Phase Behavior of Block Copolymers in Selective Solvents

Phase Behavior of Block Copolymers in Selective Solvents
Author: Yongsheng Liu
Publisher:
Total Pages: 290
Release: 2008
Genre:
ISBN:

Abstract: The goal of this research is to study the phase behavior and kinetics of order-order (OOT) and order-disorder (ODT) phase transitions in block copolymers in selective solvents. We focus on examining temperature and pressure dependence of the phase diagram and the kinetics of phase transitions using small angle x-ray scattering (SAXS). The kinetics of ODT and OOT was studied for two block copolymer solutions by time-resolved SAXS using temperature ramp and fast quench methods: (i) Poly(styrene- b -isoprene) (PS-PI) diblock copolymer in tetradecane, selective solvent for PI, which displayed face-centered-cubic (FCC) structure at low temperature, body-centered-cubic (BCC) at intermediate temperature, and was disordered at high temperature. Following a quench from 110 C to 50 C, a long-lived meta-stable BCC phase was detected prior to the formation of FCC. The data agrees very well with Cahn's model for nucleation and growth. (ii) Poly(styrene- b -ethylene- co -butylene- b -styrene) triblock copolymer in dibutyl phthaphate, selective solvent for PS, which displayed hexagonally packed cylinders (HEX) at low temperature and lamellar (LAM) phase at high temperatures. This is unusual because in most block copolymer melts LAM occurs at lower temperature than HEX. A geometric model was developed to understand the mechanism of the transition from LAM to HEX. The calculated scattering intensity agrees very well with the experimental data. A pressure network system for SAXS capable of operating in the range of 1-4000 bars with pressure jump capability was built to study the pressure dependence of phase behavior. The system was used to investigate PS-PI diblock copolymer in diethyl phthaphate. The BCC to disorder transition temperature increased with pressure at 20 C/kbar, and the lattice constant increased with pressure. Brownian Molecular Dynamics simulations were carried out to study the phase behavior of multiblock copolymers in a selective solvent. Disordered, BCC, HEX, and LAM phases were obtained depending on the concentration and number of blocks. This research provides detailed information of the kinetics of structural changes in block copolymers in selective solvents. The results provide a good understanding of the mechanism of order-disorder and order-order transitions, and are directly related to industrial applications of block copolymers.

A Soft-tetramer Model for Diblock Copolymer Melts

A Soft-tetramer Model for Diblock Copolymer Melts
Author: Claudine Groß
Publisher: Sudwestdeutscher Verlag Fur Hochschulschriften AG
Total Pages: 144
Release: 2011-03
Genre:
ISBN: 9783838124490

The ability of block copolymers to spontaneously self-assemble into a variety of ordered nano-structures not only makes them a scientifically interesting system for the investigation of order-disorder phase transitions, but also offers a wide range of nano-technological applications. The architecture of a diblock is the most simple among the block copolymer systems, hence it is often used as a model system in both experiment and theory. We introduce a new soft-tetramer model for efficient computer simulations of diblock copolymer melts. The instantaneous non-spherical shape of polymer chains in molten state is incorporated by modeling each of the two blocks as two soft spheres. The interactions between the spheres are modeled in a way that the diblock melt tends to microphase separate with decreasing temperature. Using Monte Carlo simulations, we determine the equilibrium structures at variable values of the two relevant control parameters, the diblock composition and the incompatibility of unlike components. The simplicity of the model allows us to scan the control parameter space in a completeness that has not been reached in previous molecular simulations. The resulting phase diagram shows clear similarities with the phase diagram found in experiments. Moreover, we show that structural details of block copolymer chains can be reproduced by our simple model. We develop a novel method for the identification of the observed diblock copolymer mesophases that formalizes the usual approach of direct visual observation, using the characteristic geometry of the structures. A cluster analysis algorithm is used to determine clusters of each component of the diblock, and the number and shape of the clusters can be used to determine the mesophase. We also employ methods from integral geometry for the identification of mesophases and compare their usefulness to the cluster analysis approach. To probe the properties of our model in confinement, we perform molecular dynamics simulat.