Smectites

There are several possible origins for smectites in soils inherited from parent materials, formed by weathering of other 2 1 phyllosilicates (especially micas), or precipitated from soil solutions after dissolution of other primary minerals. 

In mineralogy, the term clay is used for a variety of polycrystaUine materials that are well described in clay science, mineralogy properties, and characterization textbooks [2-5]. Clays can be present in fibrous, tubular, lath shaped, and planar geometries. In this chapter, however, our focus will be mainly on the planar clay varieties called smectites that include montmorillonites, the most commonly used clay for the produchon of polyolefin-clay nanocomposites. In this section, we wiU focus on clay characteristics that are relevant to catalyst supporting and particle break-up during polymerization clay chemistry, crystalline structure, and geometry. 

The basic smectite structure if formed by an alumina octahedral layer sandwiched between two siUca tetrahedral layers. These layers share the apical oxygen atoms 

Substitution of Al by Fe, Fe, and Mg in the octahedral sheets of smectites is a common occurrence. Silicon atoms may be substituted by aluminum atoms in tetrahedral sheets, which again creates a charge imbalance [5]. The isomorphous 

---

Clays and Other Sources. Sedimentary deposits, especially hthium-bearing clays found in the western United States, offer an additional source of lithium. These clays contain lithium-hearing trioctahedral smectites, of which hectorite [12173-47-6] NaQ23(Mg,Li)2Si402Q(F,0H)2, is one mineral. 

Of the various inorganic soil constituents, smectites (montmorillonite clays) have the greatest potential for sorption of pesticides on account of their large surface area and abundance in soils. Weak base pesticides, both protonated and neutral species, have been shown to be sorbed as interlayer complexes. Sorption of atrazine on smectites ranges from 0 to 100% of added atrazine, depending on the surface charge density of the smectite (36). 

Hydrophobic interactions and trapping of molecules in a molecular sieve formed by humic materials have been hypothesized as retention mechanisms for prometryn. It has been shown that fluridone, fluazifop, and bipyridyhum herbicides penetrate into interlamellar spaces of smectites and can become trapped. 

There are no unequivocal weathering reactions for the siUcate minerals. Depending on the nature of parent rocks and hydrauhc regimes, various secondary minerals like gibbsite, kaolinite, smectites, and iUites are formed as reaction products. Some important dissolution processes of siUcates are given, for example, by the following reactions (19). 

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). 

X-ray diffraction patterns yield typical 1.2—1.4 nm basal spacings for smectite partially hydrated in an ordinary laboratory atmosphere. Solvating smectite in ethylene glycol expands the spacing to 1.7 nm, and beating to 550°C collapses it to 1.0 nm. Certain micaceous clay minerals from which part of the metallic interlayer cations of the smectites has been stripped or degraded, and replaced by expand similarly. Treatment with strong solutions of... 

Smectite [12199-37-0] from an oxidized outcrop is stained light blue by a dilute solution of benzidine hydrochloride. The color does not arise from smectite specifically, but from reaction of a high oxidation state of elements such as Fe " and Mn " (46)46. 

Transmission electron micrographs show hectorite and nontronite as elongated, lath-shaped units, whereas the other smectite clays appear more nearly equidimensional. A broken surface of smectite clays typically shows a "com flakes" or "oak leaf surface texture (54). High temperature minerals formed upon heating smectites vary considerably with the compositions of the clays. Spinels commonly appear at 800—1000°C, and dissolve at higher temperatures. Quartz, especially cristobalite, appears and mullite forms if the content of aluminum is adequate (38). 

Bentonite is a rock rich in montmorillonite that has usually resulted from the alteration of volcanic dust (ash) of the intermediate (latitic) siliceous types. In general, reUcts of partially unaltered feldspar, quartz, or volcanic glass shards offer evidence of the parent rock. Most adsorbent clays, bleaching clays, and many clay catalysts are smectites, although some are palygorskite [1337-76 ]. 

Pillared clays are smectite minerals or iUite-smectite minerals that have been stmcturaHy modified to contain pillars of stable inorganic oxide. The pillars prop open the smectite stmcture so they have a basal space of approximately 3.0 nm. Typical metals in the pillars include Al, Zr, Ti, Ce, and Fe, and these materials are used in catalytic processes to crack heavy cmde oils (110—112). 

The original pillared clays were made by (/) mixing smectite with a polymeric cationic hydroxy metal complex such as aluminum chlorhydrol (2) allowing a minimal amount of time for the cationic hydroxy metal complex to exchange with the interlayer cations and (7) calcining the resulting material to decompose the hydroxy metal complex (110). A number of newer methods have been developed to make pillared clays (111—117). 

