Skip to main content Accessibility help
  • Get access
    Check if you have access via personal or institutional login
  • Cited by 1
  • Print publication year: 2011
  • Online publication date: August 2011

2 - Thermodynamics and kinetics of polymer–clay nanocomposites


In order for nanocomposites to be useful, they must be thermodynamically stable. It is therefore critical to ensure that clay nanoparticles have surfaces that interact with polymer in a way that yields exfoliated structures that do not spontaneously phase separate. Although some intercalated–exfoliated systems may yield useful improvements in properties, the exfoliated state is still the ultimate goal in producing a nanocomposite with the ultimate property enhancements.

The rate at which intercalation/exfoliation occurs is also of some importance in ensuring that a nanocomposite can be made on a timescale that is commercially viable. Since the level of exfoliation is critical in order that the maximum change in properties in nanocomposites is reached, the ability to measure the level of exfoliation is of paramount importance.

In this chapter, the thermodynamics of intercalation/exfoliation will be discussed in detail, including surface modification of clays, processing strategies, and the enthalpic and entropic components of the intercalation/exfoliation process. In addition, the kinetics related to intercalation/exfoliation will be presented. Finally, a critical evaluation of the analytical methods utilized commonly to determine the level of intercalation/exfoliation will be given.

Clay surface compatibility with polymers

Smectite clay structure

The discussion of clay surface compatibility with polymers in this section will focus primarily on montmorillonite as the example clay. The characteristics discussed will only vary by degree for other smectic clays.

