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024 7 _ |2 DOI
|a 10.1039/C0SM00894J
024 7 _ |2 WOS
|a WOS:000287091600030
024 7 _ |2 Handle
|a 2128/7284
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|a LundPWRCR2011
037 _ _ |a PreJuSER-14581
041 _ _ |a eng
082 _ _ |a 530
084 _ _ |2 WoS
|a Chemistry, Physical
084 _ _ |2 WoS
|a Materials Science, Multidisciplinary
084 _ _ |2 WoS
|a Physics, Multidisciplinary
084 _ _ |2 WoS
|a Polymer Science
100 1 _ |0 P:(DE-HGF)0
|a Lund, R.
|b 0
245 _ _ |a Structural and thermodynamic aspects of the cylinder-to-sphere transition in amphiphilic diblock copolymer micelles
260 _ _ |a Cambridge
|b Royal Society of Chemistry (RSC)
|c 2011
300 _ _ |a 1491 - 1500
336 7 _ |a Journal Article
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440 _ 0 |0 16881
|a Soft Matter
|v 7
|x 1744-683X
|y 4
500 _ _ |a 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.
520 _ _ |a 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.
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856 7 _ |u http://dx.doi.org/10.1039/C0SM00894J
856 4 _ |u https://juser.fz-juelich.de/record/14581/files/FZJ-14581.pdf
|y Published under German "Allianz" Licensing conditions on 2011-01-04. Available in OpenAccess from 2012-01-04
|z Published final document.
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