open access publication

Article, 2024

Hydrolysis of biobased stereocomplex polylactide: Polymorphism dependent crystals degradation and evolution of three-phase crystalline composition

Applied Materials Today, ISSN 2352-9415, 2352-9407, Volume 38, Page 102226, 10.1016/j.apmt.2024.102226

Contributors

Chen, Qi 0000-0002-6908-0040 [1] Sogut, Ece 0000-0003-4052-993X [1] Auras, Rafael A 0000-0002-4378-359X [2] Kirkensgaard, Jacob Judas Kain 0000-0001-6265-0314 [3] Uysal-Unalan, Ilke 0000-0002-0963-6166 (Corresponding author) [1]

Affiliations

  1. [1] Aarhus University
  2. [NORA names: AU Aarhus University; University; Denmark; Europe, EU; Nordic; OECD];
  3. [2] Michigan State University
  4. [NORA names: United States; America, North; OECD];
  5. [3] University of Copenhagen
  6. [NORA names: KU University of Copenhagen; University; Denmark; Europe, EU; Nordic; OECD]

Abstract

The hydrolytic degradation behavior of stereocomplex polylactide (SCPLA) with distinct polymorphisms (α, αʹ, SC) and SC fractions (the ratio of SC crystallinity to total crystallinity) was first investigated in the present study. The evolution of three-phase crystalline compositions was quantified using modulated differential scanning calorimetry. Hydrolytic degradation commenced in the mobile amorphous fraction (MAF), while both the crystal (CF) and rigid amorphous fraction (RAF) began degradation on Day 3. By the 26th day, the MAF was consumed entirely, followed by the CF and RAF degraded at similar rates, primarily through the cleavage of chains with free ends on the folding surface of the remaining lamella. This work further discussed the influence of polymorphism on homochiral (HC) and SC crystal degradation during hydrolysis. Given racemic helices' participation in SC crystallization, SC-crystal lamellae may possess a higher number of amorphous chains with free ends than HC-crystals. This attribute could account for the faster degradation of HC-crystals in samples with a higher SC fraction.

Keywords

CF, HC, HC crystallization, SC crystallization, SC fraction, amorphous chains, amorphous fraction, calorimetry, chain, cleavage, cleavage of chains, composition, crystal, crystal degradation, crystalline composition, days, degradation, differential scanning calorimetry, end, evolution, fold surface, fraction, free end, hydrolysis, hydrolytic degradation, hydrolytic degradation behavior, influence, influence of polymorphisms, lamellae, mobile amorphous fraction, modulated differential scanning calorimetry, participants, polylactide, polymorphism, rate, rigid amorphous fraction, samples, scanning calorimetry, stereocomplex polylactide, study, surface

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