Abstract: | tert‐Butyl‐substituted poly(ether ether ketone) (tBuPEEK), which does not undergo crystallization with thermal annealing, crystallizes readily when treated with compressed CO2. The dissolved CO2 causes a reduction in the glass‐transition temperature of the polymer–gas system and enhances the chain mobility of the macromolecules, thereby bringing about crystallization. In the presence of CO2, crystallization is increasingly favored with increasing CO2 pressure and treatment temperature. The melting point of tBuPEEK crystals increases linearly with the CO2 pressure applied in the treatment, indicating an increase in the order and/or size of the crystals. The extent of crystallinity increases when small amounts of methanol or dichloromethane are used as a cosolute with CO2. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1505–1512, 2001 |