature of the water changes either abruptly or gradually to that of liquid water. Ions and molecules adsorbed on the clay mineral surface exert a major influence on the thickness of the adsorbed water layers and on the nature of this water. The nonliquid water may extend out from the clay mineral surfaces as much as 60–100 Å.

      Hydroxyl ions are driven off by heating clay minerals to temperatures of 400°–700° C. The rate of loss of the hydroxyls and the energy required for their removal are specific properties characteristic of the various clay minerals. This dehydroxylation process results in the oxidation of Fe²⁺ to Fe³⁺ in ferrous-iron-bearing clay minerals.

       Cation-exchange capacities and specific surface areas of clay minerals Plastic and liquid limits of clay mineralsThe water-retention capacity of clay minerals is generally proportional to their surface area (see the Table (Cation-exchange capacities and specific surface areas of clay minerals)). As the water content increases, clays become plastic and then change to a near-liquid state. The amounts of water required for the two states are defined by the plastic and liquid limits, which vary with the kind of exchangeable cations and the salt concentration in the adsorbed water. The plastic and liquid limits for different clay minerals are given in the Table (Plastic and liquid limits of clay minerals). The plasticity index (PI), the difference between the two limits, gives a measure for the rheological (flowage) properties of clays. A good example is a comparison of the PI of montmorillonite with that of allophane or palygorskite. The former is considerably greater than either of the latter, indicating that montmorillonite has a prominent plastic nature. Such rheological properties of clay minerals have great impact on building foundations, highway construction, chemical engineering, and soil structure in agricultural practices.

Interactions with inorganic (inorganic compound) and organic compounds

      Smectite, vermiculite, and other expansible clay minerals can accommodate relatively large, inorganic cations between the layers. Because of this multivalency, the interlayer space is only partially occupied by such inorganic cations that are distributed in the space like islands. Hydroxy polymers of aluminum, iron, chromium, zinc, and titanium are known examples of the interlayering materials. Most of these are thermally stable and hold as pillars to allow a porous structure in the interlayer space. The resulting complexes, often called pillared clays, exhibit attractive properties as catalysts—namely, large surface area, high porosity, regulated pore size, and high solid acidity.

      Cationic organic (organic compound) molecules, such as certain aliphatic and aromatic amines, pyridines, and methylene blue, may replace inorganic exchangeable cations present in the interlayer of expansible minerals. Polar organic molecules may replace adsorbed water on external surfaces and in interlayer positions. Ethylene glycol and glycerol are known to form stable specific complexes with smectites and vermiculites. The formation of such complexes is frequently utilized for identifying these minerals. As organic molecules coat the surface of a clay mineral, the surface of its constituent particles changes from hydrophilic to hydrophobic, thereby losing its tendency to bind water. Consequently, the affinity of the material for oil increases, so that it can react with additional organic molecules. As a result, the surface of such clay materials can accumulate organic materials. Some of the clay minerals can serve as catalysts for reactions in which one organic substance is transformed to another on the mineral's surface. Some of these organic reactions develop particular colours that may be of diagnostic value in identifying specific clay minerals. Organically clad clay minerals are used extensively in paints, inks, and plastics.

Physical properties

      Clay mineral particles are commonly too small for measuring precise optical properties. Reported refractive (refractive index) indices of clay minerals generally fall within a relatively narrow range from 1.47 to 1.68. In general, iron-rich mineral species show high refractive indices, whereas the water-rich porous species have lower ones. Specific gravities (specific gravity) of most clay minerals are within the range from 2 to 3.3. Their hardness generally falls below 2¹/₂, except for antigorite, whose hardness is reported to be 2¹/₂–3¹/₂.

Size and shape

      These two properties of clay minerals have been determined by electron micrographs. Well-crystallized kaolinite occurs as well-formed, six-sided flakes, frequently with a prominent elongation in one direction. Halloysite commonly occurs as tubular units with an outside diameter ranging from 0.04 to 0.15 micrometre.

      Electron micrographs of smectite often show broad undulating mosaic sheets. In some cases the flake-shaped units are discernible, but frequently they are too small or too thin to be seen individually without special attention.

       illite occurs in poorly defined flakes commonly grouped together in irregular aggregates. Although their sizes vary more widely, vermiculite, chlorite, pyrophyllite, talc, and serpentine minerals except for chrysotile are similar in character to the illites. Chrysotile occurs in slender tube-shaped fibres having an outer diameter of 100–300 Å. Their lengths commonly reach several micrometres. Electron micrographs show that palygorskite occurs as elongated laths, singly or in bundles. Frequently the individual laths are many micrometres in length and 50 to 100 Å in width. sepiolite occurs in similar lath-shaped units. As mentioned above, allophane occurs in very small spherical particles (30–50 Å in diameter), individually or in aggregated forms, whereas imogolite occurs in long (several micrometres in length) threadlike tubes.

