Isomorphous substitution saponites

In montmorillonite some of the Al3 + in the octahedral sublattice are replaced by Mg2+ ions, and in hectorite some of the Mg2 + in the octahedral sublattice are replaced by Li+ ions. With beidellite and saponite, however, the isomorphous substitution takes place in the tetrahedral sublattice with Al3 + replacing some of the Si4+ ions. The residual negative charges in the layers on montmorillonite, hectorite, beidellite, and saponite are counterbalanced in the natural state by coexisting interlamellar, hydrated cations, usually Na+,... 

The material from the Hector area of California is believed to have formed by the action of hot spring waters containing Li and F on clinoptiolite. The Mg was obtained from the alkaline lake waters (Ames and Goldich, 1958). The material from Morocco is associated with marls and is believed to be authigenic. These two types of trioctahedral smectite appear to be the only ones with a relatively pure Si tetrahedral sheet. No analyses were found which indicated tetrahedral Al values between 0.02 and 0.30. Analyses of saponite indicate there is complete isomorphous substitution between the range Si3.70 Al0.3o and Si3.0s Al0.92 (Table XXXIX). Caillere and Henin (1951) reported an analysis of a fibrous expanded clay (diabantite) which had a tetrahedral composition of Si3.i7 Alo.49 Fe3+0.34. There is some question as to whether this should be classified as a smectite regardless, it indicates the possibility of Fe3+ substitution in the tetrahedral sheets of the trioctahedral 2 1 clays. 

The air dried (400°C/2h) expanded saponite exhibits bands near 3738 cm , 3668 cm , and 3590 cm , attributed to silanol groups associated with the pillars, with structural OH, and with Si-OH-Al groups in the tetrahedral layers resulting from isomorphous substitution... 

This particle is naturally occurring and found around the world. It is easily mined and purified. The reactor for the particle was a volcano. The ash from many volcanoes was spread around the earth during an intense period of activity many millions of years ago. This ash was transformed into clay (montmorillonoids or smectites) by natural processes, into uncharged species (talc and pyrophyllite) and charged species through isomorphic substitution of the crystal structure (hectorite, montmorillon-ite, saponite, suconite, volchonskoite, vermiculite, and nontronite). 

These experiments do not prove, but suggest the existence of a qualitative boundary separating saponites from vermiculites. This boundary cannot be found in the structural formula. If it exists, it can only be found in the distribution (ordered and disordered) of isomorphous replacements. The exact structure of saponites is still poorly known. Vermiculites are most often derived from biotite and phlogopite and could inherit the structure of the tetrahedral layers of micas. The A1 atoms in the tetrahedral layers of micas form unidimensional, ordered ensembles (linear chains of substitution Gatineau [1964] and Gatineau and Merino [1966]). 

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