Grain growth in a polystyrene-polyisoprene block copolymer melt is studied by time-resolved depolarized light scattering after a quiescent quench from the disordered to the ordered state. At shallow quench depths, classical nucleation and growth kinetics are observed. Grains comprising the equilibrated ordered phase nucleate and grow by consuming the surrounding disordered phase. In contrast, deep quenches result in the formation of disorganized grains with an average order parameter that is well below the equilibrium value. Small angle neutron scattering and rheological experiments were conducted to facilitate the interpretation of the light scattering data. We show that the nonequilibrium grain structure formed during deep quenches is due to extremely high nucleation density. Under these circumstances, the space required for the formation of equilibrated grains is unavailable.

The thermodynamic interactions in anionically synthesized poly(styrene-block-ferrocenyldimethylsilane) (SF) copolymers were examined using birefringence, small-angle X-ray and neutron scattering (SAXS and SANS). We show that birefringence detection of the order−disorder transition is possible in colored samples provided the wavelength of the incident beam is in the tail of the absorption spectrum. The location of the order−disorder transition was confirmed by SAXS. The temperature dependence of the Flory−Huggins parameter, χ, of SF copolymers, determined by SAXS, is similar in magnitude to that between polystyrene and polyisoprene chains. We find that χ is independent of block copolymer composition (within experimental error). We also demonstrate that the neutron scattering length densities of styrene and ferrocenyldimethylsilane moieties are identical due to a surprising cancellation of factors related to density and atomic composition.

The nature of order−disorder transitions in cross-linked diblock copolymer melts was studied using small-angle X-ray scattering (SAXS) and birefringence measurements. Experiments were conducted on cross-linked polystyrene-block-polyisoprene copolymer samples wherein the polyisoprene block was selectively cross-linked at a temperature well above the order−disorder transition temperature of the pure block copolymer. We find a reversible transition from a disordered gel to an ordered gel when the cross-linking density is below a critical value. The rheological properties of disordered block copolymer gels are very different from that of cross-linked homopolymer gels.

Novel responsive solids were prepared by randomly cross-linking the polyisoprene chains of a disordered polystyrene-polyisoprene block copolymer. Our experiments show that block copolymer chains, composed of hundreds of repeat units, can undergo reversible order-disorder transitions despite the quenched randomness that arises due to the attachment of one of the blocks to a cross-linked network. The structure, properties, and phase behavior of these materials are determined by a delicate interplay between the density of cross-links and the nature of the ordered state.