Crystallization Behavior of Elastomeric Block Copolymers: Thermoplastic Polyurethane and Polyether-block-Amide

The isothermal crystallization kinetics of melt-blown webs produced from a series of elastomeric block copolymers was studied through differential scanning calorimetry (DSC). Three hardness grades were selected for a polyester and a polyether Elastollan (R) thermoplastic polyurethane and Pebax (R) polyether-block-amide copolymers. The Avrami crystallization kinetics parameters, k and n, were derived from two different methods: (1) traditional Avrami model and (2) derivative of the Avrami model proposed by Kurajica et al. (Croat Chem Acta 2002, 75, 693). The kinetic parameters from both models were consistent and showed good correlation. For all polymer types and hardness grades, crystallization kinetics were interpreted with the derivative model (Kurijica et al.) since it could be directly fitted to untransformed DSC isothermal crystallization data, and thus reduces the errors involved in Avrami analysis. The values of the Avrami exponent, n ranged between 2.59 and 3.41, indicating similar nucleation and growth mechanisms. These n values and morphological observations indicate that crystallization occurs in these copolymers in three dimensions from pre-existing nuclei and the crystals grow under isothermal conditions. This suggests that, in these elastomeric copolymers, crystallization of the hard segments drives microphase separation into crystalline and amorphous regions rather than formation of hard and soft domains. (c) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 1246-1256, 2009