Sheet aluminosilicates structure

Silicates also exist in which each silicon atom bonds to one outer oxygen and to three inner oxygen atoms. The result is a linked network in which every silicon atom forms three Si—O—Si links, giving a planar, sheet-like structure. The empirical formula of this silicate is S12 O5. In many minerals, aluminum atoms replace some of the silicon atoms to give aluminosilicates. The micas—one has the chemical formula... 

Figure 1. Schematic illiistration of the structure of sheet aluminosilicates (After Brindley, G.W. MacEwan, D.M.C. In "Ceramics - a syn josium" Green, A.T. Stewart, G.H. Eds. Br. Ceramic Society 1953, 15).

A class of silicate and aluminosilicate minerals with sheet-like structures that have enormous surface areas that can absorb large amounts of water. 

The clay minerals are silicates and aluminosilicates with sheet-like structures. They result from the weathering of granite and other rocks. The layers have enormous inner surfaces that can absorb large amounts of H2O. Clay mixtures often occur as minute platelets with a very large total surface area. When wet, the clays are easily shaped. When heated to high temperatures, they lose H2O when fired in a furnace, they become very rigid. 

Montmorillonite is the name given to day found near MontmoriUonin in France, whereit was identified by Knight in 1896 (Utracki, 2004). Montmorillonite is a 2 1 layered hydrated aluminosilicate, with a triple-sheet sandwich structure consisting of a central, hydrous alumina octahedral sheet, bonded to two silica tetrahedral sheets by shared oxygen ions (Fig. 3). The unit cell of this ideal structure has a composition [Al2(0H)2(Si205)2]2 with a molar... 

More complex (and more common) structures result when some of the sili-con(IV) in silicates is replaced by aluminum(III) to form the aluminosilicates. The missing positive charge is made up by extra cations. These cations account for the difference in properties between the silicate talc and the aluminosilicate mica. One form of mica is KMg (Si1AlO10)(OH)2. In this mineral, the sheets of tetrahedra are held together by extra K+ ions. Although it cleaves neatly into transparent layers when the sheets are torn apart, mica is not slippery like talc (Fig. 14.40). Sheets of mica are used for windows in furnaces. 

Many varieties of clay are aluminosilicates with a layered structure which consists of silica (SiOa" ) tetrahedral sheets bonded to alumina (AlOg ) octahedral ones. These sheets can be arranged in a variety of ways in smectite clays, a 2 1 ratio of the tetrahedral to the octahedral is observed. MMT and hectorite are the most common of smectite clays. 

It is helpful in the discussion to describe silicate structures using the Q nomenclature, where Q represents [SiOJ tetrahedra and the superscript n the number of Q units in the second coordination sphere. Thus, isolated [SiO ] " are represented as Q and those fully connected to other Q units as Q. In general, minerals based on Q , Q and units are decomposed by acids. Such minerals are those containing isolated silicate ions, the orthosilicates, SiO (Q ) the pyrosilicates, Si O " (Q ) ring and chain silicates, (SiOg) (Q ). Certain sheet and three-dimensional silicates can also yield gels with acids if they contain sites vulnerable to acid attack. This occurs with aluminosilicates provided the Al/Si ratio is at least 2 3 when attack occurs at A1 sites, with scission of the network (Murata, 1943). 

Tetrahedra linked via three vertices correspond to a composition MX1 1X3 2 or MX2 5 = M2X5. Small units consisting of four tetrahedra are known in P4O10, but most important are the layer structures in the numerous sheet silicates and aluminosilicates with anions of the compositions and [AlSiOj-]. Because the terminal vertices of the single... 

Figure 4.6 Layer structure of kaolinite. Edge view showing the aluminosilicate sheets, and the stacking arrangement of these sheets. (After Evans, 1966 Figure 11.11, by permission of Cambridge University Press.)...

Fig. 2.1 Configurations of the tetrahedral units and chain, double chain, and sheet structures in the silicate and aluminosilicate minerals. (A) Two-dimensional representation of a single silicate tetrahedron. (A ) Two-dimensional representation of an extended silicate chain. (B) Three-dimensional representations of single tetra-hedra in two orientations. The apexes of the tetrahedra point above or below the plane of the paper. (B ) Three-dimensional representations of extended silicate chains showing different orientations of the tetrahedra in two of the many possible configurations. Single chain pyroxenes (C), wollastonite (D), rhodonite (E). Double chains amphiboles (F). Sheets as found in the serpentines, micas, and clays (G).

ALUMINOSILICATES WITH SHEET STRUCTURES THAT FORM FIBERS... 

Fig. 2.12 Structural components and variations in the micas. (A) Plan view of the continuous aluminosilicate sheet (T), [Si,Al205] , a portion of the mica structure. (B) Stereographic representation of an idealized mica. The structure is composed of continuous layers containing two tetrahedral aluminosilicate sheets (T) that enclose octahedrally coordinated cations, or Mg (O). This layer or sandwich," the T-O-T or 2 1 aggregate, is held together by or Na ions. (C) The two possible positions (I and II) of octahedral cations in the micas. Sets of three locations for each are superimposed on the tetrahedral hexagonal aluminosilicate sheet. (D) The three possible directions of intralayer shift when octahedral set I (upper) or II (lower) are occupied. The dashed lines and circles represent ions below the plane of the paper. (E) Distorted hexagonal rings of apical oxygens in the tetrahedral sheet of dioctahedral micas compared with the undistorted positions of the apical oxygens in the tetrahedral sheet of trioctahedral micas.

Because the clays have a basic layered structure of aluminosilicate sheets the expectation was a platy habit. The creation of tubular forms was studied by Bates (1959). He postulated that the curved forms, observed by electron microscopic investigation of halloysite and chrysotile, originated through the relief of strain between sheets of unequal dimensions. 

The potassium ions are located between the flat aluminosilicate sheets (Fig. 7.4). Crystals of micas cleave easily parallel to the sheets, and the thin transparent flakes can be used for electrical insulation (e.g., in capacitors) or as furnace windows. Phlogopite, KMg3(OH)2[Si3A10io], has a similar structure but with Mg2+ in octahedral environments instead of Al3+. 

Clays are layer silicates (phyllosilicates) of particle size less than about 4 pm, produced by the weathering of aluminosilicate rocks. Clay minerals fall roughly into two structural classes the kaolinite type, based on paired sheets of tetrahedral (SiC>44-) and octahedral [A10n(0H) g " or... 

The phenomenon of increased hardness occurs principally in minerals of sheet and chain structures, which link together through the cations (silicates and aluminosilicates, as well as hydrated sheet minerals, such as glauconite, melilite and gypsum—M ranging from 0 to about 1.25), and also in minerals of skeletal structures (borates, phosphates, sulphates, nitrates, carbonates, such as calcite, dolomite and others—Ah from 0 to about 1.15). For this reason, the hardness analysis of minerals with weak bonds demands consideration of the fact that just as the basic crystallo-chemical factors, so is hardness influenced by the form of domains (component parts of structures) in all anisodesmic minerals of chain, sheet or skeletal structure. Depending on the form of domain (and also according... 

Clays are aluminosilicates with a two-dimensional or layered structure including the common sheet 2 1 alumino- and magnesium- silicates (montmorillonite, hectorite, micas, vermiculites) (figure 7.4) and 1 1 minerals (kaolinites, chlorites). These materials swell in water and polar solvents, up to the point where there remains no mutual interaction between the clay sheets. After dehydration below 393 K, the clay can be restored in its original state, however dehydration at higher temperatures causes irreversible collapse of the structure in the sense that the clay platelets are electrostatically bonded by dehydrated cations and exhibit no adsorption. 

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