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A new self-poisoning mechanism in poly(lactic acid) crystallization was discovered, where a less stable crystal form (α′) hinders the growth of the stable form (α). This finding impacts polymer processing and material properties.

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Area of Science:

  • Polymer Science
  • Materials Science
  • Crystallization Kinetics

Background:

  • Self-poisoning is a known phenomenon in polymer crystallization, typically observed as growth rate minima.
  • Previous instances involved unstable folded or segmented chains interfering with stable crystal growth.

Purpose of the Study:

  • To identify and characterize a novel self-poisoning mechanism in poly(lactic acid) (PLA).
  • To investigate the impact of this self-poisoning on PLA crystallization kinetics and material properties.

Main Methods:

  • Experimental observation of poly(lactic acid) crystallization kinetics.
  • Development and application of a growth rate equation model.
  • Analysis of crystal form kinetics and lamellar thickness variations.

Main Results:

  • A new self-poisoning mechanism was identified in PLA, where the less stable α′ crystal form inhibits the growth of the stable α form.
  • An unexpected increase in lamellar thickness was observed below the growth rate minimum.
  • The model revealed a low fold surface free energy for the α′ form.

Conclusions:

  • Self-poisoning in PLA involves the kinetic hindrance of stable α crystal growth by the less stable α′ form.
  • This phenomenon, particularly in fast-cooling processes, leads to the formation of the low-modulus α′ phase and increased amorphous content.
  • The resulting embrittlement of PLA is attributed to physical aging of the amorphous fraction.