No abstract

Block copolymers are all around us, found in such products as upholstery foam, adhesive tape and asphalt additives. This class of macromolecules is produced by joining two or more chemically distinct polymer blocks, each a linear series of identical monomers, that may be thermodynamically incompatible (like oil and vinegar). Segregation of these blocks on the molecular scale (5–100 nm) can produce astonishingly complex nanostructures, such as the “knitting pattern” shown on the cover of this issue of PHYSICS TODAY. This striking pattern, discovered by Reimund Stadler and his coworkers, reflects a delicate free-energy minimization that is common to all block copolymer materials.

Vesicles were made from amphiphilic diblock copolymers and characterized by micromanipulation. The average molecular weight of the specific polymer studied, polyethyleneoxide-polyethylethylene (EO40-EE37), is several times greater than that of typical phospholipids in natural membranes. Both the membrane bending and area expansion moduli of electroformed polymersomes (polymer-based liposomes) fell within the range of lipid membrane measurements, but the giant polymersomes proved to be almost an order of magnitude tougher and sustained far greater areal strain before rupture. The polymersome membrane was also at least 10 times less permeable to water than common phospholipid bilayers. The results suggest a new class of synthetic thin-shelled capsules based on block copolymer chemistry.

A mean-field phase diagram for conformationally symmetric diblock melts using the standard Gaussian polymer model is presented. Our calculation, which traverses the weak- to strong-segregation regimes, is free of traditional approximations. Regions of stability are determined for disordered (DIS) melts and for ordered structures including lamellae (L), hexagonally packed cylinders (H), body-centered cubic spheres (Q Im3̄m ), close-packed spheres (CPS), and the bicontinuous cubic network with Ia3̄d symmetry (Q Ia3̄d ). The CPS phase exists in narrow regions along the order−disorder transition for χN ≥ 17.67. Results suggest that the Q Ia3̄d phase is not stable above χN ∼ 60. Along the L/Q Ia3̄d phase boundaries, a hexagonally perforated lamellar (HPL) phase is found to be nearly stable. Our results for the bicontinuous Pn3̄m cubic (Q Pn3̄m ) phase, known as the OBDD, indicate that it is an unstable structure in diblock melts. Earlier approximation schemes used to examine mean-field behavior are reviewed, and comparisons are made with our more accurate calculation.

Different polymers can be combined into a single material in many ways, which can lead to a wide range of phase behaviors that directly influence the associated physical properties and ultimate applications. Four factors control polymer-polymer phase behavior: choice of monomers, molecular architecture, composition, and molecular size. Current theories and experiments that deal with the equilibrium thermodynamics and non-equilibrium dynamics of polymer mixtures are described in terms of these experimentally accessible parameters. Two representative molecular architectures, binary linear homopolymer mixtures and diblock copolymers, exhibiting macrophase separation and microphase segregation, respectively, are examined in some detail. Although these model systems are fairly well understood, a myriad of mixing scenarios, with both existing and unrealized materials applications, remain unexplored at a fundamental level.