Self-Avoiding Random Walks as a Model to Study Athermal Linear Polymers under Extreme Plate Confinement
Monte Carlo (MC) simulations, built around chain-connectivity-altering moves and a wall-displacement algorithm, allow us to simulate freely-jointed chains of tangent hard spheres of uniform size under extreme confinement. The latter is realized through the presence of two impenetrable, flat, and par...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-04-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/12/4/799 |
| _version_ | 1797571539443384320 |
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| author | Oscar Parreño Pablo Miguel Ramos Nikos Ch. Karayiannis Manuel Laso |
| author_facet | Oscar Parreño Pablo Miguel Ramos Nikos Ch. Karayiannis Manuel Laso |
| author_sort | Oscar Parreño |
| collection | DOAJ |
| description | Monte Carlo (MC) simulations, built around chain-connectivity-altering moves and a wall-displacement algorithm, allow us to simulate freely-jointed chains of tangent hard spheres of uniform size under extreme confinement. The latter is realized through the presence of two impenetrable, flat, and parallel plates. Extreme conditions correspond to the case where the distance between the plates approaches the monomer size. An analysis of the local structure, based on the characteristic crystallographic element (CCE) norm, detects crystal nucleation and growth at packing densities well below the ones observed in bulk analogs. In a second step, we map the confined polymer chains into self-avoiding random walks (SAWs) on restricted lattices. We study all realizations of the cubic crystal system: simple, body centered, and face centered cubic crystals. For a given chain size (SAW length), lattice type, origin of SAW, and level of confinement, we enumerate all possible SAWs (equivalently all chain conformations) and calculate the size distribution. Results for intermediate SAW lengths are used to predict the behavior of long, fully entangled chains through growth formulas. The SAW analysis will allow us to determine the corresponding configurational entropy, as it is the driving force for the observed phase transition and the determining factor for the thermodynamic stability of the corresponding crystal morphologies. |
| first_indexed | 2024-03-10T20:41:41Z |
| format | Article |
| id | doaj.art-23a452af00574df9b05deec8bf0c324b |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T20:41:41Z |
| publishDate | 2020-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-23a452af00574df9b05deec8bf0c324b2023-11-19T20:35:18ZengMDPI AGPolymers2073-43602020-04-0112479910.3390/polym12040799Self-Avoiding Random Walks as a Model to Study Athermal Linear Polymers under Extreme Plate ConfinementOscar Parreño0Pablo Miguel Ramos1Nikos Ch. Karayiannis2Manuel Laso3Institute for Optoelectronic Systems and Microtechnology (ISOM) and Escuela Técnica Superior de Ingenieros Industriales (ETSII), Universidad Politecnica de Madrid (UPM), José Gutierrez Abascal 2, 28006 Madrid, SpainInstitute for Optoelectronic Systems and Microtechnology (ISOM) and Escuela Técnica Superior de Ingenieros Industriales (ETSII), Universidad Politecnica de Madrid (UPM), José Gutierrez Abascal 2, 28006 Madrid, SpainInstitute for Optoelectronic Systems and Microtechnology (ISOM) and Escuela Técnica Superior de Ingenieros Industriales (ETSII), Universidad Politecnica de Madrid (UPM), José Gutierrez Abascal 2, 28006 Madrid, SpainInstitute for Optoelectronic Systems and Microtechnology (ISOM) and Escuela Técnica Superior de Ingenieros Industriales (ETSII), Universidad Politecnica de Madrid (UPM), José Gutierrez Abascal 2, 28006 Madrid, SpainMonte Carlo (MC) simulations, built around chain-connectivity-altering moves and a wall-displacement algorithm, allow us to simulate freely-jointed chains of tangent hard spheres of uniform size under extreme confinement. The latter is realized through the presence of two impenetrable, flat, and parallel plates. Extreme conditions correspond to the case where the distance between the plates approaches the monomer size. An analysis of the local structure, based on the characteristic crystallographic element (CCE) norm, detects crystal nucleation and growth at packing densities well below the ones observed in bulk analogs. In a second step, we map the confined polymer chains into self-avoiding random walks (SAWs) on restricted lattices. We study all realizations of the cubic crystal system: simple, body centered, and face centered cubic crystals. For a given chain size (SAW length), lattice type, origin of SAW, and level of confinement, we enumerate all possible SAWs (equivalently all chain conformations) and calculate the size distribution. Results for intermediate SAW lengths are used to predict the behavior of long, fully entangled chains through growth formulas. The SAW analysis will allow us to determine the corresponding configurational entropy, as it is the driving force for the observed phase transition and the determining factor for the thermodynamic stability of the corresponding crystal morphologies.https://www.mdpi.com/2073-4360/12/4/799confinementcrystallizationentropyhard spherepolymerrandom walk |
| spellingShingle | Oscar Parreño Pablo Miguel Ramos Nikos Ch. Karayiannis Manuel Laso Self-Avoiding Random Walks as a Model to Study Athermal Linear Polymers under Extreme Plate Confinement Polymers confinement crystallization entropy hard sphere polymer random walk |
| title | Self-Avoiding Random Walks as a Model to Study Athermal Linear Polymers under Extreme Plate Confinement |
| title_full | Self-Avoiding Random Walks as a Model to Study Athermal Linear Polymers under Extreme Plate Confinement |
| title_fullStr | Self-Avoiding Random Walks as a Model to Study Athermal Linear Polymers under Extreme Plate Confinement |
| title_full_unstemmed | Self-Avoiding Random Walks as a Model to Study Athermal Linear Polymers under Extreme Plate Confinement |
| title_short | Self-Avoiding Random Walks as a Model to Study Athermal Linear Polymers under Extreme Plate Confinement |
| title_sort | self avoiding random walks as a model to study athermal linear polymers under extreme plate confinement |
| topic | confinement crystallization entropy hard sphere polymer random walk |
| url | https://www.mdpi.com/2073-4360/12/4/799 |
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