Segment Density and Coil Dimensions of Polymer Chains Anchored to Solid Surfaces

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Polymers being in direct contact with solid surfaces form interphases in which the chain segments assume shapes and segment density profiles different from those in the bulk. These interface-induced effects, their extent and location depend on parameters such as number, architecture, rigidity, and molar mass of the chains next to the solid surface. It is the aim to develop profound knowledge about this interphase, and of its consequences for the material properties, via site-resolved analysis of the segment conformation of surface-anchored polymer chains: well-defined polymers of different molar mass, constitution and architecture (linear, branched, amorphous, semi-crystalline) are synthesized, which are deuterated in specific chain segments only (“H/D block copolymers”). These chains will be immobilized on planar and bent solid substrates, thereby covering the full accessible range of grafting densities. The resulting polymer layers are analyzed when (i) in contact with air, (ii) in direct contact with each other, (iii) in contact with free polymer chains or (iv) with solvents, and (v) under strain and deformation, using neutron and X-ray small angle scattering and X-ray reflectomery. The gained insights can be used as input for simulation work, NMR and AFM studies, and will deepen understanding of the properties of polymer (nano)composites considerably.