Is Surface Roughness a “Scapegoat” or a Primary Factor When Defining Particle−Substrate Interactions?

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Extended DLVO interaction potentials were determined for spherical particles approaching nanopatterned substrates using the numerical surface element integration (SEI) technique. In most cases, nanopatterned ("rough") surfaces produced smaller interaction potentials than chemically identical planar ("smooth") surfaces. For unfavorable scenarios, electrostatic double layer and acid-base potentials were reduced to a greater extent than van der Waals potentials, which made rough surfaces "more attractive" than smooth ones. Two influential surface morphological descriptors emerged: (1) the ratio of particle size to asperity size, a/r, and (2) the ratio of asperity separation to asperity size, p/r. As a/r increased, particle-substrate interaction energy decreased, while the opposite was true for p/r. The simple morphological descriptors gave rise to an analytical model based on the Derjaguin integration (DI) method that compared reasonably well with numerical SEI results, where the size and density of nanopatterned surface features dictated the magnitude of interaction potentials. In fact, changes in the size of nanopatterned surface features impacted the magnitudes of interaction potentials to the same extent as similar changes in the magnitudes of acid-base free energy and zeta potential, which begs the question, "is surface morphology a 'scapegoat' or a primary consideration when defining particle-substrate interactions?"