Effect of chain length and topological constraints on segmental relaxation in cyclic PDMS
File(s)
Author(s)
Type
Journal Article
Abstract
We present a detailed investigation of local dynamics of linear and cyclic poly(dimethylsiloxane) (PDMS) covering a wide range of molar masses. To aid interpretation of the experimental data, QENS measurements in the time scale from 2 to 200 ps and at Q = 0.3 to 1.8 Å–1 are complemented by theoretical calculations. These make use of a methodology developed by us elsewhere applicable to both simple chain models and real chains and applied here, for the first time, to cyclic PDMS. Analysis of the incoherent dynamic structure factor at T < Tm shows that the rotational motion of the methyl groups is unaffected by polymer topology. At higher temperatures, the QENS data are described by a model that consists of two dynamic contributions: methyl group rotation and segmental motion, the latter described by a stretched exponential function. Relaxation times of both linear and cyclic PDMS increase with increasing molar mass. Several features predicted by theory are also reproduced by the experimental data. We show, unambiguously, that rings have higher relaxation times for the segmental motion compared to linear chains of the same number of monomer units. Theoretical calculations support the idea that such slowing down of local dynamics is due to the topological constraint imposed by the ring closure, a constraint which becomes negligible for very large molar masses. Our calculations suggest that due to its albeit small conformational rigidity, cyclic PDMS undergoes an additional constraint which further increases the relaxation time, producing a shallow maximum for N ≈ 50 repeat units. A similar feature is also observed in the experimental QENS data. Values of activation energy, Ea, are derived from analysis of the temperature dependence of the quasi-elastic broadening and are found to be in agreement with viscosity measurements reported in the literature. Although the pronounced molar mass dependence of Ea for linear PDMS is certainly linked to the presence of mobile chain ends, for the cyclic polymers the behavior appears to be more complex than anticipated.
Date Issued
2018-09-25
Date Acceptance
2018-09-01
Citation
Macromolecules, 2018, 51 (18), pp.7209-7223
ISSN
0024-9297
Publisher
American Chemical Society
Start Page
7209
End Page
7223
Journal / Book Title
Macromolecules
Volume
51
Issue
18
Copyright Statement
© 2018 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acs.macromol.8b00397
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000445971800022&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Polymer Science
LINEAR POLY(DIMETHYL SILOXANES)
CONCENTRATED POLYMER SYSTEMS
METHYL-GROUP DYNAMICS
GLASS-TRANSITION TEMPERATURES
INCOHERENT-NEUTRON-SCATTERING
MOLECULAR-WEIGHT DEPENDENCE
SPIN-SPIN RELAXATION
RING POLYMERS
VISCOELASTIC PROPERTIES
POLYDIMETHYLSILOXANE MELTS
Publication Status
Published
Date Publish Online
2018-09-11