Simultaneously Tailoring Surface Energies and Thermal Stabilities of Cellulose Nanocrystals Using Ion Exchange: Effects on Polymer Composite Properties for Transportation, Infrastructure, and Renewable Energy Applications

Authors: Douglas M. Fox,*,† Rebeca S. Rodriguez, Mackenzie N. Devilbiss, Jeremiah Woodcock, Chelsea S. Davis, Robert Sinko,§ Sinan Keten,§ and Jeffrey W. Gilman

Department of Chemistry, American University, Washington, D.C. 20016-8014, United States
Materials Science and Engineering Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-8664, United States,
§Department of Civil and Environmental Engineering and Department of Mechanical Engineering, Northwestern University, Evanston, Illinois 60208-3109, United States

ABSTRACT: Cellulose nanocrystals (CNCs) have great potential as sustainable reinforcing materials for polymers, but there are a number of obstacles to commercialization that must first be overcome. High levels of water absorption, low thermal stabilities, poor miscibility with nonpolar polymers, and irreversible aggregation of the dried CNCs are among the greatest challenges to producing cellulose nanocrystal−polymer nanocomposites. A simple, scalable technique to modify sulfated cellulose nanocrystals (Na-CNCs) has been developed to address all of these issues. By using an ion exchange process to replace Na+ with imidazolium or phosphonium cations, the surface energy is altered, the thermal stability is increased, and the miscibility of dried CNCs with a nonpolar polymer (epoxy and polystyrene) is enhanced. Characterization of the resulting ion exchanged CNCs (IE-CNCs) using potentiometry, inverse gas chromatography, dynamic vapor sorption, and laser scanning confocal microscopy reveals that the IE-CNCs have lower surface energies, adsorb less water, and have thermal stabilities of up to 100 °C higher than those of prepared protonated cellulose nanocrystals (H-CNCs) and 40 °C higher than that of neutralized Na-CNC. Methyl(triphenyl)phosphonium exchanged cellulose nanocrystals (MePh3P-CNC) adsorbed 30% less water than Na-CNC, retained less water during desorption, and were used to prepare well-dispersed epoxy composites without the aid of a solvent and well-dispersed polystyrene nanocomposites using a melt blending technique at 195 °C. Predictions of dispersion quality and glass transition temperatures from molecular modeling experiments match experimental observations. These fiber reinforced polymers can be used as lightweight composites in transportation, infrastructure, and renewable energy applications.

KEYWORDS: cellulose nanocrystals, ionic liquids, polymer composites, epoxy, extrusion, dispersion

Link to the article: https://pubs.acs.org/doi/abs/10.1021/acsami.6b06083

Articles on DVS and iGC-SEA instruments: https://www.surfacemeasurementsystems.com/articles-dvs-igc-sea/

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