Interlayer cations

Figure 10-1 shows the scanning electron micrographs of sample El (Li+) (upper) and sample E4 (NH4+) (lower). These layer silicates consist of small aggregates of platelets showing various morphology in relationship to the monovalent cation (interlayer material) used in the synthesis. These two samples are well-crystallized and virtually pure as shown by XRD. 

FIGURE 7 Proposed interlayer arrangements of exchangeable cations and associated macrocyclic ligands in complexes with montmorillonite and vermiculite. r< = radius of the macrocyclic cavity = radius of cations = interlayer distance. 

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... 

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). 

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)... 

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). 

Cs NMR results for Cs on the surfaces of illite, kaolinite, boehmite and silica gel (Figure 3) show that for this large, low charge cation the surface behavior is quite similar to the interlayer behavior. They also illustrate the capabilities of NMR methods to probe surface species and the effects of RH on the structural environments and dynamical behavior of the Cs. The samples were prepared by immersing 0.5 gm of powdered solid in 50 ml of O.IM CsCl solution at 2 5°C for 5 days. Final pHs were between 4.60 and 7.77, greater than the zero point of charge, except for boehmite, which has a ZPC... 

V. Laperche, J. F. Lambert, R. Prost, R., and J. J. Fripiat, High-resolution solid-state NMR of exchangeable cations in the interlayer surface of a swelling mica %a. 

Variations in interlayer cation sites in clay minerals as studied by Cs MAS nuclear magnetic resonance spectroscopy. Am. Mineral. 75 970 (1990). ... 

In the pyroaurite structure the brucite layers are cationic. However, on oxidation the resultant brucite layers in y - NiOOH are anionic. To preserve electroneutrality, cations and anions are exchanged in the intercalated layer during the oxidation-reduction process. This is illustrated in Fig. 4. In the case of Mn-substituted materials, some Mn can be reduced to Mn(II). This neutralizes the charge in the brucite layer this part of the structure reverts to the P - Ni(OH)2 structure and the intercalated water and anions are expelled from the lattice. With this there is a concomitant irreversible contraction of the interlayer spacing from 7.80 to 4.65A [72]. 

Two classes of clays are known [3] (i) cationic clays (or clay minerals) that have negatively charged alumino-silicate layers balanced by small cations in the interlayer space (e.g. K-10 montmorillonite) and (ii) anionic clays which have positively charged brucite-type metal hydroxide layers balanced by anions and water molecules located interstitially (e.g. hydrotalcite, Mg6Al2(0H)igC034H20. 

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