Zinc oxide superstructures in colloidal polymer nanocomposite films: Enhanced antibacterial activity through slow drying

Achieving control over the distribution of biocides across the thickness of polymer nanocomposite films is one of the largest challenges to develop efficient antibacterial surfaces. In such applications, it is key to maximize the biocide presence at the film top surface to ensure contact with bacteria. Here, we make use of evaporation driven colloidal self-assembly to control the vertical distribution of biocides in polymer composite films cast from colloidal blends of polymer and zinc oxide (ZnO) nanoparticles. We present a thorough study which shows that the evaporation rate and ZnO volume fraction have a strong impact on the final film architecture and on its wetting and antibacterial properties. For high enough ZnO volume fraction, the ZnO nanoparticles assemble in superstructures on top of the film, which are higher the slower the evaporation rate used, and maximum ZnO surface coverage achieved through slow film drying. At high ZnO volume fraction (ϕ = 0.29), the zone of inhibition diameter against Escherichia coli increases as evaporation rate decreases, with the nanocomposite films having the strongest antibacterial activity when formed at slow evaporation rate. We propose a model for the formation of these colloidal superstructures based on the segregation of large (polymer) and small (ZnO) particles during drying, followed by the assembly of small particles around packed large particles due to differences in the surface charge of the two populations. Our work provides valuable guidelines for the design and assembly of not only antibacterial colloidal films but also a wider range of functional colloidal polymer films including abrasion resistant, self-cleaning, and others.