Molecular rheology of branched polymers: Decoding and exploring the role of architectural dispersity through a synergy of anionic synthesis, interaction chromatography, rheometry and modeling

Handle URI:
http://hdl.handle.net/10754/563208
Title:
Molecular rheology of branched polymers: Decoding and exploring the role of architectural dispersity through a synergy of anionic synthesis, interaction chromatography, rheometry and modeling
Authors:
Van Ruymbeke, Evelyne; Lee, Heecheong; Chang, Taihyun; Nikopoulou, Anastasia; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 ) ; Snijkers, Frank; Vlassopoulos, Dimitris
Abstract:
An emerging challenge in polymer physics is the quantitative understanding of the influence of a macromolecular architecture (i.e., branching) on the rheological response of entangled complex polymers. Recent investigations of the rheology of well-defined architecturally complex polymers have determined the composition in the molecular structure and identified the role of side-products in the measured samples. The combination of different characterization techniques, experimental and/or theoretical, represents the current state-of-the-art. Here we review this interdisciplinary approach to molecular rheology of complex polymers, and show the importance of confronting these different tools for ensuring an accurate characterization of a given polymeric sample. We use statistical tools in order to relate the information available from the synthesis protocols of a sample and its experimental molar mass distribution (typically obtained from size exclusion chromatography), and hence obtain precise information about its structural composition, i.e. enhance the existing sensitivity limit. We critically discuss the use of linear rheology as a reliable quantitative characterization tool, along with the recently developed temperature gradient interaction chromatography. The latter, which has emerged as an indispensable characterization tool for branched architectures, offers unprecedented sensitivity in detecting the presence of different molecular structures in a sample. Combining these techniques is imperative in order to quantify the molecular composition of a polymer and its consequences on the macroscopic properties. We validate this approach by means of a new model asymmetric comb polymer which was synthesized anionically. It was thoroughly characterized and its rheology was carefully analyzed. The main result is that the rheological signal reveals fine molecular details, which must be taken into account to fully elucidate the viscoelastic response of entangled branched polymers. It is important to appreciate that, even optimal model systems, i.e., those synthesized with high-vacuum anionic methods, need thorough characterization via a combination of techniques. Besides helping to improve synthetic techniques, this methodology will be significant in fine-tuning mesoscopic tube-based models and addressing outstanding issues such as the quantitative description of the constraint release mechanism. © 2014 the Partner Organisations.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Polymer Synthesis Laboratory
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Soft Matter
Issue Date:
2014
DOI:
10.1039/c4sm00105b
Type:
Article
ISSN:
1744683X
Sponsors:
We are very grateful to Paul Kim for his precious help with the samples characterization. We acknowledge partial support from EU (ITN DYNACOP, grant 214627; FP7 Infrastructure ESMI, GA 262348). EVR thanks the Fonds National de la Recherche Scientique (FNRS) for financial support. TC acknowledges the supports from NRF (2012R1A2A2A01015148).
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorVan Ruymbeke, Evelyneen
dc.contributor.authorLee, Heecheongen
dc.contributor.authorChang, Taihyunen
dc.contributor.authorNikopoulou, Anastasiaen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.contributor.authorSnijkers, Franken
dc.contributor.authorVlassopoulos, Dimitrisen
dc.date.accessioned2015-08-03T11:38:11Zen
dc.date.available2015-08-03T11:38:11Zen
dc.date.issued2014en
dc.identifier.issn1744683Xen
dc.identifier.doi10.1039/c4sm00105ben
dc.identifier.urihttp://hdl.handle.net/10754/563208en
dc.description.abstractAn emerging challenge in polymer physics is the quantitative understanding of the influence of a macromolecular architecture (i.e., branching) on the rheological response of entangled complex polymers. Recent investigations of the rheology of well-defined architecturally complex polymers have determined the composition in the molecular structure and identified the role of side-products in the measured samples. The combination of different characterization techniques, experimental and/or theoretical, represents the current state-of-the-art. Here we review this interdisciplinary approach to molecular rheology of complex polymers, and show the importance of confronting these different tools for ensuring an accurate characterization of a given polymeric sample. We use statistical tools in order to relate the information available from the synthesis protocols of a sample and its experimental molar mass distribution (typically obtained from size exclusion chromatography), and hence obtain precise information about its structural composition, i.e. enhance the existing sensitivity limit. We critically discuss the use of linear rheology as a reliable quantitative characterization tool, along with the recently developed temperature gradient interaction chromatography. The latter, which has emerged as an indispensable characterization tool for branched architectures, offers unprecedented sensitivity in detecting the presence of different molecular structures in a sample. Combining these techniques is imperative in order to quantify the molecular composition of a polymer and its consequences on the macroscopic properties. We validate this approach by means of a new model asymmetric comb polymer which was synthesized anionically. It was thoroughly characterized and its rheology was carefully analyzed. The main result is that the rheological signal reveals fine molecular details, which must be taken into account to fully elucidate the viscoelastic response of entangled branched polymers. It is important to appreciate that, even optimal model systems, i.e., those synthesized with high-vacuum anionic methods, need thorough characterization via a combination of techniques. Besides helping to improve synthetic techniques, this methodology will be significant in fine-tuning mesoscopic tube-based models and addressing outstanding issues such as the quantitative description of the constraint release mechanism. © 2014 the Partner Organisations.en
dc.description.sponsorshipWe are very grateful to Paul Kim for his precious help with the samples characterization. We acknowledge partial support from EU (ITN DYNACOP, grant 214627; FP7 Infrastructure ESMI, GA 262348). EVR thanks the Fonds National de la Recherche Scientique (FNRS) for financial support. TC acknowledges the supports from NRF (2012R1A2A2A01015148).en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.titleMolecular rheology of branched polymers: Decoding and exploring the role of architectural dispersity through a synergy of anionic synthesis, interaction chromatography, rheometry and modelingen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalSoft Matteren
dc.contributor.institutionBio and Soft Matter, Institute on Condensed Matter and Nano-science, Université Catholique de Louvain, Louvain-la-Neuve 1348, Belgiumen
dc.contributor.institutionPohang University of Science and Technology, Division of Advanced Materials Science, Department of Chemistry, Pohang 790-784, South Koreaen
dc.contributor.institutionUniversity of Athens, Department of Chemistry, Athens 15771, Greeceen
dc.contributor.institutionFORTH, Institute of Electronic Structure and Laser, Heraklion, 70013 Crete, Greeceen
dc.contributor.institutionUniversity of Crete, Department of Materials Science and Technology, Heraklion, 71003 Crete, Greeceen
kaust.authorHadjichristidis, Nikolaosen
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