High-Pressure Micellar Solutions of Polystyrene-block-polybutadiene and Polystyrene-block-polyisoprene in Propane Exhibit Cloud-Pressure Reduction and Distinct Micellization End Points

Micellar solutions of polystyrene-block-polybutadiene and polystyrene-block-polyisoprene in propane are found to exhibit significantly lower cloud pressures than the corresponding hypothetical nonmicellar solutions. Such a cloud-pressure reduction indicates the extent to which micelle formation enhances the apparent diblock solubility in near-critical and hence compressible propane. Concentration-dependent pressure-temperature points beyond which no micelles can be formed, referred to as the micellization end points, are found to depend on the block type, size, and ratio. The cloud-pressure reduction and the micellization end point measured for styrene-diene diblocks in propane should be characteristic of all amphiphilic diblock copolymer solutions that form micelles in compressible solvents.

Morphology and Deformation Mechanisms and Tensile Properties of Tetrafunctional Multigraft Copolymers

Morphology and deformation mechanisms and tensile properties of tetrafunctional multigraft (MG) polystrene-g-polyisoprene (PS-g-PI) copolymers were investigated dependent on PS volume fraction and number of branch points. The combination of various methods such as TEM, real time synchrotron SAXS, rheo-optical FTIR, and tensile tests provides comprehensive information at different dimension levels.TEMand SAXS studies revealed that the number of branch points has no obvious influence on the microphase-separated morphology of tetrafunction MG copolymers with 16 wt % PS. But for tetrafunctional MG copolymers with 25 wt % PS, the size and integrity of PS microdomains decrease with increasing number of branch point. The deformation mechanisms ofMGcopolymers are highly related to the morphology. Dependent on the microphase-separated morphology and integrity of the PS phase, the strain-induced orientation of the PS phase is at different size scales. Polarized FT-IR spectra analysis reveals that, for all investigated MG copolymers, the PI phase shows strain-induced orientation along SD at molecular scale. The proportion of the PI block effectively bridging PS domains controls the tensile properties of the MGcopolymers at high strain, while the stress-strain behavior in the low-mediate strain region is controlled by the continuity of PS microdomains. The special molecular architecture, which leads to the higher effective functionality of PS domains and the higher possibility for an individual PI backbone being tethered with a large number of PS domains, is proposed to be the origin of the superelasticity for MG copolymers.

Stability of Order in Solvent-Annealed Block Copolymer Thin Films

ABSTRACT: One way to produce high order in a block copolymer thin film is by solution casting a thin film and slowly evaporating the solvent in a sealed vessel. Such a solvent-annealing process is a versatile method to produce a highly ordered thin film of a block copolymer. However, the ordered structure of the film degrades over time when stored under ambient conditions. Remarkably, this aging process occurs in mesoscale thin films of polystyrene-polyisoprene triblock copolymer where the monolayer of vitrified 15 nm diameter polystyrene cylinders sink in a 20 nm thick film at 22 °C. The transformation is studied by atomic force microscopy (AFM). We describe the phenomena, characterize the aging process, and propose a semiquantitative model to explain the observations. The residual solvent effects are important but not the primary driving force for the aging process. The study may lead to effective avenue to improve order and make the morphology robust and possibly the solvent-annealing process more effective.