Onset of entanglements revisited. Topological analysis

Tzoumanekas, C; Lahmar, F; Rousseau, B; Theodorou, DN

dc.contributor.author	Tzoumanekas, C	en
dc.contributor.author	Lahmar, F	en
dc.contributor.author	Rousseau, B	en
dc.contributor.author	Theodorou, DN	en
dc.date.accessioned	2014-03-01T01:31:35Z
dc.date.available	2014-03-01T01:31:35Z
dc.date.issued	2009	en
dc.identifier.issn	0024-9297	en
dc.identifier.uri	https://dspace.lib.ntua.gr/xmlui/handle/123456789/19829
dc.subject	Topological Analysis	en
dc.subject.classification	Polymer Science	en
dc.subject.other	Coarse-grained	en
dc.subject.other	Contour length fluctuations	en
dc.subject.other	Crossover length	en
dc.subject.other	Dissipative particle dynamics	en
dc.subject.other	Dynamic aspects	en
dc.subject.other	Length scale	en
dc.subject.other	Long chains	en
dc.subject.other	Monodisperse systems	en
dc.subject.other	Primitive path	en
dc.subject.other	Random Walk	en
dc.subject.other	Rate of increase	en
dc.subject.other	Reptation	en
dc.subject.other	Scaling model	en
dc.subject.other	Static and dynamic	en
dc.subject.other	Thin rods	en
dc.subject.other	Topological analysis	en
dc.subject.other	Chain length	en
dc.subject.other	Electric load shedding	en
dc.subject.other	Topology	en
dc.subject.other	Polymer melts	en
dc.title	Onset of entanglements revisited. Topological analysis	en
heal.type	journalArticle	en
heal.identifier.primary	10.1021/ma901131c	en
heal.identifier.secondary	http://dx.doi.org/10.1021/ma901131c	en
heal.language	English	en
heal.publicationDate	2009	en
heal.abstract	In a series of two papers, we study the onset of entanglements and the transition from Rouse-type to reptation dynamics, in the context of dissipative particle dynamics (DPD) simulations of a coarse-grained polymer melt. A set of monodisperse systems with increasing chain length is examined. We consider both static and dynamic aspects of the problem. Part I, this paper, deals with the continuous change of the polymer topology, from unentangled (short chains), to entangled (long chains). We show that as chain length increases the rate of increase of chain overlap increases asymptotically. It becomes constant when chains are sufficiently long, and in this regime a long chain topology is established. Next, we examine the onset by probing static length scales at the level of primitive paths (PPs). A simple scaling model based on a transformation of PPs from thin rods (short chains) to random walks (RWs) (long chains) is discussed qualitatively and quantitatively. The model predicts a crossover in the underlying topology, which leads to a Rouse to reptation transition in dynamics when PP conformations change from rods to to RWs. The entanglement molecular weight is interpreted as the crossover length of this transition. The predicted Mc/Me ratio is one, which, though small, is compatible with packing length independence and the suppression of contour length fluctuations within the model. Part II, the following paper (DOI 10.1021/ma9011329), deals with dynamic aspects of the onset of entanglements, making possible a comparison between static and dynamic length scales. © 2009 American Chemical Society.	en
heal.publisher	AMER CHEMICAL SOC	en
heal.journalName	Macromolecules	en
dc.identifier.doi	10.1021/ma901131c	en
dc.identifier.isi	ISI:000270461600034	en
dc.identifier.volume	42	en
dc.identifier.issue	19	en
dc.identifier.spage	7474	en
dc.identifier.epage	7484	en