Transient solidlike behavior near the cylinder/disorder transition in block copolymer solutions

Park, MJ; Char, K; Lodge, TP; Kim, JK

HERO ID

1315355

Reference Type

Journal Article

Year

2006

Language

English

PMID

16884248

HERO ID 1315355
In Press No
Year 2006
Title Transient solidlike behavior near the cylinder/disorder transition in block copolymer solutions
Authors Park, MJ; Char, K; Lodge, TP; Kim, JK
Journal Journal of Physical Chemistry B
Volume 110
Issue 31
Page Numbers 15295-15301
Abstract A nearly symmetric polystyrene-block-polyisoprene diblock copolymer dissolved at a concentration of 40% in styrene-selective solvents exhibited a cylinder-to-disorder transition upon heating. The solvents used were diethyl phthalate (DEP) and 75:25 and 50:50 mixtures of DEP with di-n-butyl phthalate (DBP). In DEP, the most styrene-selective of the three solvents, rheological measurements indicated a distinct plateau in the temperature-dependent elastic modulus across the 8 degrees C interval above the order-disorder transition temperature, T(ODT) = 116 degrees C. Previous small-angle neutron scattering measurements in this regime indicated the equilibrium phase to be a liquidlike solution of approximately spherical micelles. An isothermal frequency sweep in this regime indicated a very long relaxation time. Annealing eventually led to the recovery of liquidlike rheological response, over a time scale of hours. Qualitatively similar phenomena were also observed in 75:25 DEP/DBP and 50:50 DEP/DBP solutions, except the fact that the temperature window of the transient response is narrow and the time scale for the recovery diminishes significantly. Neither small-angle X-ray scattering nor static birefringence gave any clear signature of the transient structure. The structure that leads to the transient rheological response is attributed to micellar congestion due to the slow relaxation of anisotropic micelles into an equilibrium distribution of micelles. Possible origins of the remarkable solvent selectivity dependence are also discussed.
Doi 10.1021/jp056336i
Pmid 16884248
Wosid WOS:000239463300037
Is Certified Translation No
Dupe Override No
Comments Scopus URL: https://www.scopus.com/inward/record.uri?eid=2-s2.0-33748268716&doi=10.1021%2fjp056336i&partnerID=40&md5=6ee29abf0d5afa6e73adb8ce7fdce8cd
Is Public Yes
Language Text English