Isothermal and non-isothermal cold crystallization kinetics of polylactide/cellulose nanocrystal (PLA/CNC) nanocomposites

Alanalp, Mine Begum; Özdemir, Burcu; Nofar, Mohammadreza; Durmuş, Ali

doi:10.1007/s10973-022-11598-9

Cited by 10 publications

(3 citation statements)

References 77 publications

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“…Subsequently, these smaller crystallites then melt earlier as seen by the reduction in the melting onset. 59,60 The polymer-modified CNFs further decreased these onsets, with PNIPAM-MetCNFs and PMAM-MetCNFs reducing T cc and T m by approximately 12 and 7 °C, respectively, at 30 wt % loading and POEGMA-MetCNFs reducing them by 24 and 13 °C, respectively, at 30 wt % loading. This further depression of the onset temperatures may be a result of PLA matrix plasticization by the grafted polymer chains, which enables earlier crystallization through increased chain mobility.…”

Section: Composite Melt Rheology and Thermal Propertiesmentioning

confidence: 98%

Polymer-Grafted Cellulose Nanofibrils with Enhanced Interfacial Compatibility for Stronger Poly(lactic acid) Composites

Kelly

Es‐haghi

Lamm

et al. 2023

ACS Appl. Polym. Mater.

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Cellulose nanofibrils (CNFs) are a promising reinforcement for biodegradable composite matrices such as poly(lactic acid) (PLA), but they require commercially scalable drying methods that preserve their fibrillar morphology along with improved interfacial interactions with polymer matrices. In this work, a water-based grafting-through polymerization scheme to modify CNFs improved spray drying behavior and reinforcement capacity in PLA composites. All polymer modifications yielded CNFs with a more fibrillar morphology after spray drying, increasing specific surface area by up to 490% compared to unmodified CNFs, values similar to conventional freeze drying. Polymer-grafted CNFs in PLA composites improved the tensile strength by 16% at 20 wt % loading and stiffness by 22% at a 10 wt % loading with two different graft-polymer chemistries compared to unmodified CNF composites. Surface energy heterogeneity measurements of the reinforcements and PLA matrix were employed to understand the improvements in composite properties. Polymer modifications lowered the total surface energy of the CNFs, and calculated ratios of work of adhesion to work of cohesion suggested improved interfacial compatibility for four of the modified CNFs with PLA. Rheological oscillatory shear studies of the composites correlated solid-like melt behavior, as demonstrated by storage moduli dominance, with higher tensile strength. Thermal analysis of the composites revealed that excessive plasticization by the poly(oligoethylene glycol methyl ether methacrylate)-grafted sample potentially offset mechanical property improvements imparted by the more fibrillar morphology. This work provides an opportunity for large-scale manufacturing of CNF/PLA composites via an entirely aqueous modification scheme and industrially relevant spray drying process.

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Section: Composite Melt Rheology and Thermal Propertiesmentioning

confidence: 98%

Polymer-Grafted Cellulose Nanofibrils with Enhanced Interfacial Compatibility for Stronger Poly(lactic acid) Composites

Kelly

Es‐haghi

Lamm

et al. 2023

ACS Appl. Polym. Mater.

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“…When heating slowly in the DSC, the cold crystallization temperature (T cc ) of the PLA in the composites with 5 and 10 wt% reinforcement reduced, which may be due to the PMMA-MetCNFs nucleating crystallization in the PLA. 57 At higher reinforcement (30 wt%), the T cc increased, which was likely due to cellulose network formation inhibiting chain mobility. 58 The inhibition of crystallization could also be observed in the significantly lower enthalpy of crystallization (Table S5 †).…”

Section: Paper Rsc Applied Polymersmentioning

confidence: 99%

Strengthening polylactic acid (PLA) composites with poly(methyl methacrylate)-functionalized cellulose nanofibrils created through grafting-through emulsion polymerization

Senkum,

Kelly,

Ahmad

et al. 2024

RSC Appl. Polym.

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“…Borkotoky explored the thermal degradation and crystallization behavior of PLA and PLA/CNC [ 35 ]. CNC addition improved the crystallization rate of PLA, possibly following thermal nucleation and two-dimensional discotic growth [ 36 ]. PLA and CNC were compounded by a reactive extrusion process using dicarbonyl peroxide (DCP) as the free radical initiator.…”

Section: Introductionmentioning

confidence: 99%

Mechanical Properties and Non-Isothermal Crystallization Kinetics of Polylactic Acid Modified by Polyacrylic Elastomers and Cellulose Nanocrystals

Meng,

Zhang,

et al. 2023

Polymers

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In this paper, a polyacrylic elastomer latex with butyl acrylate (BA) as the core and methyl methacrylate (MMA) copolymerized with glycidyl methacrylate (GMA) as the shell, named poly(BA-MMA-GMA) (PBMG), was synthesized by seeded emulsion polymerization. Cellulose nanocrystal (CNC) was dispersed in the polyacrylic latex to prepare PBMG/CNC dispersions with different CNC contents. The dried product was mixed with polylactic acid (PLA) to fabricate PLA/PBMG/CNC blends. The addition of PBMG and PBMG/CNC improved the mechanical properties of the PLA matrix. Differential scanning calorimetry (DSC) was used to investigate the non-isothermal crystallization kinetics. The Avrami equation modified by the Jeziorny, Ozawa and Mo equations was used to analyze the non-isothermal crystallization kinetics of PLA and its blends. Analysis of the crystallization halftime of non-isothermal conditions indicated that the overall rate of crystallization increased significantly at 1 wt% content of CNC. This seemed to result from the increase of nucleation density and the acceleration of segment movement in the presence of the CNC component. This phenomenon was verified by polarizing microscope observation.

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Isothermal and non-isothermal cold crystallization kinetics of polylactide/cellulose nanocrystal (PLA/CNC) nanocomposites

Cited by 10 publications

References 77 publications

Polymer-Grafted Cellulose Nanofibrils with Enhanced Interfacial Compatibility for Stronger Poly(lactic acid) Composites

Polymer-Grafted Cellulose Nanofibrils with Enhanced Interfacial Compatibility for Stronger Poly(lactic acid) Composites

Strengthening polylactic acid (PLA) composites with poly(methyl methacrylate)-functionalized cellulose nanofibrils created through grafting-through emulsion polymerization

Mechanical Properties and Non-Isothermal Crystallization Kinetics of Polylactic Acid Modified by Polyacrylic Elastomers and Cellulose Nanocrystals

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