FTIR Study of Deuterated Montmorillonites: Structural Features Relevant to Pillared Clay Stability

Krishna Bukka, J. D. Miller and Joseph Shabtai
Department of Metallurgy and Metallurgical Engineering University of Utah, Salt Lake City, Utah 84112-1183
Department of Fuels Engineering, University of Utah Salt Lake City, Utah 84112-1183

Abstract: FTIR studies of six partially-deuterated montmorillonites (MS) reveal the presence of two O-D stretching bands, one between 2702–2728 cm-1 and another near 2680 cm-1. For homoionic (Li, Na, Mg, Ca, or La) Wyoming-type MS, the position of the higher frequency band, designated as (O-D)h, is between 2714–2728 cm-1, whereas for homoionic Cheto-type MS it is between 2702–2706 cm-1. The lower frequency band, designated as (O-D)l, is in the narrow range of 2674–2684 cm-1. Resolution of two corresponding O-H bands, appearing near 3670 and 3635 cm-1, was observed only after partial dehydroxylation of the smectites. The changes in the relative intensities of the two O-D stretching bands as a function of the smectite type and of the Lewis acidity (charge density) of the exchangeable ion were determined. For Wyoming-type MS, the intensity of the (O-D)h band is much lower than that of the (O-D)l band, whereas for Cheto-type MS, the intensity of the (O-D)h band is about equal or slightly higher than that of the (O-D)l band. The observed resolution can be ascribed tentatively to the presence of (at least) two types of octahedral OH groups in the smectites, the (O-D)h band being assigned to AlMgOH and the (O-D)l band to AlAlOH groups. Pillaring of Cheto-type MS with hydroxy-Al13 oligocations resulted in products showing much higher thermal stability between 400–600°C compared to that of identically pillared Wyoming-type MS. Compositional and other factors, e.g., CEC values and mode of pillaring, may cause this difference in stability.

Key Words: Deuterated montmorillonites • FITR • Pillared smectites • Thermal stability

Clays and Clay Minerals; February 1992 v. 40; no. 1; p. 92-102; DOI: 10.1346/CCMN.1992.0400110
© 1992, The Clay Minerals Society
Clay Minerals Society (www.clays.org)