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Crystal Growth: Principles of Crystallization01:25

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Crystallization is a phase transformation process in which crystals are precipitated from a supersaturated solution or formed from other sources. During crystallization, atoms or molecules arrange themselves into a well-defined, rigid crystal lattice to minimize energy.
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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Homogeneous Crystal Nucleation of Poly(3-hydroxybutyrate): Kinetics, Stability, and Cluster-Size Distribution.

Katalee Jariyavidyanont1, Rui Zhang1, Christoph Schick2

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Homogeneous crystal nuclei in poly-(3-hydroxybutyrate) (P3HB) form rapidly near its glass transition temperature. These nuclei exhibit remarkable thermal stability, persisting even when heated significantly above their formation temperature.

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Area of Science:

  • Polymer Science
  • Materials Science
  • Physical Chemistry

Background:

  • Understanding polymer crystallization kinetics is crucial for material properties.
  • Poly(3-hydroxybutyrate) (P3HB) is a biodegradable polymer with complex crystallization behavior near its glass transition temperature (Tg).
  • Homogeneous nucleation is a fundamental process influencing crystallization rates and morphology.

Purpose of the Study:

  • To investigate the kinetics of homogeneous crystal nucleation in P3HB.
  • To determine the influence of temperature and cooling rates on nucleation.
  • To assess the thermal stability of P3HB crystal nuclei.

Main Methods:

  • Fast scanning calorimetry (FSC) was employed to study nucleation kinetics.
  • Tammann's two-stage crystal nuclei development method was adapted for P3HB.
  • Modified nucleation experiments with temperature spikes evaluated nuclei thermal stability.

Main Results:

  • Crystallization on cooling is suppressed at rates of a few K/s; nucleation is inhibited above ~100 K/s.
  • Homogeneous nucleation is fastest ~40 °C (30 K above Tg) with a 1s onset time.
  • P3HB nuclei are stable up to ~100 K above formation temperature, with dissolution around 120 K above.

Conclusions:

  • Homogeneous crystal nuclei in P3HB exhibit exceptional thermal stability.
  • Nuclei stability suggests a sharp truncation of the nuclei-size distribution.
  • FSC and Tammann's method provide insights into P3HB nucleation kinetics and stability.