Topological and Thermal Properties of Surfactant-Modified Clinoptilolite Studied by Tapping-Mode™ Atomic Force Microscopy and High-Resolution Thermogravimetric Analysis

E.J. Sullivan1, D.B. Hunter2 and R.S. Bowman1
1 Department of Earth and Environmental Science and Geophysical Research Center, New Mexico Institute of Mining and Technology, Socorro, New Mexico 87801
2 Division of Biogeochemistry, University of Georgia, Savannah River Ecology Laboratory, Aiken, South Carolina 29801

Abstract: Unmodified and surfactant-modified clinoptilolite-rich tuff (referred to here as “clinoptilolite”) and muscovite mica were examined with tapping-mode atomic force microscopy (TMAFM) and high-resolution thermogravimetric analysis (HR-TGA) in order to elucidate patterns of hexadecyltrimethylammonium bromide (HDTMA) sorption on the treated surface and to understand the mechanisms of this sorption. TMAFM images were obtained to a scale of 50 nm by 50 nm. The images of unmodified clinoptilolite showed a framework pattern on the ac plane, comparable to previously reported images. Images of modified clinoptilolite at 12.5% and 25% of external cation exchange capacity (ECEC) coverage by HDTMA showed evidence of the HDTMA molecules arranged as elongated, topographically raised features on the ac plane. At 50% HDTMA coverage, the images contained what appeared to be agglomerations of surfactant tail groups. The z-direction thickness of the raised features on the 12.5% coverage sample corresponded to the thickness of the carbon chain of the surfactant tail-group (0.4 nm), whereas the z-thickness on the 25% coverage sample was between 0.4 and 0.8 nm, indicating crossing or doubling of tail groups. Repulsive forces between the modified clinoptilolite and the silicon TMAFM probe increased with increasing HDTMA coverage. HR-TGA showed a 100 ° increase in HDTMA pyrolysis temperatures at coverages of less than 50%, probably due to an increased stabilization of the HDTMA due to direct tail interactions with the clinoptilolite surface at lower coverages versus smaller stabilization due to surfactant tail-tail interactions at higher coverages. Our results indicate that buildup of HDTMA admicelles or some form of a bilayer begins before full monolayer coverage is complete.

Key Words: Hexadecyltrimethylammonium • Muscovite Mica • Surface Imaging • Thermal Analysis • Zeolite

Clays and Clay Minerals; February 1997 v. 45; no. 1; p. 42-53; DOI: 10.1346/CCMN.1997.0450105
© 1997, The Clay Minerals Society
Clay Minerals Society (www.clays.org)