The Influence of Hydroxyl Orientation, Stacking Sequence, and Ionic Substitutions on the Interlayer B O N D I N G of Micas

-Hydroxyl orientation has a major influence on the strength of the ionic interlayer bonding in micas because of the strong repulsion between the hydrogen and the interlayer cation (IC). In order to determine if other factors also influence the magnitude of the interlayer bond energy, the effect due to the varying H-IC distance, as one finds, for example, between a dioctahedral and a trioctahedral mica, must be removed. This can be done by calculating the bond energy as a function of the H IC distance; a plot of which is a smooth curve with a minimum energy for the minimum H-IC distance. If there are no other factors which substantially contribute to the interlayer bonding energy, such curves for all micas should be superimposed. If, however, the curves are not superimposed but fall into groups with common attributes (stacking sequence, ionic substitutions, etc.) the energy separations between groups of curves indicate the influence of these other factors. The results of such calculations for four dioctahedral micas (2M 1 muscovite, 3T mus6ovite, and two 1M muscovites) and four trioctahedral micas (2M1 biotite, 1M phlogopite, 2M 2 lepidolite and a 1M MgIV mica) indicate that these curves are at higher energy for dioctahedral than for trioctahedral micas and this energy increase is due to the filling of the octahedral sites. The dioctahedral micas are arranged in terms of energy as 1M >_ 3T ~> 2M~ while the order for the trioctahedral micas is 1M > 2M~ ~ 2M2. In addition, the calculated energies suggest that the distribution of the layer charge between the octahedral and tetrahedral sheets affects the strength of the interlayer bond such that the greater the charge on the octahedral sheet, the stronger the interlayer bond.