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We have used neutron reflection and phase contrast microscopy to investigate the morphology and surface topology of thin films of nearly symmetric (f=0.55) and asymmetric (f=0.77), poly (ethylene–propylene)–poly (ethylethylene) (PEP–PEE) diblock copolymers (f being the PEP volume fraction) and have identified three important differences in their ordering properties. First, annealed films of the asymmetric diblocks do not form the lamellar microstructure found in symmetric diblocks; their structure can instead be modeled in terms of the hexagonal packing of PEE cylinders observed in bulk small-angle neutron scattering measurements. However, the cylinders show in-plane distortions, which we interpret in the context of nonintegral layering. These distortions are amplified at the surfaces where the PEE assumes lamellarlike form. Second, as-cast films of the asymmetric diblock are characterized by a microstructure lacking long-range order, pinned between strongly segregated PEE at both surfaces. These films can be equilibrated through annealing, leading to the well-ordered structures described earlier. The changes with annealing are surprising given that both PEP and PEE are well above their glass transitions at room temperature. Finally, the block asymmetry and the associated cylindrical structure in the interior are also manifested in the surface topology. Thin films of asymmetric PEP–PEE are smooth on a macroscopic scale unlike their symmetric counterparts, which form islands on the surface to accommodate films of nonintegral lamellar thicknesses.

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Neutron Reflection (NR) and Dynamic Secondary Ion Mass Spectroscopy (DSIMS) experiments were conducted on symmetrically deuterated polystyrene triblock bilayers (HDH/DHD) which directly probed the interdiffusion dynamics of the chains during welding. The HDH chains had their centers deuterated 50%, the DHD chains had their ends deuterated (25% at each end) such that each chain contained approximately 50% D. During welding, anisotropic motion of the chains produces a time‐dependent oscillation (ripple) in the H and D concentration at the interface, which bears the characteristic signature of the polymer dynamics. These oscillations were compared with those predicted by Rouse, polymer mode coupling (PMC), and reptation dynamics. The following conclusions can be made from this study. (a) During the interdiffusion of high molecular weight HDH/DHD pairs, higher mobility of the chain ends caused a concentration oscillation which increased to a maximum amplitude, and eventually vanished at times, t > τD. The amplitude, or excess enrichment found, was appreciably more than that predicted by Rouse and PMC simulations, and was only slightly less than that predicted from reptation simulations. (b) The oscillations were completely missing in the 30 and 50K HDH/DHD polymers, which are only weakly entangled. The lack of oscillations for the 30 and 50K pairs may be due to a combination of surface roughness and fluctuations of order 30 Å. (c) It was found that the position of the maximum in this ripple stayed at the interface during its growth. This is also consistent with reptation and has not been explained by other theories. (d) All dynamics models for linear polymers produce ripples, many of which are qualitatively similar to that predicted for reptation. However, each ripple bears the fingerprint of the dynamics in terms of its time‐dependent shape, position, and magnitude, and the models are clearly distinguishable. Our results, in summary, support reptation as a candidate mechanism of interdiffusion at polymer(SINGLEBOND) polymer interfaces and its uniqueness is being further pursued. © 1996 John Wiley & Sons, Inc.

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