High-temperature reactions

      When heated at temperatures beyond dehydroxylation, the clay mineral structure may be destroyed or simply modified, depending on the composition and structure of the substance. In the presence of fluxes, such as iron or potassium, fusion may rapidly follow dehydroxylation. In the absence of such components, particularly for aluminous dioctahedral minerals, a succession of new phases may be formed at increasing temperatures prior to fusion. Information concerning high-temperature reactions is important for ceramic science and industry.

Solubility

      The solubility of the clay minerals in acids varies with the nature of the acid and its concentration, the acid-to-clay ratio, the temperature, the duration of treatment, and the chemical composition of the clay mineral attacked. In general, ferromagnesian clay minerals are more soluble in acids than their aluminian counterparts. Incongruent dissolutions may result from reactions in a low-acid-concentration medium where the acid first attacks the adsorbed or interlayer cations and then the components of the octahedral sheet of the clay mineral structure. When an acid of higher concentration is used, such stepwise reactions may not be recognizable, and the dissolution appears to be congruent. One of the important factors controlling the rate of dissolution is the concentration in the aquatic medium of the elements extracted from the clay mineral. Higher concentration of an element in the solution hinders to a greater degree the extractions of the element.

      In alkaline solutions, a cation-exchange reaction first takes place, and then the silica part of the structure is attacked. The reaction depends on the same variables as those stated for acid reactions.

Occurrence

Soils (soil)

      All types of clay minerals have been reported in soils. Allophane, imogolite, hydrated halloysite, and halloysite are dominant components in ando soils, which are the soils developed on volcanic ash. Smectite is usually the sole dominant component in vertisols (Vertisol), which are clayey soils. Smectite and illite, with occasional small amounts of kaolinite, occur in mollisols (Mollisol), which are prairie chernozem soils. Illite, vermiculite, smectite, chlorite, and interstratified clay minerals are found in podzolic (Podzol) soils. Sepiolite and palygorskite have been reported in some aridisols (Aridisol) (desert soils), and kaolinite is the dominant component in oxisols (lateritic soils). Clay minerals other than those mentioned above usually occur in various soils as minor components inherited from the parent materials of those soils.

      Soils composed of illite and chlorite are better suited for agricultural use than kaolinitic soils because of their relatively high ion-exchange properties and hence their capacity to hold plant nutrients. Moderate amounts of smectite, allophane, and imogolite in soils are advantageous for the same reason, but when present in large amounts these clay minerals are detrimental because they are impervious and have too great a water-holding capacity.

Recent sediments

      Sediment accumulating under nonmarine conditions may have any clay mineral composition. In the Mississippi River system, for example, smectite, illite, and kaolinite are the major components in the upper Mississippi and Arkansas rivers, whereas chlorite, kaolinite, and illite are the major components in the Ohio and Tennessee rivers. Hence, in the sediments at the Gulf of Mexico, as a weighted average, smectite, illite, and kaolinite are found to be the major components in the clay mineral composition. Although kaolinite, illite, chlorite, and smectite are the principal clay mineral components of deep-sea sediments, their compositions vary from place to place. In general, illite is the dominant clay mineral in the North Atlantic Ocean (greater than 50 percent), while smectite is the major component in the South Pacific and Indian oceans. In some limited regions, these compositions are significantly altered by other factors such as airborne effects, in which sediments are transported by winds and deposited when the carrying force subsides. The high kaolinite concentration off the west coast of Africa near the Equator reflects this effect.

      Under highly saline conditions in desert areas, as in soils, palygorskite and sepiolite also form in lakes and estuaries (perimarine environments).

Ancient sediments

      Analyses of numerous ancient sediments in many parts of the world indicate that smectite is much less abundant in sediments formed prior to the Mesozoic Era (from 245 to 66.4 million years ago) with the exception of those of the Permian Period (from 286 to 245 million years ago) and the Carboniferous Period (360 to 286 million years ago), in which it is relatively abundant.

