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@ARTICLE{Lund:201683,
author = {Lund, Reidar and Willner, Lutz and Richter, Dieter and
Lindner, Peter and Narayanan, Theyencheri},
title = {{K}inetic {P}athway of the {C}ylinder-to-{S}phere
{T}ransition in {B}lock {C}opolymer {M}icelles {O}bserved in
{S}itu by {T}ime-{R}esolved {N}eutron and {S}ynchrotron
{S}cattering},
journal = {ACS Macro Letters},
volume = {2},
number = {12},
issn = {2161-1653},
address = {Washington, DC},
publisher = {ACS},
reportid = {FZJ-2015-03977},
pages = {1082 - 1087},
year = {2013},
abstract = {Here we present an in situ study of the nonequilibrium
cylinder-to-sphere morphological transition kinetics on the
millisecond range in a model block copolymer micelle system
revealing the underlying mechanism and pathways of the
process. By employing the stopped-flow mixing technique, the
system was rapidly brought (≈100 μs) deep into the
instability region, and the kinetics was followed on the
time scale of milliseconds using both time-resolved
small-angle neutron and X-ray scattering (TR-SANS and
TR-SAXS, respectively). Due to the difference in contrast
and resolution, SAXS and SANS provide unique complementary
information. Our analysis shows that the morphological
transition is characterized by a single rate constant
indicating a two-state model where the transition proceeds
through direct decomposition (fragmentation) of the
cylinders without any transient intermediate structures. The
cylindrical segments formed in the disintegration process
subsequently grow into spherical micelles possibly through
the molecular exchange mechanism until near equilibrium
micelles are formed. The observation of a two-step kinetic
mechanism, fluctuation-induced fragmentation and
″ripening″ processes, provides unique insight into the
nonequilibrium behavior of block copolymer micelles in
dilute solutions},
cin = {Neutronenstreuung ; JCNS-1 / ICS-1},
ddc = {540},
cid = {I:(DE-Juel1)JCNS-1-20110106 / I:(DE-Juel1)ICS-1-20110106},
pnm = {451 - Soft Matter Composites (POF2-451) / 54G - JCNS
(POF2-54G24)},
pid = {G:(DE-HGF)POF2-451 / G:(DE-HGF)POF2-54G24},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000328797600009},
doi = {10.1021/mz400521p},
url = {https://juser.fz-juelich.de/record/201683},
}