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@ARTICLE{Hofmann:825917,
author = {Hofmann, M. and Kresse, B. and Heymann, L. and Privalov, A.
F. and Willner, L. and Fatkullin, N. and Aksel, N. and
Fujara, F. and Rössler, E. A.},
title = {{D}ynamics of a {P}aradigmatic {L}inear {P}olymer: {A}
{P}roton {F}ield-{C}ycling {NMR} {R}elaxometry {S}tudy on
{P}oly(ethylene–propylene)},
journal = {Macromolecules},
volume = {49},
number = {22},
issn = {1520-5835},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2017-00196},
pages = {8622 - 8632},
year = {2016},
abstract = {The dynamics of melts of linear
poly(ethylene-alt-propylene) (PEP) of different molar masses
(M) is investigated by 1H field-cycling (FC) NMR
relaxometry. Employing a commercial and a home-built
relaxometer the spin-lattice relaxation rate R1(ω) is
measured in the frequency range of 200 Hz to 30 MHz and the
temperature range of 200–400 K. Transforming the FC NMR
relaxation data to the susceptibility representation and
applying frequency–temperature superposition, master
curves for the dipolar correlation function CDD(t/τα)
(containing intra- and intermolecular contributions) are
constructed which extend up to six decades in amplitude and
eight in time. Here, τα is the time scale of the
structural (α-) relaxation, which is obtained over several
decades. Comparison with previously reported FC data for
polybutadiene (PB) discloses very similar CDD(t). Depending
on M, all the five relaxation regimes of a polymer melt are
covered: in addition to the α-process (0) and the terminal
relaxation (IV), which are immanent to all liquids, three
polymer-specific power-law regimes (Rouse, I; constraint
Rouse, II; and reptation, III) are found, i.e. CDD(t) ∝
t–ε. The corresponding exponents (εI–III) are close to
those predicted by the tube-reptation (TR) model for the
segmental translation. In contrast to previous
interpretation the intermolecular relaxation dominates
CDD(t), in particular in regime II and beyond. The
decomposition into intra- (mediated by segmental
reorientation) and intermolecular relaxation (mediated by
segmental translation) via isotope dilution experiments
yields Cinter(t) = Ctrans(t) ∝ t-0.28±0.05 concerning PEP
and Cinter(t) ∝ t-0.30±0.05 concerning PB for regime II
(high-M limit). For the reorientational correlation function
Cintra(t) = C2(t) ∝ t–0.50±0.05 (PEP) and C2(t) ∝
t–0.45±0.05 (PB) are obtained. These exponents εIIintra
are at variance with εIITR = 0.25 predicted by the TR
model. The fact that translation conforms to the TR model,
while reorientation does not, now confirmed for the two
polymers PEP and PB, challenges de Gennes’
return-to-origin hypothesis which assumes strong
translational-rotational coupling in the TR model.},
cin = {ICS-1 / Neutronenstreuung ; JCNS-1},
ddc = {540},
cid = {I:(DE-Juel1)ICS-1-20110106 / I:(DE-Juel1)JCNS-1-20110106},
pnm = {551 - Functional Macromolecules and Complexes (POF3-551) /
6G4 - Jülich Centre for Neutron Research (JCNS) (POF3-623)
/ 6215 - Soft Matter, Health and Life Sciences (POF3-621)},
pid = {G:(DE-HGF)POF3-551 / G:(DE-HGF)POF3-6G4 /
G:(DE-HGF)POF3-6215},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000388913500025},
doi = {10.1021/acs.macromol.6b01906},
url = {https://juser.fz-juelich.de/record/825917},
}