Resonantly enhanced off-specular X-ray scattering from polymer/polymer interfaces⋆
Abstract.We have used measurements of the absolute intensity of diffuse X-ray scattering to extract the interfacial tension of a buried polymer/polymer interface. Diffuse scattering was excited by an X-ray standing wave whose phase was adjusted to have a high intensity at the polymer/polymer interface and simultaneously a node at the polymer/air interface. This method permits the capillary-wave-induced roughness of the interface, and hence the interfacial tension, to be measured independently of the polymer/polymer interdiffusion.
Interfacial roughness in a near-critical binary fluid mixture: X-ray reflectivity and near-specular diffuse scattering
Abstract:Measurements are presented of the X-ray specular reflectivity and near-specular diffuse scattering of the interface in a near-critical mixture of hexane and perfluorohexane. A lineshape analysis of the scattered intensity at each temperature yields values for the interfacial tension and interfacial width. The temperature variation of the tension and width so-obtained are consistent with current understanding of this interface, which holds that there is, firstly, an intrinsic width over which the fluid density varies smoothly from one coexistence composition to the other, and, secondly, that the interface acquires an additional and larger statistical interfacial width as a result of capillary fluctuations.
Collective diffusion, nucleation, and spinodal decomposition in polymer mixtures
The dynamics of concentration fluctuations in binary polymer mixtures AB, A and B being long and flexible chains, is studied near the critical point of unmixing. A ‘‘hydrodynamic’’ theory in close analogy to the treatments of Cahn–Hilliard and Cook for the dynamics of unmixing alloys is developed, and its validity is carefully analyzed. It is shown that homogeneous nucleation for long chains is negligible except in a narrow region of volume fraction φ0 near the spinodal curve φs0 of width (φs0−φ0)/φ0∝N−1, where N is the number of subunits of the chains. For N→∞ the spinodal curve hence is well defined, in contrast to mixtures with short‐range forces, and also the linearized theory of spinodal decomposition is predicted to have wider validity. The collective relaxation in the one‐phase region is described by a characteristic time involving the collective diffusion constant Dcoll τq=(Dcoll q2)−1, if the wave vector q is smaller than the inverse correlation length ξ−1coll, while in the range ξ−1coll≪q≪R−1 (R...