      The available data also suggest that kaolinite is less abundant in very ancient sediments than in those deposited after the Devonian Period (408 to 360 million years ago). Stated another way, the very old argillaceous (clay-rich) sediments called physilites are composed largely of illite and chlorite. Palygorskite and sepiolite have not been reported in sediments older than Tertiary age—i.e., those more than about 66 million years old.

      Kaolinite and illite have been reported in various coals (coal). bentonite generally is defined as a clay composed largely of smectite that occurs in sediments of pyroclastic materials as the result of devitrification of volcanic ash in situ.

Sediments affected by diagenesis

      As temperature and pressure increase with the progression of diagenesis, clay minerals in sediments under these circumstances change to those stable under given conditions. Therefore, certain sensitive clay minerals may serve as indicators for various stages of diagenesis. Typical examples are the crystallinity of illite, the polytypes of illite and chlorite, and the conversion of smectite to illite. Data indicate that smectite was transformed into illite through interstratified illite-smectite mineral phases as diagenetic processes advanced. Much detailed work has been devoted to the study of the conversion of smectite to illite in lower Cenozoic-Mesozoic sediments because such conversion appears to be closely related to oil-producing processes.

Hydrothermal deposits

      All the clay minerals, except palygorskite and sepiolite, have been found as alteration products associated with hot springs and geysers and as aureoles around metalliferous deposits. In many cases, there is a zonal (biozone) arrangement of the clay minerals around the source of the alteration, a process which involves changes in the composition of rocks caused by hydrothermal solutions. The zonal arrangement varies with the type of parent rock and the nature of the hydrothermal solution. An extended kaolinite zone occurs around the tin-tungsten mine in Cornwall-Devon, Eng. Mica (sericite), chlorite, tosudite, smectite, and mica-smectite interstratifications are contained in an extensive clay zone formed in a close association with kuroko (black ore) deposits. Smectites are known to occur as alteration products of tuff and rhyolite. Pottery stones consisting of kaolinite, illite, and pyrophyllite occur as alteration products of acidic volcanic rocks, shales, and mudstone.

Origin

Synthetic formation

      All the clay minerals, with the possible exception of halloysite, have been synthesized from mixtures of oxides or hydroxides and water at moderately low temperatures and pressures. Kaolinite tends to form in alumina-silica systems without alkalies or alkaline earths. Illite is formed when potassium is added to such systems; and either smectite or chlorite results upon the addition of magnesium, depending on its concentration. The clay minerals can be synthesized at ordinary temperatures and pressures if the reactants are mixed together very slowly and in greatly diluted form.

      Clay minerals of certain types also have been synthesized by introducing partial structural changes to clay minerals through the use of chemical treatments. Vermiculite can be formed by a prolonged reaction in which the potassium of mica is exchanged with any hydrated alkali or alkaline earth cation. Chloritic minerals can be synthesized by precipitating hydroxide sheets between the layers of vermiculite or montmorillonite. The reverse reactions of these changes are also known. A mechanism of mineral formation involving a change from one mineral to another is called transformation and can be distinguished from neoformation, which implies a mechanism for the formation of minerals from solution.

Formation in nature

      In nature both mineral formation mechanisms, neoformation and transformation, are induced by weathering and hydrothermal and diagenetic actions.

      The formation of the clay minerals by weathering processes is determined by the nature of the parent rock, climate, topography, vegetation, and the time period during which these factors operated. Climate, topography, and vegetation influence weathering processes by their control of the character and direction of movement of water through the weathering zone.

      In the development of clay minerals by natural hydrothermal processes, the presence of alkalies and alkaline earths influences the resulting products in the same manner as shown by synthesis experiments. Near-neutral hydrothermal solutions bring about rock alteration, including the formation of illite, chlorite, and smectite, whereas acid hydrothermal solutions result in the formation of kaolinite.

Industrial uses

      Clays are perhaps the oldest materials from which humans have manufactured various artifacts. The making of fired bricks possibly started some 5,000 years ago and was most likely humankind's second earliest industry after agriculture. The use of clays (probably smectite) as soaps and absorbents was reported in Natural History by the Roman author Pliny the Elder (c. AD 77).

      Clays composed of kaolinite are required for the manufacture of porcelain, whiteware, and refractories. Talc, pyrophyllite, feldspar, and quartz are often used in whiteware bodies, along with kaolinite clay, to develop desirable shrinkage and burning properties. Clays composed of a mixture of clay minerals, in which illite is most abundant, are used in the manufacture of brick, tile, stoneware, and glazed products. In addition to its use in the ceramic industry, kaolinite is utilized as an extender in aqueous-based paints and as a filler in natural and synthetic polymers.

