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Quantitative DSC Assessment of the Polymorph-Specific Crystallinity of Poly(Lactic Acid) and the Impact of a Self-Assembling Nucleating Agent and PEG Plasticizer

Title: Quantitative DSC Assessment of the Polymorph-Specific Crystallinity of Poly(Lactic Acid) and the Impact of a Self-Assembling Nucleating Agent and PEG Plasticizer
Authors: Colaers, Maarten; Thielemans, Wim; Goderis, Bart
Source: ISSN:2073-4360 ; Polymers, vol. 17 (9), Art.No. ARTN 1267.
Publisher Information: Multidisciplinary Digital Publishing Institute (MDPI)
Publication Year: 2025
Subject Terms: Science & Technology; Physical Sciences; Polymer Science; poly(lactic acid); DSC; nucleating agent; plasticizer; crystallization behavior; STEREOCOMPLEX FORMATION; PHASE-BEHAVIOR; TAILORING CRYSTALLIZATION; POLY(L-LACTIC ACID); OXALAMIDE COMPOUNDS; THERMAL-PROPERTIES; POLYLACTIDE; MORPHOLOGY; TEMPERATURE; 03 Chemical Sciences; 09 Engineering; 34 Chemical sciences; 40 Engineering
Description: This study examines the temperature-resolved, polymorph-specific crystallinity of poly(lactic acid), PLA, during cooling and heating at 10 °C/min, with a focus on the effects of N, N-bis(benzoyl) hexanedioic acid dihydrazide (BHAD, commercially known as TMC306) as nucleating agent and PEG 1000 as plasticizer. A semicrystalline (PLA-1) and amorphous (PLA-2) PLA grade were investigated. The study emphasizes the importance of using temperature-dependent, polymorph-specific transition enthalpies to accurately calculate crystallinities from Differential Scanning Calorimetry (DSC). Polymorphism is independently confirmed using Wide Angle X-ray Diffraction (WAXD). Pure PLA-1 reached an α' crystallinity of 2% during cooling, which increased to 38% through cold crystallization upon heating. At BHAD concentrations of at least 0.4%, α crystallites formed instead of α', reaching a maximum crystallinity of 38% during cooling. The addition of 10 wt% PEG to PLA-1 facilitated primary α crystallization during cooling, followed by secondary intraspherulitic α' crystallization upon heating, resulting ultimately in a crystallinity of 34%. Adding 1 wt% BHAD into PLA-1 with 10 wt% PEG shifted the crystallization temperature upward by 40 °C and enhanced the α crystallinity to 44%, highlighting the synergistic effect of PEG and BHAD on crystallization. ; sponsorship: This research was funded by a doctoral (PhD) strategic basic research grant of FWO Vlaanderen to Maarten Colaers (1S64417N). FWO Vlaanderen is acknowledged for funding the DUBBLE project (I001223N). (doctoral (PhD) strategic basic research grant of FWO Vlaanderen to Maarten Colaers, FWO Vlaanderen|I001223N, DUBBLE project) ; status: Published
Document Type: article in journal/newspaper
File Description: application/pdf
Language: English
Relation: https://lirias.kuleuven.be/handle/20.500.12942/765958; https://doi.org/10.3390/polym17091267; https://pubmed.ncbi.nlm.nih.gov/40363051
DOI: 10.3390/polym17091267
Availability: https://lirias.kuleuven.be/handle/20.500.12942/765958; https://hdl.handle.net/20.500.12942/765958; https://lirias.kuleuven.be/retrieve/274db7e2-e9e3-476c-be98-4ce417a1ac4c; https://doi.org/10.3390/polym17091267; https://pubmed.ncbi.nlm.nih.gov/40363051
Rights: info:eu-repo/semantics/openAccess ; public ; https://creativecommons.org/licenses/by/4.0/
Accession Number: edsbas.DB82A84E
Database: BASE