Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent
This study reports a general scenario for the out-of-equilibrium features of collapsing polymeric architectures. We use molecular dynamics simulations to characterize the coarsening kinetics, in bad solvent, for several macromolecular systems with an increasing degree of structural complexity. In pa...
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doaj-b483d51290db4444bab407986df9f1c32020-11-25T00:32:38ZengMDPI AGPolymers2073-43602020-03-0112353110.3390/polym12030531polym12030531Coarsening Kinetics of Complex Macromolecular Architectures in Bad SolventMariarita Paciolla0Daniel J. Arismendi-Arrieta1Angel J. Moreno2Centro de Física de Materiales (CSIC, UPV/EHU) and Materials Physics Center MPC, Paseo Manuel de Lardizabal 5, 20018 San Sebastián, SpainDonostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018 San Sebastián, SpainCentro de Física de Materiales (CSIC, UPV/EHU) and Materials Physics Center MPC, Paseo Manuel de Lardizabal 5, 20018 San Sebastián, SpainThis study reports a general scenario for the out-of-equilibrium features of collapsing polymeric architectures. We use molecular dynamics simulations to characterize the coarsening kinetics, in bad solvent, for several macromolecular systems with an increasing degree of structural complexity. In particular, we focus on: flexible and semiflexible polymer chains, star polymers with 3 and 12 arms, and microgels with both ordered and disordered networks. Starting from a powerful analogy with critical phenomena, we construct a density field representation that removes fast fluctuations and provides a consistent characterization of the domain growth. Our results indicate that the coarsening kinetics presents a scaling behaviour that is independent of the solvent quality parameter, in analogy to the time−temperature superposition principle. Interestingly, the domain growth in time follows a power-law behaviour that is approximately independent of the architecture for all the flexible systems; while it is steeper for the semiflexible chains. Nevertheless, the fractal nature of the dense regions emerging during the collapse exhibits the same scaling behaviour for all the macromolecules. This suggests that the faster growing length scale in the semiflexible chains originates just from a faster mass diffusion along the chain contour, induced by the local stiffness. The decay of the dynamic correlations displays scaling behavior with the growing length scale of the system, which is a characteristic signature in coarsening phenomena.https://www.mdpi.com/2073-4360/12/3/531coarseningdeswellingmicrogelssoft nanoparticlessimulations |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Mariarita Paciolla Daniel J. Arismendi-Arrieta Angel J. Moreno |
spellingShingle |
Mariarita Paciolla Daniel J. Arismendi-Arrieta Angel J. Moreno Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent Polymers coarsening deswelling microgels soft nanoparticles simulations |
author_facet |
Mariarita Paciolla Daniel J. Arismendi-Arrieta Angel J. Moreno |
author_sort |
Mariarita Paciolla |
title |
Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent |
title_short |
Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent |
title_full |
Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent |
title_fullStr |
Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent |
title_full_unstemmed |
Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent |
title_sort |
coarsening kinetics of complex macromolecular architectures in bad solvent |
publisher |
MDPI AG |
series |
Polymers |
issn |
2073-4360 |
publishDate |
2020-03-01 |
description |
This study reports a general scenario for the out-of-equilibrium features of collapsing polymeric architectures. We use molecular dynamics simulations to characterize the coarsening kinetics, in bad solvent, for several macromolecular systems with an increasing degree of structural complexity. In particular, we focus on: flexible and semiflexible polymer chains, star polymers with 3 and 12 arms, and microgels with both ordered and disordered networks. Starting from a powerful analogy with critical phenomena, we construct a density field representation that removes fast fluctuations and provides a consistent characterization of the domain growth. Our results indicate that the coarsening kinetics presents a scaling behaviour that is independent of the solvent quality parameter, in analogy to the time−temperature superposition principle. Interestingly, the domain growth in time follows a power-law behaviour that is approximately independent of the architecture for all the flexible systems; while it is steeper for the semiflexible chains. Nevertheless, the fractal nature of the dense regions emerging during the collapse exhibits the same scaling behaviour for all the macromolecules. This suggests that the faster growing length scale in the semiflexible chains originates just from a faster mass diffusion along the chain contour, induced by the local stiffness. The decay of the dynamic correlations displays scaling behavior with the growing length scale of the system, which is a characteristic signature in coarsening phenomena. |
topic |
coarsening deswelling microgels soft nanoparticles simulations |
url |
https://www.mdpi.com/2073-4360/12/3/531 |
work_keys_str_mv |
AT mariaritapaciolla coarseningkineticsofcomplexmacromoleculararchitecturesinbadsolvent AT danieljarismendiarrieta coarseningkineticsofcomplexmacromoleculararchitecturesinbadsolvent AT angeljmoreno coarseningkineticsofcomplexmacromoleculararchitecturesinbadsolvent |
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