Smectite group

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). 

Products of this type seem to protect the humus from rapid incorporation into new biological processes. Additional factors that appear to be associated with the accumulation of organic matter in Mollisols are high exchange capacities, saturation with calcium, an abundance of mineral colloids and a high content of minerals of the smectite group (Fenton, 1983). 

Figure 4.7 Structure of one of the smectite group of clay minerals montmorillonite, Al2Si40io(OH)2.nH20. (After Evans, 1966 Figure 11.08b, by permission of Cambridge University Press.)...

The smectite group of clay minerals is also poorly crystalline but perhaps better known because of their cation exchange capacity and their occurrence in the bentonite clays. A general formula for montmorillonite, which is one of the dioctahedral smectites is... 

The three-sheet or 2 1 layer lattice silicates consist of two silica tetrahedral sheets between which is an octahedral sheet. These three sheets form a layer approximately 10 A thick. The oxygens at the tips of the tetrahedra point towards the center octahedral sheet and substitute for two-thirds of the octahedrally coordinated hydroxyls. The 2 1 clay minerals include the mica and smectite groups which are by far the most abundant of the clay minerals. The pure end members of this type are talc, a hydrous magnesium silicate pyrophyllite, a hydrous aluminum silicate and minnesotaite, a hydrous iron silicate. 

Clays, natural or synthetic, are the most widely investigated and understood nanoadditives used to enhance the flame retardancy of polymers through nanocomposite technology, because of their unique properties, particularly the ease of surface treatment and application in polymer matrices. Clay can be cationic and anionic materials, in accordance with the charge on the clay layers. In this chapter, the focus is on two kinds of clays montmorillonite (MMT), a naturally occurring cationic clay that belongs to the smectite group of silicates, and LDH, an anionic clay that does occur naturally but for which the synthetic form is more common. Other clays will also be mentioned as appropriate. 

As indicated in Table 1, the three 2 1 groups differ from one another in two principal ways. The layer charge decreases in the order illite > vermiculite > smectite, and the vermiculite group is further distinguished from the smectite group by the extent of isomorphic substitution in the tetrahedral sheets. Among the smectites, those in which substitution of Al for Si exceeds that of Fe2+ or Mg for Al are called beidellite, and those in which the reverse is true are called montmorillonite. The sample chemical formula in Table 1 for smectite thus represents montmorillonite. In any of these 2 1 clay... 

The amount of substitution in the tetrahedral and octahedral sheets and the ratio of octahedral to tetrahedral sheets are the primary differentiating characteristics between the many clay minerals (Fig. 3.6). For example, clays that have one tetrahedral sheet and one octahedral sheet are known as 1 1 clay minerals (e.g., kaolin group) (Fig. 3.7) clays that have two tetrahedral sheets and one octahedral sheet are known as 2 1 clay minerals (e.g., smectite group) (Fig. 3.8) or mica and vermiculite (Fig. 3.9), while clays that have two tetrahedral sheets and two octahedral sheets are known as 2 2 clay minerals (e.g., chlorite) (Fig. 3.10). These sheet arrangements give rise to various mineral surface identities such as magnitude (specific surface), functional groups, and interactions with solution species. 

The montmorillonite (Chapter 1, Table 1.2) clay mineral can be used as a model substance in the study of the interfacial processes of rocks and soils. It is a layer silicate, a member of the smectite group. Its structure is appropriate for modeling the most important interfacial processes in geological formations. Besides, it is a fairly widespread mineral in rocks and soils, and plays an important role in the nutrient cycle of soils. In addition, it has many agricultural, industrial, and environmental applications. 

The three-layer phyllosilicates include talc and pyrophyllite, illite and the smectite group clays, various mixed-layer clays, vermiculite, and the micas (e.g., muscovite, phlogopite, and biotite). We will limit ourselves to a discussion of the more environmentally important of these minerals, which include the micas, the smectites and illites, interlayered (mixed-layer) smectite-illites and vermiculite. 

The smectite group [see Table 9.1 and Fig. 9.3(a)] includes any clay whose interlayer repeat distance (thickness of individual T 0 T layers plus interlayer spacing) expands to 17 A on treatment with ethylene glycol (cf. Drever 1988). This is indicative of a structure in which the number of interlayer cations is smaller than 0.65 (Greenland and Hayes 1978), and is usually about 0.2 to 0.5 per formula unit Ojo(OH)2 (Drever 1988). The interlayer cations are adsorbed, and are necessary to balance the unsatisfied net charge (usually negative) of the clay crystal lattice caused by structural substitutions or vacancies in the octahedral and/or tetrahedral layers. For example Mg or another divalent cation may substitute for Al in the octahedral layer, or Al or Fe may replace Si" " in the tetrahedral layer. 

Lipase B from Candida antarctica Smectite group (Laponite, SWy-2 and Kunipia) and organically modified derivatives Oxidation of terpenes [56, 57]... 

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