Tuning Polymer Crystallization for Properties

Crystallization plays a major role in determining the thermal and mechanical behavior of polymers as it permits polymers to retain rigidity at temperatures exceeding the Tg. Crystallization also enhances the barrier properties and solvent resistance, as small molecules cannot diffuse through crystalline domains. Crystallization of polymers can be tuned, and thus can provide very usefiil control over 

Crystallization in step-growth polymers such as polyesters and nylons is known to assist their subsequent solid-state polymerization because exclusion of reactive end-groups from crystalline domains enhances their effective concentration in the amorphous domains [14,15]. However, the condensation reaction between the last fraction of end-groups may be hindered by crystallization [16, 17]. The possibility and rate of crystallization can also be enhanced by processes that enhance orientation, such as shearing and fiber drawing [18]. For example, partial replacement of terephthalic units with isophthalic units in PET reduces crystallinity, so that no crystallization in seen in 70 30 random poly(ethylene terephthalate-co-ethylene iso-phthalate) under quiescent conditions. However, heating its amorphous fiber above its Tg under a moderate tensile force results in rapid stress-induced crystallization [19]. The reduction in crystallization by copolymerization has been employed to enhance drawability of melt-spun polyester and polyamide fibers [20]. 

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