Octahedral layers, clay minerals

Talc and Pyrophyllite. Talc (qv) and pyrophjlhte are 2 1 layer clay minerals having no substitution in either the tetrahedral or octahedral layer. These are electrostatically neutral particles (x = 0) and may be considered ideal 2 1 layer hydrous phyUosiHcates. The stmctural formula of talc, the trioctahedral form, is Mg3Si402Q(0H)2 and the stmctural formula of pyrophylUte, the dioctahedral form, is Al2Si402Q (OH)2 (106). Ferripyrophyllite has the same stmcture as pyrophylUte, but has ferric iron instead of aluminum in the octahedral layer. Because these are electrostatically neutral they do not contain interlayer materials. These minerals are important in clay mineralogy because they can be thought of as pure 2 1 layer minerals (106). 

Many clay minerals have aluminosilicate layer structures. For example, in kaolinite, Al2(0H)4[Si205] (Fig. 7.5), the Al3+ are all in octahedral locations. Clay minerals of the smectite or swelling type, such as montmo-rillonite, can absorb large amounts of water between the aluminosilicate... 

Talc and Pyrophyllile. Talc and pyrophyllite are 2 1 layer clay minerals having no substitution in eiflier the tetrahedral or octahedral layer. These are electrostatically neutral particles i t = 0) and may be considered ideal 2 1 layer hydrous phyllosilieates. Talc and pyrophyllite are found in metamorphic rocks that arc rich in Mg and Al. respectively... 

Gastuche, M.C., 1963. The octahedral layer. Clays Clay Miner., Proc., 12 471-493. 

In the case of layered clay minerals, isomorphic substitutions occur not only in the tetrahedral layers but in the octahedral layers, too. When Al3+ is in the central... 

Fig. 3. Schematic of a montmorillonite, layered clay mineral with a triple-sheet sandwich structure consisting of a central, hydrous alumina octahedral sheet (O), bonded to two silica tetrahedral sheets (T) by shared oxygens.

The natural montmorillonite clays consist of several hundred individual platelike particles of dimensions 1 jum x 1 jum x 1 nm, held together by electrostatic forces with a gap of approximately 0.3 nm between two adjacent particles. The structure at the atomic level is shown in Figure 13.28 (77). The sodium montmorillonite layer is a crystalline 2 1 layered clay mineral in which a central alumina octahedral sheet is sandwiched between two silica tetrahedral sheets. These structures are sometimes called smectite clays, because of their layered structure see Figure 7.1. Note that this clay mineral comprises silicate layers in which the fundamental unit is planar. In the gap between the silicate layers are sodium ions. The gap is widely known as a gallery or an interlayer. The density of montmorillonite clays vary slightly with composition, but is generally near 2.5 g/crn (78). 

Aspect ratios (length/thickness) greater than a thousand are possible [29]. MMT is the most commonly used layered silicate. It is a hydrated alumina-silicate layered clay mineral consisting of an edge-shared octahedral sheet of aluminum hydroxide between two silica tetrahedral layers [6,30]. Highly favorable polymer-surface interactions are essential for thorough clay sheet dispersion [31,32]. Thus, it is conventional to organo-modify these clays with cationic surfactants in order to improve compatibility with the polymer matrix and to faciUtate delamination and exfoliation [3]. 

The least compHcated clay minerals are the 1 1 clay minerals composed of one tetrahedral (T) layer and one octahedral (O) layer (see Fig. 1). These 1 1 clay minerals are also referred to as TO minerals. The TO package has a basal spacing (nominal thickness) of 0.7 nm (7 E) and they are commonly referred to as 7 E minerals. Kaolinite, the dioctahedral 1 1 mineral, has filling two of three octahedral sites, and serpentine [12168-92-2J, (Mg)3Si205(0H)4, the trioctahedral 1 1 mineral has filling all three octahedral sites. The kaolin minerals have limited substitution in the octahedral... 