      Smectitic clays ( bentonite) are employed primarily in the preparation of muds for drilling oil wells. This type of clay, which swells to several times its original volume in water, provides colloidal and wall-building properties. Palygorskite and sepiolite clays also are used because of their resistance to flocculation under high salinity conditions. Certain clay minerals, notably palygorskite, sepiolite, and some smectites, possess substantial ability to remove coloured bodies from oil. These so-called fuller's earths (fuller's earth) are used in processing many mineral and vegetable oils. Because of their large absorbing capacity, fuller's earths are also used commercially for preparing animal litter trays and oil and grease absorbents. Acid treatment of some smectite clays increases their decolorizing ability. Much gasoline is manufactured by using catalysts prepared from a smectite, kaolinite, or halloysite type of clay mineral.

      Tons of kaolinite clays are used as paper fillers and paper coating pigments. Palygorskite-sepiolite minerals and acid-treated smectites are used in the preparation of no-carbon-required paper because of the colour they develop during reactions with certain colourless organic compounds.

      Clays have a tremendous number of miscellaneous uses, and for each application a distinct type with particular properties is important. Recently, clays have become important for various aspects of environmental science (conservation) and remediation. Dense smectite clays can be compacted as bentonite blocks to serve as effective barriers to isolate radioactive wastes. Various clays may absorb various pollutants including organic compounds (such as atrazine, trifluraline, parathion, and malathion) and inorganic trace metals (such as copper, zinc, cadmium, and mercury) from soils and groundwater. Clay is also used as an effective barrier in landfills and mine tailing ponds to prevent contaminants from entering the local groundwater system. For the most part, clays are not a health hazard except possibly palygorskites, which may damage respiratory health. As research continues, clay minerals are playing an increasing role in solving modern environmental problems.

Ralph E. Grim Hideomi Kodama

Additional Reading

Ralph E. Grim, Clay Mineralogy, 2nd ed. (1968); Karl Jasmund, Die silicatischen Tonminerale, 2nd enlarged ed. (1955); Georges Millot, Géologie des Argiles; altérations, sédimentologie, géochimie (1964); H. Beutelspacher and H.W. van der Marel, Atlas of Electron Microscopy of Clay Minerals and Their Admixtures (1968); J.A. Gard (ed.), The Electron-Optical Investigation of Clays (1971); Rex W. Grimshaw, The Chemistry and Physics of Clays and Allied Ceramic Materials, 4th ed. rev. (1971); Charles E. Weaver and Lin D. Pollard, The Chemistry of Clay Minerals (1973); John E. Gieseking (ed.), Soil Components, vol. 2, Inorganic Components (1975); Raymond N. Yong and Benno P. Warkentin, Soil Properties and Behaviour (1975); H. Van Olphen and J.J. Fripiat (eds.), Data Handbook for Clay Materials and Other Non-metallic Minerals (1979); G.W. Brindley and G. Brown (eds.), Crystal Structures of Clay Minerals and Their X-ray Identification, new ed. (1980); Duane M. Moore and Robert C. Reynolds, Jr., X-ray Diffraction and Identification and Analysis of Clay Minerals, 2nd ed. (1997); Ernő Nemecz, Clay Minerals (1981); Toshio Sudō et al., Electron Micrographs of Clay Minerals (1981); Simonne Caillère, Stéphane Hénin, and Michel Rautureau, Minéralogie des Argiles, 2nd ed. rev., 2 vol. (1982); Friedrich Liebau, Structural Chemistry of Silicates: Structure, Bonding, and Classification (1985); Robert H.S. Robertson, Fuller's Earth: A History of Calcium Montmorillonite (1986); A.C.D. Newman (ed.), Chemistry of Clays and Clay Minerals (1987); S.W. Bailey (ed.), Hydrous Phyllosilicates (Exclusive of Micas) (1988); J.B. Dixon and S.B. Weed (eds.), Minerals in Soil Environments, 2nd ed. (1989); Charles E. Weaver, Clays, Muds, and Shales (1989); Bruno Velde, Introduction to Clay Minerals: Chemistry, Origins, Uses, and Environmental Significance (1992); B. Velde, Origin and Mineralogy of Clays (1995); A. Parker and J.E. Rae (eds.), Environmental Interactions of Clays (1998).Hideomi Kodama

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