Molecular Dynamics Study of Polystyrene-b-poly(ethylene oxide) Asymmetric Diblock Copolymer Systems.

Two polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers differing in molecular mass (49 and 78 kDa) but possessing the same PEO cylindrical morphology are examined to elucidate their molecular dynamics. Of particular interest here is the molecular motion of the PEO blocks involved in the rigid amorphous fraction (RAF). An analysis of complementary thermal calorimetry and X-ray scattering data confirms the presence of microphase-separated morphology as well as semicrystalline structure in each copolymer. Molecular motion within the copolymer systems is monitored by dielectric and nuclear magnetic resonance spectroscopies. The results reported herein reveal the existence of two local Arrhenius-type processes attributed to the noncooperative local motion of PEO segments involved in fully amorphous and rigid amorphous PEO microphases. In both systems, two structural relaxations governed by glass-transition phenomena are identified and assigned to cooperative segmental motion in the fully amorphous phase (the α process) and the RAF (the αc process). We measure the temperature dependence of the dynamics associated with all of the processes mentioned above and propose that these local processes are associated with corresponding cooperative segmental motion in both copolymer systems. In marked contrast to the thermal activation of the α process as discerned in both copolymers, the αc process appears to be a sensitive probe of the copolymer nanostructure. That is, the copolymer with shorter PEO blocks exhibits more highly restricted cooperative dynamics of PEO segments in the RAF, which can be explained in terms of the greater constraint imposed by the glassy PS matrix on the PEO blocks comprising smaller cylindrical microdomains.

Ultrapermeable, reverse-selective nanocomposite membranes.

Polymer nanocomposites continue to receive tremendous attention for application in areas such as microelectronics, organic batteries, optics, and catalysis. We have discovered that physical dispersion of nonporous, nanoscale, fumed silica particles in glassy amorphous poly(4-methyl-2-pentyne) simultaneously and surprisingly enhances both membrane permeability and selectivity for large organic molecules over small permanent gases. These highly unusual property enhancements, in contrast to results obtained in conventional filled polymer systems, reflect fumed silica-induced disruption of polymer chain packing and an accompanying subtle increase in the size of free volume elements through which molecular transport occurs, as discerned by positron annihilation lifetime spectroscopy. Such nanoscale hybridization represents an innovative means to tune the separation properties of glassy polymeric media through systematic manipulation of molecular packing.

Platinum-containing hyper-cross-linked polystyrene as a modifier-free selective catalyst for L-sorbose oxidation.

Impregnation of hyper-cross-linked polystyrene (HPS) with tetrahydrofuran (THF) or methanol (ML) solutions containing platinic acid results in the formation of Pt(II) complexes within the nanocavities of HPS. Subsequent reduction of the complexes by H2 yields stable Pt nanoparticles with a mean diameter of 1.3 nm in THF and 1.4 nm in ML. The highest selectivity (98% at 100% conversion) measured during the catalytic oxidation of L-sorbose in water is obtained with the HPS-Pt-THF complex prior to H2 reduction. During an induction period of about 100 min, L-sorbose conversion is negligible while catalytic species develop in situ. The structure of the catalyst isolated after the induction period is analyzed by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. Electron micrographs reveal a broad distribution of Pt nanoparticles, 71% of which measure less than or equal to 2.0 nm in diameter. These nanoparticles are most likely responsible for the high catalytic activity and selectivity observed. The formation of nanoparticles measuring up to 5.9 nm in diameter is attributed to the facilitated intercavity transport and aggregation of smaller nanoparticles in swollen HPS. The catalytic properties of these novel Pt nanoparticles are highly robust, remaining stable even after 15 repeated uses.

Interfacial and topological measurements of bicontinuous polymer morphologies.

Bicontinuous morphologies are ubiquitous in nature and occur at various length scales. Topological features of two such morphologies arising in an ordered block copolymer at equilibrium and a polymer blend during spinodal decomposition are measured from three-dimensional images. Interfacial curvature, coordination number, and interjunction distance distributions exhibit remarkable similarity in these systems, despite vastly different length scales. A channel coordination of 3 is dominant in both morphologies, and topological measurements such as the Euler-Poincaré characteristic and genus are reported.

Direct measurement of interfacial curvature distributions in a bicontinuous block copolymer morphology.

Self-consistent field theory predicts that the complex phase behavior of block copolymers does not originate solely from the interface seeking constant mean curvature as once thought, but instead reflects competing minimization of interfacial tension and packing frustration. To test this prediction, we directly measure interfacial curvature distributions from a 3D image reconstruction of the bicontinuous gyroid morphology. Results obtained here reveal that the gyroid interface is not constant mean curvature and confirm the importance of packing frustration in the stabilization of such complex nanostructures.

Molecular-weight factors affecting formation of the OBDD morphology in block copolymer blends.

Block copolymers undergo self-organization when the blocks are sufficiently incompatible, and generate a variety of periodic morphologies in the limit of strong segregation. An equilibrium morphology only recently added to the diblock copolymer phase diagram is the ordered bicontinuous double-diamond (OBDD) morphology, which possess a Pn3m space group. It has been observed over a very narrow composition range (ca. 4 vol%), thereby making it difficult to obtain in pure copolymers. This obstacle can, however, be surmounted by blending a copolymer with one of the parent homopolymers. In the present study, several symmetric poly(styrene-b-isoprene) diblock copolymers varying in molecular weight (M) have been blended with homopolystyrene to produce the OBDD morphology. Transmission electron microscopy is employed here to identify the morphologies in cryosections of each blend and reveals that, at intermediate molecular weights, the OBDD morphology is indeed observed. At low M, near the order-disorder transition, however, a lamellar catenoid or disordered morphology is preferred. At the other extreme, high-M blends are frustrated by molecular entanglements and adopt a cylindrical morphology.