Hydroxyl Stretching Frequencies of Synthetic Ni-, Al-, and Mg-Hydroxy Interlayers in Expanding Clays

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Abstract
Interlayers were produced in montmorillonite, vermiculite and hectorite in aqueous suspensions by precipitation from metal chloride salt, by hydrolysis of metal amalgams, and by slow hydrolysis of metal acetate during refluxing. In several systems an external phase of bayerite, gibbsite, or brucite was also formed. A prominent high frequency OH stretching vibration is associated with the interlayer in montmorillonites with approximate frequencies of 3660 cm−1 with nickel interlayers, 3690 cm−1 with aluminium interlayers and 3710 cm−1 with magnesium interlayers. Pleochroism studies indicate transition moment of interlayer OH to be at a relatively high angle to the planar surface of the clay crystals. Aluminium interlayers show some evidence of an additional weak absorption in the lower frequency region of 3570–3600 cm−1. In differential studies the lower frequency absorption is more evident and is shown to be unaffected by orientation. Techniques involving balancing of water deformation bands in differential spectra and D2O exchange suggest that it is not a water band. D2O flushing to remove water leaves the low frequency interlayer OH band more prominent in hectorite where the clay crystal OH is at 3680 cm−1. Deuteration studies show that flushing with D2O at room temperature removes water, and heating at 100°C in D2O vapor exchanges interlayer OH but not the clay crystal OH. Study of the OD stretching of the systems with deuterated interlayers supports observations made in the OH stretching bands.