Structure of Negative Spherulites of Even–Even Polyamides. Introducing a Complex Multicomponent Spherulite Architecture

Even–even polyamides are known to grow as positive spherulites, which implies that the radial, fastest growth direction is parallel to the a-axis and hydrogen bond direction. However, after annealing/self-seeding close to Tm, crystallization in a limited Tc window (down to ≈20 °C below Tm) yields profuse negative spherulites and, frequently stemming from the latter, less frequent and ill-defined entities named “spherulitic aggregates”. The detailed structure and origin of these two entities, and especially of the negative spherulites, are still not clearly established although they were first observed some 70 years ago. The recent recognition that polymer spherulites (specifically, spherulites of PVDF in its γ phase) are made of scrolled, radiating lamellae and the observation and analysis of solution grown, scrolled nylon-66 single crystals provide useful guidelines for a renewed analysis of this structural puzzle. The present analysis relies heavily on the approach and on the detailed diffraction data o...

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