Interlayer expanded

We have seen that experimental data suggest high temperatures for dioctahedral montmorillonite stabilities, especially the Na-Ca types with beidellitic substitution. Yet in most studies of montmorillonite stabilities under natural conditions, the fully expandable phase is lost rather early, near 100°C. This phase appears to be succeeded by an interlayered expandable-non-expandable mineral. Apparently two sets of information do not agree. 

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... 

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. 

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)... 

Micro-composites are formed when the polymer chain is unable to intercalate into the silicate layer and therefore phase separated polymer/clay composites are formed. Their properties remain the same as the conventional micro-composites as shown in Figure 2(a). Intercalated nano-composite is obtained when the polymer chain is inserted between clay layers such that the interlayer spacing is expanded, but the layers still bear a well-defined spatial relationship to each other as shown in Figure 2(b). Exfoliated nano-composites are formed when the layers of the day have been completely separated and the individual layers are distributed throughout the organic matrix as shown in Figure 2(c). 

Fig. 3. Possible arrangements of long-chain quaternary ammonium cations (here tetradecyltrimethylammonium) in the interlayer space of expanding 2 1 layer silicates. After Lagaly (1982) and Jaynes and Boyd (1991a).

Sorption depends on Sorption Sites. The sorption of alkaline and earth-alkaline cations on expandable three layer clays - smectites (montmorillonites) - can usually be interpreted as stoichiometric exchange of interlayer ions. Heavy metals however are sorbed by surface complex formation to the OH-functional groups of the outer surface (the so-called broken bonds). The non-swellable three-layer silicates, micas such as illite, can usually not exchange their interlayer ions but the outside of these minerals and the weathered crystal edges ("frayed edges") participate in ion exchange reactions. 

Our approach has been to study a very simple clay-water system in which the majority of the water present is adsorbed on the clay surfaces. By appropriate chemical treatment, the clay mineral kao-linite will expand and incorporate water molecules between the layers, yielding an effective surface area of approximately 1000 m2 g . Synthetic kaolinite hydrates have several advantages compared to the expanding clays, the smectites and vermiculites they have very few impurity ions in their structure, few, if any, interlayer cations, the structure of the surfaces is reasonably well known, and the majority of the water present is directly adsorbed on the kaolinite surfaces. 

Figure 1. Cross-sectional diagram of an expanding 2 1 layer silicate showing the octahedral layer, tetrahedral layer, and hydrated exchange cations in the interlayer.

The interlayer space of LDHs can be expanded to some extent in a suitable solvent medium, which favors the ion exchange process. An aqueous medium, for example, favors the exchange by inorganic anions, whilst an organic solvent favors exchange by organic anions [14]. 

In both the above cases, we have 2D processes. Following nucleation, the reaction may be either phase boimdary controlled (i.e. the rate is limited by the rate at which the interlayer space expands to accommodate the guest) or diffusion controlled (i.e. the reaction rate is controlled by the rate at which the guests diffuse between the layers - the interlayer spacing expands instantly as the guests move). 

The CEC of clay minerals is partly the result of adsorption in the interlayer space between repeating layer units. This effect is greatest in the three-layer clays. In the case of montmorillonite, the interlayer space can expand to accommodate a variety of cations and water. This causes montmorillonite to have a very high CEC and to swell when wetted. This process is reversible the removal of the water molecules causes these clays to contract. In illite, some exchangeable potassium is present in the interlayer space. Because the interlayer potassium ions are rather tightly held, the CEC of this illite is similar to that of kaolinite, which has no interlayer space. Chlorite s CEC is similar to that of kaolinite and illite because the brucite layer restricts adsorption between the three-layer sandwiches. 

Layers of silicate-bearing hectorites were expanded by the intercalation of the lengthwise alkyl quaternary ammonium cation and simultaneously the interlayer anisotropic silicates stood normally to the layer. 

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