Clay minerals that are composed of two tetrahedral layers and one octahedral layer are referred to as 2 1 clay minerals or TOT minerals. The apical oxygens of the two tetrahedral sheets project into the octahedral sheet. The 2 1 stmcture has a basal spacing (nominal thickness) of 1.0 nm (10 E). Pyrophjlhte [12269-78-2] Al2Si40 Q(0H)2, is the dioctahedral mineral, ie, AF" in the octahedral sites, and talc [14807-96-6], Mg3Si402Q(0H)2, is the trioctahedral, ie, in the octahedral sites. Both these minerals are essentially free of substitution in the octahedral site and therefore do not have a net... 

The multitude of variation in clay minerals is caused by substitution in the octahedral and tetrahedral layers resulting in charge deficits. The manner in which the charge deficit is balanced leads to many of the useful and unique properties of clay minerals. 

Palygorskite and sepioHte minerals are 2 1 layered phyUosiHcates that differ from the above mentioned clays because the octahedral sheets have significant intracrystalline void space caused by discontinuous octahedral layers. The basal tetrahedral unit is connected to an adjacent inverted basal tetrahedral creating a void space or channel. Charge deficits are balanced by hydrated cations in the intracrystalline space. 

Smectites (Montmorillonites). Smectites are the 2 1 clay minerals that carry a lattice charge and characteristically expand when solvated with water and alcohols, notably ethylene glycol and glycerol. In earUer Uterature, the term montmorillonite was used for both the group (now smectite) and the particular member of the group in which Mg is a significant substituent for Al in the octahedral layer. Typical formulas are shown in Table 2. Less common smectites include volkhonskoite [12286-87-2] hich. contains Cr " medmontite [12419-74-8], Cu " andpimeUte [12420-74-5], (12). 

Smectites are stmcturaUy similar to pyrophylUte [12269-78-2] or talc [14807-96-6], but differ by substitutions mainly in the octahedral layers. Some substitution may occur for Si in the tetrahedral layer, and by F for OH in the stmcture. Deficit charges in smectite are compensated by cations (usually Na, Ca, K) sorbed between the three-layer (two tetrahedral and one octahedral, hence 2 1) clay mineral sandwiches. These are held relatively loosely, although stoichiometricaUy, and give rise to the significant cation exchange properties of the smectite. Representative analyses of smectite minerals are given in Table 3. The deterrnination of a complete set of optical constants of the smectite group is usually not possible because the individual crystals are too small. Representative optical measurements may, however, be found in the Uterature (42,107). 

Palygorskite and sepioHte are different from other clay minerals in the manner in which the 2 1 layers are joined. Rather than being joined in a continuous manner, the tetrahedral sheets are joined to an adjacent inverted tetrahedral layer, making the octahedral layers noncontinuous and leaving an open channel in the mineral stmcture (37,38,148). The dimension of palygorskite is teI.S nm (18 E) the dimension of sepioHte is 9e2.7 nm (27 E) (37). 

In terms of composition, the simplest of the marine clay minerals is kaolinite in which tetrahedral and octahedral layers alternate (Figure 14.5a) creating a two-layer repeating imit. In three-layer clays, the repeating unit is composed of an octahedral... 

As shown in Figure 14.4, each clay mineral exhibits a large range in the type and degree of isomorphic substitution. The central silicon atom in the tetrahedral layers can be replaced by aluminum, alkali, alkaline earth, and trace metal atoms. In the octahedral layers, the central Al and Mg atoms can be similarly replaced. The large range in composition within each mineral type reflects variability in the environmental conditions under which crystallization and chemical weathering occur. Thus, the... 

Most serpentines and other layered silicate minerals, such as micas and clays, are composed of tetrahedral and octahedral sheets that lie virtually flat. In chrysotile samples, however, the layers curl, rolling up like a carpet, to form concentric hollow cylinders (Fig. 2.4). The average diameter of a cylinder, which is a chrysotile fibril, is about 25 nanometers (25 nm = 0.025 mi-... 

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