skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Kinetics of Phase Transition from Lamellar to Hexagonally Packed Cylinders for a Triblock Copolymer in a Selective Solvent

Abstract

We examined the kinetics of the transformation from the lamellar (LAM) to the hexagonally packed cylinder (HEX) phase for the triblock copolymer, polystyrene-b-poly (ethylene-co-butylene)-b-polystyrene (SEBS) in dibutyl phthalate (DBP), a selective solvent for polystyrene (PS), using time-resolved small-angle X-ray scattering (SAXS). We observe the HEX phase with the EB block in the cores at a lower temperature than that observed for the LAM phase due to the solvent selectivity of DBP for the PS block. Analysis of the SAXS data for a deep temperature quench well below the LAM-HEX transition shows that the transformation occurs in a one-step process. We calculate the scattering using a geometric model of rippled layers with adjacent layers totally out of phase during the transformation. The agreement of the calculations with the data further supports the continuous transformation mechanism from the LAM to HEX for a deep quench. In contrast, for a shallow quench close to the order-order transition, we find agreement with a two-step nucleation and growth mechanism.

Authors:
; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
959889
Report Number(s):
BNL-82875-2009-JA
TRN: US201016%%1033
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Macromolecules; Journal Volume: 40
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; COPOLYMERS; KINETICS; NUCLEATION; PHTHALATES; POLYSTYRENE; SCATTERING; SOLVENTS; TRANSFORMATIONS; PHASE TRANSFORMATIONS; QUENCHING; national synchrotron light source

Citation Formats

Liu,Y., Li, M., Bansil, R., and Steinhart, M. Kinetics of Phase Transition from Lamellar to Hexagonally Packed Cylinders for a Triblock Copolymer in a Selective Solvent. United States: N. p., 2007. Web. doi:10.1021/ma071192m.
Liu,Y., Li, M., Bansil, R., & Steinhart, M. Kinetics of Phase Transition from Lamellar to Hexagonally Packed Cylinders for a Triblock Copolymer in a Selective Solvent. United States. doi:10.1021/ma071192m.
Liu,Y., Li, M., Bansil, R., and Steinhart, M. Mon . "Kinetics of Phase Transition from Lamellar to Hexagonally Packed Cylinders for a Triblock Copolymer in a Selective Solvent". United States. doi:10.1021/ma071192m.
@article{osti_959889,
title = {Kinetics of Phase Transition from Lamellar to Hexagonally Packed Cylinders for a Triblock Copolymer in a Selective Solvent},
author = {Liu,Y. and Li, M. and Bansil, R. and Steinhart, M.},
abstractNote = {We examined the kinetics of the transformation from the lamellar (LAM) to the hexagonally packed cylinder (HEX) phase for the triblock copolymer, polystyrene-b-poly (ethylene-co-butylene)-b-polystyrene (SEBS) in dibutyl phthalate (DBP), a selective solvent for polystyrene (PS), using time-resolved small-angle X-ray scattering (SAXS). We observe the HEX phase with the EB block in the cores at a lower temperature than that observed for the LAM phase due to the solvent selectivity of DBP for the PS block. Analysis of the SAXS data for a deep temperature quench well below the LAM-HEX transition shows that the transformation occurs in a one-step process. We calculate the scattering using a geometric model of rippled layers with adjacent layers totally out of phase during the transformation. The agreement of the calculations with the data further supports the continuous transformation mechanism from the LAM to HEX for a deep quench. In contrast, for a shallow quench close to the order-order transition, we find agreement with a two-step nucleation and growth mechanism.},
doi = {10.1021/ma071192m},
journal = {Macromolecules},
number = ,
volume = 40,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • Time-resolved small-angle X-ray scattering (SAXS) was used to examine the kinetics of the transition from hexagonal (hex) cylinders to body-centered cubic (bcc) spheres at various temperatures in poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) in mineral oil, a selective solvent for the middle ethylene-co-butylene (EB) block. Temperature-ramp SAXS and rheology measurements show the hex to bcc order-order transition (OOT) at 127 C and order-disorder transition (ODT) at 180 C. We also observed the metastability limit of hex in bcc with a spinodal temperature, Ts 150 C. The OOT exhibits three stages and occurs via a nucleation and growth mechanism when the final temperature Tf <more » Ts. Spinodal decomposition in a continuous ordering system was seen when Ts < Tf < TODT. We observed that hex cylinders transform to disordered spheres via a transient bcc state. We develop a geometrical model of coupled anisotropic fluctuations and calculate the scattering which shows very good agreement with the SAXS data. The splitting of the primary peak into two peaks when the cylinder spacing and modulation wavelength are incommensurate predicted by the model is confirmed by analysis of the SAXS data.« less
  • No abstract prepared.
  • We have established the existence of a line of congruent first-order lamellar-to-disorder (LAM–DIS) transitions when appropriate amounts of poly(cyclohexylethylene) (C) and poly(ethylene) (E) homopolymers are mixed with a corresponding compositionally symmetric CE diblock copolymer. The line of congruent transitions, or the congruent isopleth, terminates at the bicontinuous microemulsion (BμE) channel, and its trajectory appears to be influenced by the critical composition of the C/E binary homopolymer blend. Blends satisfying congruency undergo a direct LAM–DIS transition without passing through a two-phase region. We present complementary optical transmission, small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and dynamic mechanical spectroscopy (DMS) resultsmore » that establish the phase behavior at constant copolymer volume fraction and varying C/E homopolymer volume ratios. Adjacent to the congruent composition at constant copolymer volume fraction, the lamellar and disordered phases are separated by two-phase coexistence windows, which converge, along with the line of congruent transitions, at an overall composition in the phase prism coincident with the BμE channel. Hexagonal and cubic (double gyroid) phases occur at higher diblock copolymer concentrations for asymmetric amounts of C and E homopolymers. These results establish a quantitative method for identifying the detailed phase behavior of ternary diblock copolymer–homopolymer blends, especially in the vicinity of the BμE.« less
  • The evolution of molecular morphology in bulk samples of comb diblock copolymer pNdc 12-b-pNte 21 across the lamellar order-disorder transition (ODT) is studied using resonant x-ray scattering at the oxygen K edge, with the goal of determining whether the molecules remain extended or collapse above the ODT. The distinct spectral resonances of carbonyl oxygen on the backbone and ether oxygen in the pNte side chains combine with their different site symmetry within the molecule to yield strong differences in bulk structural sensitivity at all temperatures. Comparison with simple models for the disordered phase clearly reveals that disordering at the ODTmore » corresponds to loss of positional order of molecules with extended backbones that retain orientational order, rather than backbone collapse into a locally isotropic disordered phase. This conclusion is facilitated directly by the distinct structural sensitivity at the two resonances. Lastly, we discuss the roles of depolarized scattering in enhancing this sensitivity, and background fluorescence in limiting dynamic range, in oxygen resonant scattering.« less