Regularly interstratified (1 1) chlorite and vermiculite has been attributed to the mineral corrensite [12173-14-7] (141). Chlorite mixed layers have been documented with talc, vermicuhte, smectite, iUite, biotite, kaolinite, serpentine, and muscovite. The mixed-layer mineral is named after the components, eg, talc—chlorite. The eadier Hterature, however, has reference to specific minerals such as kulkeite [77113-95-2] (talc—chlorite and tosudite... 

Vermicuhte is an expandable 2 1 mineral like smectite, but vermiculite has a negative charge imbalance of 0.6—0.9 per 02q(0H)2 compared to smectite which has ca 0.3—0.6 per 02q(0H)2. The charge imbalance of vermiculite is satisfied by incorporating cations in two water layers as part of its crystal stmcture (144). Vermiculite, which can be either trioctahedral or dioctahedral, often forms from alteration of mica and can be viewed as an intermediate between UHte and smectite. Also, vermiculite is an end member in a compositional sequence involving chlorite (37). Vermiculite may be viewed as a mica that has lost part of its K+, or a chlorite that has lost its interlayer, and must balance its charge with hydrated cations. 

The chemical composition of vermiculite can be quite variable (145). The megascopic varieties are generally trioctahedral, and the clay-si2e varieties contain both dioctahedral and trioctahedral varieties (144). Smectite minerals do not commonly occur as macroscopic single crystals. 

Mixed-layer clays, particularly lUite—smectite, are very common minerals and illustrate the transitional nature of the 2 1 layered siHcates. The transition from smectite to iUite occurs when smectite, in the presence of potassium from another mineral such as potassium feldspar, or from thermal fluids, is heated and/or buried. With increasing temperature smectite plus potassium is converted to iUite (37,39). 

The physical stmcture of mixed-layer minerals is open to question. In the traditional view, the MacEwan crystallite is a combination of 1.0 nm (10 E) non-expandable units (iUite) that forms as an epitaxial growth on 1.7 nm expandable units (smectite) that yield a coherent diffraction pattern (37). This view is challenged by the fundamental particle hypothesis which is based on the existence of fundamental particles of different thickness (160—162). 

An alternative description of iUite—smectite mixed-layer clays begins with megacrystals of smectite that incorporate smaller packets of iUite (163). These constituents are observed as mixed-layer minerals in x-ray analysis. Diagenesis increases the percentage of iUite layer and with increasing alteration the mixed-layer mineral takes on the characteristics of an iUite dominated iUite—smectite. 

Chlorite is another mineral that is commonly associated with mixed-layered clays. Complete soHd solutions of chlorite mixed-layer minerals have not been identified. In contrast to iUite—smectite mixed-layer minerals, chlorite mixed-layer minerals occur either as nearly equal proportions of end-member minerals (Rl) or dominated by one end member (RO) (142). Mixed-layer chlorite may consist of any of the di—tri combinations of chlorite and chlorite mixed-layering occurs with serpentine, kaolinite, talc, vermicuhte, smectite, and mica. References of specific chlorite mixed-layer minerals of varied chemical compositions are available (142,156). 

Allophane and Imogolite. AUophane is an amorphous clay that is essentially an amorphous soHd solution of sUica, alumina, and water (82). In allophane less than one-half of the aluminum is held in tetrahedral coordinations and the Si02 to AI2O2 ratio typically varies between 1.3 and 2.0, but values as low as 0.83 have been reported. The typical morphology of allophane is cylindrical (37). AUophane may be associated with haUoysite, smectite minerals, or it may occur as a homogeneous mixture with evansite, an amorphous soHd solution of phosphoms, alumina, and water. Its composition, hydration, and properties vary. Chemical analyses of two allophane samples are given in Table 5. 

Cations exchanged into the interlayers of expandable clays (smectites) are comparatively easy to study with NMR methods because the cations become major components of the phase and their concentrations are often several wt %. In addition to Cs Li, Na, K, and Cd have been studied by NMR. We have chosen to investigate Cs because it is a significant component of nuclear waste, because it provides an end-member case as the least electronegative cation, and because it has desirable nuclear properties (100% abundance, relatively high frequency, 65.5 MHz at H = 11.7 T, and small quadrupole moment)... 

We have done our experiments with hectorite, which is a 2 1 smectite that develops negative layer charge by substitution of Li for Mg in the octahedral sheet.Samples were prepared by multiple exchange in 1.0 and 0.1 M CsCl solutions until essentially complete Cs-exchange was reached (97% of the interlayer cations). Temperature dependent data are essential to interpret the results, because there is rapid exchange of Cs among different interlayer sites at room temperature (RT). 

Assignment of the observed peaks just described parallels that for Cs in smectite inter layers. Peaks that are more... 

---