Controlled modulation of short- and long-range adhesion of microscale biogenic replicas

Abstract

The generation of nanostructured microscale assemblies with complex, three-dimensional (3-D) morphologies possessing multicomponent inorganic compositions tailored for adhesion is of considerable scientific and technological interest. This dissertation demonstrates that self-assembled 3-D organic templates of biogenic origin can be converted into replicas comprised of numerous other functional nanocrystalline inorganic materials and, further, how such replicas can tailored for adhesion. Nature provides a spectacular variety of biologically-assembled 3-D organic structures with intricate, hierarchical (macro-to-micro-to-nanoscale) morphologies designed for particle adhesion. The conformal coating of such structurally-complex biotemplates with synthetic materials provides a framework for chemical transformation of other, complex synthetic organic templates and the basis to study imparted adhesion properties. Three specific research thrusts are detailed in this document. First, freestanding magnetite (Fe3O4) replicas of bio-organic templates are synthesized via a layer-by-layer (LbL) wet chemical deposition process and subsequent morphology-preserving thermal treatments to allow for structures with tailorable long-range magnetic adhesion. Second, freestanding spinel ferrite replicas of bio-organic templates are synthesized (via LbL coating and thermal treatment) for grain size controlled long-range magnetic adhesion and short range van der Waals adhesion. The final research thrust focuses on the use of a low temperature (≤ 250°C) wet-chemical based process to convert bioorganic templates into magnetically-coated structures retaining both the size and morphology of the template. The rate-limiting kinetic mechanism(s) of the partial reduction of the inorganic coatings have been examined via quartz crystal microbalance analysis. The effects of the coating micro/nanostructure on magnetic behavior and on surface adhesion, have been investigated.