Homogeneous Crystal Nucleation of Poly(3-hydroxybutyrate): Kinetics, Stability, and Cluster-Size Distribution
Katalee Jariyavidyanont, Rui Zhang, Christoph Schick, René Androsch
TL;DR
This study examines how poly(3-hydroxybutyrate) forms crystals at high cooling rates, revealing insights into the speed and stability of crystal nucleation.
Contribution
The paper presents new findings on the high thermal stability and sharp size distribution truncation of homogeneous P3HB crystal nuclei.
Findings
Homogeneous nuclei form fastest at around 40 °C, with an onset time of about 1 second.
Homogeneous nuclei remain stable up to about 100 K above their formation temperature.
Nuclei numbers sharply decrease beyond 100 K and fully dissolve at 120 K above formation temperature.
Abstract
The kinetics of homogeneous crystal nucleation in poly(3-hydroxybutyrate) (P3HB) near its glass transition temperature (T g) was investigated using fast scanning calorimetry (FSC) combined with Tammann’s two-stage crystal nuclei development method. Crystallization on cooling is fully suppressed at rates of a few K/s, while the formation of crystal nuclei is inhibited only at higher rates, above around 100 K/s. The formation of homogeneous nuclei is fastest at around 40 °C (approximately 30 K above T g), with an onset time of their formation of about 1 s, which is two orders of magnitude shorter than the crystallization onset time. To evaluate their thermal stability, a modified Tammann nucleation experiment involving a temperature spike before the growth stage was employed. The number of homogeneous nuclei of supercritical size at the growth temperature formed under the given…
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Taxonomy
TopicsPolymer crystallization and properties · biodegradable polymer synthesis and properties · Thermal and Kinetic Analysis