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@ARTICLE{Lund:14581,
author = {Lund, R. and Pipich, V. and Willner, L. and Radulescu, A.
and Colmenero, J. and Richter, D.},
title = {{S}tructural and thermodynamic aspects of the
cylinder-to-sphere transition in amphiphilic diblock
copolymer micelles},
journal = {Soft matter},
volume = {7},
issn = {1744-683X},
address = {Cambridge},
publisher = {Royal Society of Chemistry (RSC)},
reportid = {PreJuSER-14581},
pages = {1491 - 1500},
year = {2011},
note = {The authors acknowledge the University of the Basque
Country and Basque Country Government (Ref. No. IT-436-07,
Depto. Educacion, Universidades e InvestigacionS, and
iNANOGUNE research project within Etortek program) and the
Spanish Minister of Education (Grant No. MAT 2007-63681) for
their support. The support of the European Community within
the SOFTCOMP Network of Excellence (NoE) program is also
gratefully acknowledged.},
abstract = {The structure of diblock copolymers micelles depends on a
delicate balance of thermodynamic forces driving the system
towards equilibrium and kinetic factors which limit the
systems' exploration of the phase space. The factors
governing the morphological transition between cylindrical
and spherical micelles are related to a fine balance between
entropic forces from chains within the micellar core and
corona. In order to understand and control these structures,
it is important to gain insight into the fundamental
thermodynamic driving forces governing the structure and
answer fundamental questions concerning its equilibrium
nature. In this work we aim to understand the relationship
between thermodynamics and morphological transitions by
investigating the detailed structure of a system undergoing
a cylinder-to-sphere transition. We focus on the structural
properties of micelles constituted of
poly(ethylene-alt-propylene)-poly(ethylene oxide)
(PEP1-PEO1, the numbers indicate the molar mass in kg/mole)
diblock copolymers in dimethylformamide (DMF)/water solvent
mixtures. This system is ideal for fundamental studies as it
represents a classical well-segregated block copolymer
micelle system where the interfacial tension can be
controlled in detail without significantly changing other
thermodynamic properties. Using small-angle neutron
scattering (SANS) it is shown that the system undergoes a
cylinder-to-sphere transition upon addition of DMF which
lowers the interfacial tension. By applying a detailed
thermodynamic model we show that both the dependence of the
structural parameters with the interfacial tension as well
as the morphological transition can be quantitatively
understood. The transition itself is governed by the
interfacial tension which dictates the stretching of chains
within both corona and core. At high interfacial tensions
(in water-rich solutions) discrepancies between structural
data and predictions from the thermodynamic model are
observed. A qualitative comparison with some preliminary
results on the chain exchange kinetics in the system show
that these deviations coincide with the region where this
equilibration mechanism is not active, i.e. when the
kinetics are frozen at high interfacial tensions.},
keywords = {J (WoSType)},
cin = {PGI-4 / ICS-1 / JCNS-2 / Jülich Centre for Neutron Science
JCNS (JCNS) ; JCNS / JCNS-1},
ddc = {530},
cid = {I:(DE-Juel1)PGI-4-20110106 / I:(DE-Juel1)ICS-1-20110106 /
I:(DE-Juel1)JCNS-2-20110106 / I:(DE-Juel1)JCNS-20121112 /
I:(DE-Juel1)JCNS-1-20110106},
pnm = {BioSoft: Makromolekulare Systeme und biologische
Informationsverarbeitung / Großgeräte für die Forschung
mit Photonen, Neutronen und Ionen (PNI)},
pid = {G:(DE-Juel1)FUEK505 / G:(DE-Juel1)FUEK415},
experiment = {EXP:(DE-MLZ)KWS2-20140101},
shelfmark = {Chemistry, Physical / Materials Science, Multidisciplinary
/ Physics, Multidisciplinary / Polymer Science},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000287091600030},
doi = {10.1039/c0sm00894j},
url = {https://juser.fz-juelich.de/record/14581},
}