Collective Motions and Mechanical Response of a Bulk of Single-Chain Nano-Particles Synthesized by Click-Chemistry
We investigate the effect of intra-molecular cross-links on the properties of polymer bulks. To do this, we apply a combination of thermal, rheological, diffraction, and neutron spin echo experiments covering the inter-molecular as well as the intermediate length scales to melts of single-chain nano...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-12-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/13/1/50 |
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| author | Jon Maiz Ester Verde-Sesto Isabel Asenjo-Sanz Peter Fouquet Lionel Porcar José A. Pomposo Paula Malo de Molina Arantxa Arbe Juan Colmenero |
| author_facet | Jon Maiz Ester Verde-Sesto Isabel Asenjo-Sanz Peter Fouquet Lionel Porcar José A. Pomposo Paula Malo de Molina Arantxa Arbe Juan Colmenero |
| author_sort | Jon Maiz |
| collection | DOAJ |
| description | We investigate the effect of intra-molecular cross-links on the properties of polymer bulks. To do this, we apply a combination of thermal, rheological, diffraction, and neutron spin echo experiments covering the inter-molecular as well as the intermediate length scales to melts of single-chain nano-particles (SCNPs) obtained through ‘click’ chemistry. The comparison with the results obtained in a bulk of the corresponding linear precursor chains (prior to intra-molecular reaction) and in a bulk of SCNPs obtained through azide photodecomposition process shows that internal cross-links do not influence the average inter-molecular distances in the melt, but have a profound impact at intermediate length scales. This manifests in the structure, through the emergence of heterogeneities at nanometric scale, and also in the dynamics, leading to a more complex relaxation behavior including processes that allow relaxation of the internal domains. The influence of the nature of the internal bonds is reflected in the structural relaxation that is slowed down if bulky cross-linking agents are used. We also found that any residual amount of cross-links is critical for the rheological behavior, which can vary from an almost entanglement-free polymer bulk to a gel. The presence of such inter-molecular cross-links additionally hinders the decay of density fluctuations at intermediate length scales. |
| first_indexed | 2024-03-10T13:46:40Z |
| format | Article |
| id | doaj.art-9ac0b33dfe7547a1bed34c8ed1ebc15a |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T13:46:40Z |
| publishDate | 2020-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-9ac0b33dfe7547a1bed34c8ed1ebc15a2023-11-21T02:32:36ZengMDPI AGPolymers2073-43602020-12-011315010.3390/polym13010050Collective Motions and Mechanical Response of a Bulk of Single-Chain Nano-Particles Synthesized by Click-ChemistryJon Maiz0Ester Verde-Sesto1Isabel Asenjo-Sanz2Peter Fouquet3Lionel Porcar4José A. Pomposo5Paula Malo de Molina6Arantxa Arbe7Juan Colmenero8Centro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizábal 5, 20018 Donostia-San Sebastián, SpainCentro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizábal 5, 20018 Donostia-San Sebastián, SpainCentro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizábal 5, 20018 Donostia-San Sebastián, SpainInstitut Laue-Langevin, 71 Avenue des Martyrs, CEDEX 9, 38042 Grenoble, FranceInstitut Laue-Langevin, 71 Avenue des Martyrs, CEDEX 9, 38042 Grenoble, FranceCentro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizábal 5, 20018 Donostia-San Sebastián, SpainCentro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizábal 5, 20018 Donostia-San Sebastián, SpainCentro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizábal 5, 20018 Donostia-San Sebastián, SpainCentro de Física de Materiales (CFM) (CSIC-UPV/EHU)-Materials Physics Center (MPC), Paseo Manuel de Lardizábal 5, 20018 Donostia-San Sebastián, SpainWe investigate the effect of intra-molecular cross-links on the properties of polymer bulks. To do this, we apply a combination of thermal, rheological, diffraction, and neutron spin echo experiments covering the inter-molecular as well as the intermediate length scales to melts of single-chain nano-particles (SCNPs) obtained through ‘click’ chemistry. The comparison with the results obtained in a bulk of the corresponding linear precursor chains (prior to intra-molecular reaction) and in a bulk of SCNPs obtained through azide photodecomposition process shows that internal cross-links do not influence the average inter-molecular distances in the melt, but have a profound impact at intermediate length scales. This manifests in the structure, through the emergence of heterogeneities at nanometric scale, and also in the dynamics, leading to a more complex relaxation behavior including processes that allow relaxation of the internal domains. The influence of the nature of the internal bonds is reflected in the structural relaxation that is slowed down if bulky cross-linking agents are used. We also found that any residual amount of cross-links is critical for the rheological behavior, which can vary from an almost entanglement-free polymer bulk to a gel. The presence of such inter-molecular cross-links additionally hinders the decay of density fluctuations at intermediate length scales.https://www.mdpi.com/2073-4360/13/1/50single-chain nano-particlespolymer meltsintra-molecular cross-linksdynamic structure factorrheology |
| spellingShingle | Jon Maiz Ester Verde-Sesto Isabel Asenjo-Sanz Peter Fouquet Lionel Porcar José A. Pomposo Paula Malo de Molina Arantxa Arbe Juan Colmenero Collective Motions and Mechanical Response of a Bulk of Single-Chain Nano-Particles Synthesized by Click-Chemistry Polymers single-chain nano-particles polymer melts intra-molecular cross-links dynamic structure factor rheology |
| title | Collective Motions and Mechanical Response of a Bulk of Single-Chain Nano-Particles Synthesized by Click-Chemistry |
| title_full | Collective Motions and Mechanical Response of a Bulk of Single-Chain Nano-Particles Synthesized by Click-Chemistry |
| title_fullStr | Collective Motions and Mechanical Response of a Bulk of Single-Chain Nano-Particles Synthesized by Click-Chemistry |
| title_full_unstemmed | Collective Motions and Mechanical Response of a Bulk of Single-Chain Nano-Particles Synthesized by Click-Chemistry |
| title_short | Collective Motions and Mechanical Response of a Bulk of Single-Chain Nano-Particles Synthesized by Click-Chemistry |
| title_sort | collective motions and mechanical response of a bulk of single chain nano particles synthesized by click chemistry |
| topic | single-chain nano-particles polymer melts intra-molecular cross-links dynamic structure factor rheology |
| url | https://www.mdpi.com/2073-4360/13/1/50 |
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