Hostname: page-component-848d4c4894-x5gtn Total loading time: 0 Render date: 2024-05-29T15:51:57.462Z Has data issue: false hasContentIssue false
  • English
  • Français

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

Published online by Cambridge University Press:  28 February 2024

E. J. Sullivan ,
D. B. Hunter  and
R. S. Bowman
E. J. Sullivan
Affiliation:
Department of Earth and Environmental Science and Geophysical Research Center, New Mexico Institute of Mining and Technology, Socorro, New Mexico 87801
D. B. Hunter
Affiliation:
Division of Biogeochemistry, University of Georgia, Savannah River Ecology Laboratory, Aiken, South Carolina 2981
R. S. Bowman
Affiliation:
Department of Earth and Environmental Science and Geophysical Research Center, New Mexico Institute of Mining and Technology, Socorro, New Mexico 87801
Get access Rights & Permissions [Opens in a new window]

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-directionthickness 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-thicknesson 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 °C 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.

Keywords

HexadecyltrimethylammoniumMuscovite MicaSurface ImagingThermal AnalysisZeolite
Type
Research Article
Information
Clays and Clay Minerals , Volume 45 , Issue 1 , February 1997 , pp. 42 - 53
Copyright
Copyright © 1997, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Bish, D.L.. 1988. Effects of composition on the dehydration behavior of clinoptilolite and heulandite. Kalló D, Sherry HS, editors. Occurrence, properties, and utilization of natural zeolites. Budapest, Hungary: Akadémiai Kiadó. p 565–576.Google Scholar
Bowman, R.S., Haggerty, G.M., Huddleston, R.G., Neel, D. and Flynn, M.M.. 1995. Sorption of nonpolar organic compounds, inorganic cations, and inorganic oxyanions by surfactant-modified zeolites. Sabatini DA, Knox RC, Harwell JH, editors. Surfactant-enhanced subsurface remediation. ACS symposium series 594. Washington, DC: Am Chem Soc. p 54–64.Google Scholar
Brunauer, S., Emmett, P.H. and Teller, E.. 1938. Adsorption of gases in multimolecular layers. J Am Chem Soc 60: 309–319.CrossRefGoogle Scholar
Chen, Y.L., Chen, S., Frank, C. and Israelachvili, J.. 1992. Molecular mechanisms and kinetics during the self-assembly of surfactant layers. J Colloid Interface Sci 153(1): 244–265.CrossRefGoogle Scholar
Chipera, S.J. and Bish, D.L.. 1995. Multireflection RIR and intensity normalizations for quantitative analyses: Applications to feldspars and zeolites. Powder Diffract 10: 47–55.CrossRefGoogle Scholar
Haggerty, G.M. and Bowman, R.S.. 1994. Sorption of chromate and other inorganic anions by organozeolite. Environ Sci Technol 28(3): 452–458.CrossRefGoogle ScholarPubMed
Israelachvili, J.N.. 1991. Intermolecular and surface forces. 2nd ed. San Diego, CA: Academic Pr. 450 p.Google Scholar
Komiyama, M. and Yashima, T.. 1994. Atomic force microscopy images of natural zeolite surfaces observed under ambient conditions. Jpn J Appl Phys 33(1,6B): 3761–3763.Google Scholar
MacDougall, J.E., Cox, S.D., Stucky, G.D., Weisenhorn, A.L., Hansma, P.K. and Wise, W.S.. 1991. Molecular resolution of zeolite surfaces as imaged by atomic force microscopy. Zeolites 11: 429–433.CrossRefGoogle Scholar
Malliaris, A., Lang, J. and Zana, R.. 1986. Micellar aggregation numbers at high surfactant concentration. J Colloid Interface Sci 110(1): 237–242.CrossRefGoogle Scholar
Manne, S. and Gaub, H.E.. 1995. Molecular organization of surfactants at solid-liquid interfaces. Science 270: 1480–1482.CrossRefGoogle Scholar
Maurice, P.A.. 1995. Applications of atomic-force microscopy in mineral-water interface chemistry. American Chemical Society preprint extended abstract, Division of Environmental Chemistry; 1995 April 2-7; Anaheim, CA. p 521–524.Google Scholar
Ming, D.W. and Dixon, J.B.. 1987. Quantitative determination of clinoptilolite in soils by a cation-exchange capacity method. Clays Clay Miner 35: 463–468.CrossRefGoogle Scholar
Ming, D.W. and Mumpton, F.A.. 1989. Zeolites in soils. In: Dixon, J.B., Weed, S.B., editors. Minerals in soil environments. 2nd ed. Madison, WI: Soil Sci Soc Am. p 873–911.Google Scholar
Neel, D. and Bowman, R.S.. 1992. Sorption of organics to surface-altered zeolites. Proc 36th Annu New Mexico Water Conf; Las Cruces; 1991 November 7-8. Las Cruces: New Mexico Water Research Inst. p 57–61.Google Scholar
Ong, S.K. and Lion, L.W.. 1991. Effects of soil properties and moisture on the sorption of trichloroethylene vapor. Water Res 25: 29–36.CrossRefGoogle Scholar
Petersen, L.W., Moldrup, P., El-Farhan, Y.H., Jacobsen, O.H. and Rolston, D.E.. 1995. The effect of moisture and soil texture on the adsorption of organic vapors. J Environ Qual 24: 752–759.CrossRefGoogle Scholar
Reiss-Husson, F. and Luzzati, V.. 1964. The structure of the micellar solutions of some amphiphilic compounds in pure water as determined by absolute small-angle X-ray scattering techniques. J Phys Chem 68: 3504–3510.CrossRefGoogle Scholar
Scandella, L., Kruse, N. and Prins, R.. 1993. Imaging of zeolite surface structures by atomic force microscopy. Surf Sci Lett 281: 331–334.CrossRefGoogle Scholar
Smyth, J.R., Spaid, A.T. and Bish, D.L.. 1990. Crystal structures of a natural and a Cs-exchanged clinoptilolite. Am Mineral 75: 522–528.Google Scholar
Stipp, S.L.S., Eggleston, C.M. and Nielsen, B.S.. 1994. Calcite surface structure observed at microtopographic and molecular scales with atomic force microscopy (AFM). Geochim Cosmochim Acta 58(14): 3023–3033.CrossRefGoogle Scholar
Sullivan, E.J., Bowman, R.S. and Haggerty, G.M.. 1994. Sorption of inorganic oxyanions by surfactant-modified zeolite. Spectrum 94, Proc Nuclear and Hazardous Waste Management International Topical Meeting, vol 2; 1994 August 14-18; Atlanta, GA. p 940–945.Google Scholar
Weisenhorn, A.L., MacDougall, J.E., Gould, A.C., Cox, S.D., Wise, W.S., Massie, J., Maivald, P., Elings, V.B., Stucky, G.D. and Hansma, P.K.. 1991. Imaging and manipulating molecules on a zeolite surface with an atomic force microscope. Science 24: 1330–1333.Google Scholar
Zhang, Z.Z., Sparks, D.L. and Scrivner, N.C.. 1993. Sorption and desorption of quaternary amine cations on clays. Environ Sci Technol 27: 1625–1631.CrossRefGoogle Scholar
Zhong, Q., Inniss, D., Kjoller, K. and Elings, V.B.. 1993. Fractured polymer/silica fiber surface studied by tapping mode atomic force microscopy. Surf Sci Lett 290: L688–L692.Google Scholar