TY - JOUR
T1 - Nanocrystallisation and self-assembly of biosourced ferulic acid derivative in polylactic acid elastomeric blends
AU - Raghuwanshi, Vikram Singh
AU - Gallos, Antoine
AU - Mendoza, David Joram
AU - Lin, Maoqi
AU - Allais, Florent
AU - Garnier, Gil
N1 - Funding Information:
The authors would like to acknowledgment the Australian Research Council (ARC) - Industrial Transformation Hub Grant IH130100016. The authors thank to Nigel Kirby, Tim Ryan and the SAXS/WAXS beamline at the Australian Synchrotron for the SAXS measurements and Australian nuclear science and technology organisation (ANSTO) for the beamtime. The authors thank to the Monash X-ray platform facilities for the XRD measurement. The R?gion Grand Est, the Conseil D?partemental de la Marne, and the Grand Reims are gratefully acknowledged for supporting these works.
Funding Information:
The authors would like to acknowledgment the Australian Research Council (ARC) - Industrial Transformation Hub Grant IH130100016. The authors thank to Nigel Kirby, Tim Ryan and the SAXS/WAXS beamline at the Australian Synchrotron for the SAXS measurements and Australian nuclear science and technology organisation (ANSTO) for the beamtime. The authors thank to the Monash X-ray platform facilities for the XRD measurement. The Région Grand Est, the Conseil Départemental de la Marne, and the Grand Reims are gratefully acknowledged for supporting these works.
Publisher Copyright:
© 2021 Elsevier Inc.
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2022/1/15
Y1 - 2022/1/15
N2 - Hypothesis. The crystallisation of biosourced ferulic acid derivatives - Bis-O-feruloyl-1,4-butanediol (BDF) - in a polylactic acid (PLA) matrix produces thermoplastic elastomeric blends that are transparent and biodegradable. Elastomeric and transparency are controlled by the domain size. PLA-BDF blends up to a threshold BDF concentration providing elastomeric properties show no evidence of BDF crystallisation. Heat treatment weakens the PLA-BDF interaction, give BDF molecules mobility to interact with nearby BDF molecules, leading to BDF nano-crystallisation. Experiments. PLA-BDF blends were synthesised by hot-melt processing by mixing pure PLA with different concentrations of BDF (0–40 wt%) at 180 °C for 13 min. One set of blends was annealed at 50 °C for 24 h and compared with the unannealed set. The BDF crystallisation in the blends is studied by combining SAXS, SEM, XRD and Polarised Optical Microscopy. Monte-Carlo simulations were performed to validate SAXS data analysis. Findings. Unannealed PLA-BDF blends of up to the threshold of 20 wt% BDF are dominated by the semicrystalline behaviour of PLA, without any trace of BDF crystallisation. Surprisingly, the PLA-BDF 40 wt% blend shows BDF crystallisation in the form of large and nanoscale structures bonded together by weak interparticle interaction. At concentrations up to 20 wt%, the BDF molecules are homogenously dispersed and bonded with PLA. Increasing BDF to 40 wt% brings the BDF molecules close enough to crystallise at room temperature, as the BDF molecules are still bonded with the PLA network. Annealing of PLA-BDF blends led to BDF nanocrystallisation and self-assembling in the PLA network. Both BDF nanoparticle size and interparticle distance decrease as the BDF concentration increases. However, the number density of BDF nanocrystals increases. The formed BDF nanocrystals have size ranging between 100 and 380 Å with interparticle distance of 120–180 Å. The structure factor and potential mean force confirm the strong interparticle interaction at the higher BDF concentration. Heat treatment weakens the PLA -BDF interaction, which provides mobility to the BDF molecules to change conformation and interact with the nearby BDF molecules, leading to BDF crystallisation. This novel BDF crystallisation and self-assembly mechanism can be used to develop biodegradable shape memory PLA blends for biomedical, shape memory, packaging and energy applications.
AB - Hypothesis. The crystallisation of biosourced ferulic acid derivatives - Bis-O-feruloyl-1,4-butanediol (BDF) - in a polylactic acid (PLA) matrix produces thermoplastic elastomeric blends that are transparent and biodegradable. Elastomeric and transparency are controlled by the domain size. PLA-BDF blends up to a threshold BDF concentration providing elastomeric properties show no evidence of BDF crystallisation. Heat treatment weakens the PLA-BDF interaction, give BDF molecules mobility to interact with nearby BDF molecules, leading to BDF nano-crystallisation. Experiments. PLA-BDF blends were synthesised by hot-melt processing by mixing pure PLA with different concentrations of BDF (0–40 wt%) at 180 °C for 13 min. One set of blends was annealed at 50 °C for 24 h and compared with the unannealed set. The BDF crystallisation in the blends is studied by combining SAXS, SEM, XRD and Polarised Optical Microscopy. Monte-Carlo simulations were performed to validate SAXS data analysis. Findings. Unannealed PLA-BDF blends of up to the threshold of 20 wt% BDF are dominated by the semicrystalline behaviour of PLA, without any trace of BDF crystallisation. Surprisingly, the PLA-BDF 40 wt% blend shows BDF crystallisation in the form of large and nanoscale structures bonded together by weak interparticle interaction. At concentrations up to 20 wt%, the BDF molecules are homogenously dispersed and bonded with PLA. Increasing BDF to 40 wt% brings the BDF molecules close enough to crystallise at room temperature, as the BDF molecules are still bonded with the PLA network. Annealing of PLA-BDF blends led to BDF nanocrystallisation and self-assembling in the PLA network. Both BDF nanoparticle size and interparticle distance decrease as the BDF concentration increases. However, the number density of BDF nanocrystals increases. The formed BDF nanocrystals have size ranging between 100 and 380 Å with interparticle distance of 120–180 Å. The structure factor and potential mean force confirm the strong interparticle interaction at the higher BDF concentration. Heat treatment weakens the PLA -BDF interaction, which provides mobility to the BDF molecules to change conformation and interact with the nearby BDF molecules, leading to BDF crystallisation. This novel BDF crystallisation and self-assembly mechanism can be used to develop biodegradable shape memory PLA blends for biomedical, shape memory, packaging and energy applications.
KW - Bis-O-feruloyl-1,4-butanediol
KW - Crystallisation
KW - Ferulic Acid
KW - Polylactic acid
KW - Self-assembly
KW - Small angle X-ray scattering
UR - http://www.scopus.com/inward/record.url?scp=85114773593&partnerID=8YFLogxK
U2 - 10.1016/j.jcis.2021.08.123
DO - 10.1016/j.jcis.2021.08.123
M3 - Article
C2 - 34507175
AN - SCOPUS:85114773593
SN - 0021-9797
VL - 606
SP - 1842
EP - 1851
JO - Journal of Colloid and Interface Science
JF - Journal of Colloid and Interface Science
IS - Part 2
ER -