Related content

Powered by UNSILO
Beall, G. W., Tsipursky, S., Sorokin, A., and Goldman, A.. Intercalates and exfoliates formed with oligomers and polymers and composite materials containing same, US patent number 5552469, 1996-09-03.
Vaia, R. A., Vasudevan, S., Krawiec, W., Scanlon, L. G., and Giannelis, E. P.. New polymer electrolyte nanocomposites. Melt intercalation of poly(ethylene oxide) in mica-type silicates. Advanced Materials, 7:2 (1995), 154–156.
Siptak, D.. Smectite organoclay chemistry: organically modified bentonite reacted with organic cations. Chemistry and Manufacture of Cosmetics (3rd edn) (2002), 3(Bk 2), 845–855.
Nahin, P. G.. Perspectives in applied organoclay chemistry. In Clays and Oxford, National Clay Minerals, Proceedings of the 10th Conference on Clays and Clay Minerals (Pergamon, 1963), Austin, Texas, 1961, pp. 257–271.
Hedley, C. B., Yuan, G., and Theng, B. K. G.. Thermal analysis of montmorillonites modified with quaternary phosphonium and ammonium surfactants. Applied Clay Science, 35:3–4 (2007), 180–188.
Beall, G. W.. The use of organo-clays in water treatment. Applied Clay Science, 24:1–2 (2003), 11–20.
Bartels, J., Beall, G. W., Grah, M., Jin, K., Speer, D., and Yarbrough, J.. Intercalated clays from pentaerythritol stearate for use in polymer nanocomposites. Journal of Applied Polymer Science, 108:3 (2008), 1908–1916.
Fischer, H.. Polymer nanocomposites: from fundamental research to specific applications. Materials Science & Engineering, C: Biomimetic and Supramolecular Systems, C23:6–8 (2003), 763–772.
Chiem, L. T., Huynh, L., Ralston, J., and Beattie, D. A.. An in situ ATR–FTIR study of polyacrylamide adsorption at the talc surface. Journal of Colloid and Interface Science, 297:1(2006), 54–61.
Wittmann, J. C. and Lotz, B.. Polymer decoration of layer silicates: crystallographic interactions at the polyethylene–talc interface. Journal of Materials Science, 21:2 (1986), 659–668.
Yatsenko, V. V., Isaenya, L. A., Revyako, M. M., and Markina, A. Y.. Modification of the surface of fillers in polyethylenimine-based composite materials. Issled. Obl. Khim. Polietilenimina Ego Primen. Prom-sti. (1977), 154–5.
Peterson, E. A.. Fundamental studies of clay surface treatments to facilitate exfoliation, MA thesis, Texas State University, San Marcos, TX (2005).
Kracalik, M., Studenovsky, M., Mikesova, J., Sikora, A., Thomann, R., Friedrich, C., Fortelny, I., and Simonik, J.. Recycled PET nanocomposites improved by silanization of organoclays. Journal of Applied Polymer Science, 106:2 (2007), 926–937.
Kim, D.-W., Park, K.-W., Chowdhury, S. R., Kim, G.-H.. Effect of compatibilizer and silane coupling agent on physical properties of ethylene vinyl acetate copolymer/ethylene-1-butene copolymer/clay nanocomposite foams. Journal of Applied Polymer Science, 102:4 (2006), 3259–3265.
Kumar, S. and Jayaraman, K.. The use of silane coupling agents in polypropylene/clay nanocomposites. In Proceedings of the 29th Annual Meeting of the Adhesion Society (2006), pp. 235–236.
Kim, K., Utracki, L. A., and Kamal, M. R.. Numerical simulation of polymer nanocomposites using self-consistent mean-field model. Journal of Chemical Physics 121:21 (2004), 10766–10777.
Kudryavtsev, Y. V., Govorun, E. N., Litmanovich, A. D., and Fischer, H. R.. Polymer melt intercalation in clay modified by diblock copolymers. Macromolecular Theory and Simulations, 13:5 (2004), 392–399.
Chen, B., Evans, J. R. G., Greenwell, H. C., Boulet, P., Coveney, P. V., Bowden, A. A., and Whiting, A.. A critical appraisal of polymer–clay nanocomposites. Chemical Society Reviews, 37:3 (2008), 568–594.
Zhulina, E., Singh, C., and Balazs, A. C.. Attraction between surfaces in a polymer melt containing telechelic chains: guidelines for controlling the surface separation in intercalated polymer–clay composites. Langmuir, 15:11 (1999), 3935–3943.
Vaia, R. A., Jandt, K. D., Kramer, E. J., and Giannelis, E. P.. Kinetics of polymer melt intercalation. Macromolecules, 28:24 (1995), 8080.
Limpanart, S., Khunthon, S., Taepaiboon, P., Supaphol, P., Srikhirin, T., Udomkichdecha, W., and Boontongkong, Y.. Effect of the surfactant coverage on the preparation of polystyrene–clay nanocomposites prepared by melt intercalation. Materials Letters, 59:18 (2005), 2292–2295.
Nowicki, W.. Structure and entropy of a long polymer chain in the presence of nanoparticles. Macromolecules, 35:4 (2002), 1424–1436.
Nowicki, W.. Properties of systems composed of nanosized particles and very-high-molecular-weight linear polymers. Seria Chemia (Uniwersytet im. Adama Mickiewicza w Poznaniu), 73 (2002), 1–170.
Wu, D., Zhou, C., and Zheng, H.. A rheological study on kinetics of poly(butylene terephthalate) melt intercalation. Journal of Applied Polymer Science, 99:4 (2006), 1865–1871.
Li, J., Zhou, C., Wang, G., and Zhao, D.. Study on kinetics of polymer melt intercalation by a rheological approach. Journal of Applied Polymer Science, 89:2 (2003), 318–323.
Li, Y. and Ishida, H.. A study of morphology and intercalation kinetics of polystyrene–organoclay nanocomposites. Macromolecules, 38:15 (2005), 6513–6519.
Chen, H., Schmidt, D. F., Pitsikalis, M., Hadjichristidis, N., Zhang, Y., Wiesner, U., and Giannelis, E. P.. Poly(styrene-block-isoprene) nanocomposites: kinetics of intercalation and effects of copolymer on intercalation behaviors. Journal of Polymer Science, Part B: Polymer Physics, 41:24 (2003), 3264–3271.
Chen, H., Shah, D., and Giannelis, E. P.. Polymer nanocomposites: interplay between thermodynamics and kinetics. Polymer Preprints (American Chemical Society, Division of Polymer Chemistry), 44:2 (2003), 243–244.
Manias, E., Chen, H., Krishnamoorti, R., Genzer, J., Kramer, E. J., and Giannelis, E. P.. Intercalation kinetics of long polymers in 2 nm confinements. Macromolecules, 33:21 (2000), 7955–7966.
Lee, J. Y., Baljon, A. R. C., Sogah, D. Y., and Loring, R. F., Molecular dynamics study of the intercalation of diblock copolymers into layered silicates. Journal of Chemical Physics, 112:20 (2000), 9112–9119.