Abstract: Angewandte Chemie International EditionVolume 43, Issue 17 p. 2239-2243 Communication Surface Structure of Organoclays† Hendrik Heinz Dr., Hendrik Heinz Dr. Institute of Polymers, Department of Materials, ETH Zürich, 8092 Zürich, Switzerland, Fax: (+41) 163-21592Search for more papers by this authorUlrich W. Suter Prof. Dr., Ulrich W. Suter Prof. Dr. [email protected] Institute of Polymers, Department of Materials, ETH Zürich, 8092 Zürich, Switzerland, Fax: (+41) 163-21592Search for more papers by this author Hendrik Heinz Dr., Hendrik Heinz Dr. Institute of Polymers, Department of Materials, ETH Zürich, 8092 Zürich, Switzerland, Fax: (+41) 163-21592Search for more papers by this authorUlrich W. Suter Prof. Dr., Ulrich W. Suter Prof. Dr. [email protected] Institute of Polymers, Department of Materials, ETH Zürich, 8092 Zürich, Switzerland, Fax: (+41) 163-21592Search for more papers by this author First published: 16 April 2004 https://doi.org/10.1002/anie.200352747Citations: 74 † We thank Prof. Dr. Wolfgang Paul, Department of Physics, University of Mainz (Germany), and Prof. Dr. Andrey Milchev, Department of Physics and Astronomy, University of Athens, Georgia (USA), for helpful discussions. We acknowledge support from the ETH Zürich, the Swiss National Science Foundation, and the Studienstiftung des Deutschen Volkes. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract While long and very short alkyl chains in alkylammonium-mica form a homogeneous mixture with remaining alkali ions on the mica surface, chains of medium length (≈C12) prefer island structures (see picture showing the type of system found for various degrees of surface coverage and chain length). This observation is described in detail and a thermodynamic explanation is given. References 1G. Wypych, Handbook of Fillers, 2nd ed., ChemTec, Toronto, 1999. 2C. A. Helm, J. N. Israelachvili, P. M. McGuiggan, Science 1989, 246, 919. 3aY. Tsao, S. X. Yang, D. F. Evans, H. Wennerström, Langmuir 1991, 7, 3154; 3bY. Tsao, D. F. Evans, H. Wennerström, Science 1993, 262, 547. 4S. Manne, H. E. Gaub, Science 1995, 270, 1480. 5W. A. Hayes, D. K. Schwartz, Langmuir 1998, 14, 5913. 6M. A. Osman, G. Seyfang, U. W. Suter, J. Phys. Chem. B 2000, 104, 4433. 7M. A. Osman, M. Ernst, B. H. Meier, U. W. Suter, J. Phys. Chem. B 2002, 106, 653. 8T. C. Merkel, B. D. Freeman, R. J. Spontak, Z. He, I. Pinnau, P. Meakin, A. J. Hill, Science 2002, 296, 519. 9F. M. Haas, R. Hilfer, K. Binder, J. Chem. Phys. 1995, 102, 2960. 10E. Hackett, E. Manias, E. P. Giannelis, J. Chem. Phys. 1998, 108, 7410. 11S. Karaborni, B. Smit, W. Heidug, J. Urai, E. van Oort, Science 1996, 271, 1102. 12J. A. Greathouse, K. Refson, G. Sposito, J. Am. Chem. Soc. 2000, 122, 11 459. 13H. Heinz, H.-J. Castelijns, U. W. Suter, J. Am. Chem. Soc. 2003, 125, 9500. 14H. Heinz, W. Paul, U. W. Suter, K. Binder, J. Chem. Phys. 2004, 120, 3847. 15L.-Q. Wang, J. Liu, G. J. Exarhos, K. Y. Flanigan, R. Bordia, J. Phys. Chem. B 2000, 104, 2810. 16H. Heinz, U. W. Suter, submitted. 17The parameter for the periodic boundary condition in z direction is chosen >4 nm larger than the z extension of the real system so that interactions in this direction are negligible. 18E. Leontidis, H. Heinz, K. Palewska, E.-U. Wallenborn, U. W. Suter, J. Chem. Phys. 2001, 114, 3224. 19H. Heinz, U. W. Suter, E. Leontidis, J. Am. Chem. Soc. 2001, 123, 11 229. 20MSI. Cerius2 and Discover program. Discover User Guide, Version 96.0/4.0.0, Molecular Simulations, San Diego, CA, 1996. 21The moduli are approximated in z direction from the compressibility of liquid n-hexadecane and in the x and the y directions from the elastic modulus for mica, which is reduced to approximately 20 % owing to intercalation of the organic layers. 22M. Lipsicas, R. H. Raythatha, T. J. Pinnavaia, I. D. Johnson, R. F. Giese, P. M. Constanzo, J. L. Robert, Nature 1984, 309, 604. 23J. Sanz, J. M. Serratosa, J. Am. Chem. Soc. 1984, 106, 4790. 24C. P. Herrero, J. Sanz, J. Phys. Chem. Solids 1991, 52, 1129. 25M. Copel, M. C. Reuter, E. Kaxiras, R. M. Tromp, Phys. Rev. Lett. 1989, 63, 632. 26ΔShead is approximated by the negative mixing entropy (−ΔSmix) of ideal gases by using the mole fractions x1=0.2 for the alkali ions and x2=0.8 for the organic ions: ΔSmix=n R(x1 ln x1+x2 ln x2); R is the universal gas constant and n the total amount of ions. Citing Literature Volume43, Issue17April 19, 2004Pages 2239-2243 ReferencesRelatedInformation