PNIPAM hydrogel micro/nanostructures for bulk fluid and droplet control
Silva, James Emanuel
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Poly(N-isopropylacrylamide) (PNIPAM) belongs to a class of stimuli-responsive materials known as “smart” polymers. When cast in the form of a hydrogel, PNIPAM’s lower critical solution temperature (LCST) of 32°C serves as a threshold for volumetric change. For solution temperatures below LCST, PNIPAM hydrogels exist as swollen, hydrophilic networks of polymer and water, spontaneously expelling the bound water molecules to shrink (and become increasingly hydrophobic) as temperature increases beyond LCST. This thesis centers on PNIPAM hydrogel layers grafted along the inner diameter of glass capillaries in order to form a temperature-responsive gating mechanism that spontaneously seals for solution temperatures below LCST. Surprisingly, very thin layers (10-20µm) of PNIPAM have dramatic effects on bulk fluid flow through the capillary due to complex interactions at the swelling interface. Specifically, for the case of capillary pressure driven flow, the swelling PNIPAM interface gives rise to "stick-and-slip" motion for bulk flow. Experiments explore the extent of this phenomenon, while a theoretical framework is proposed to model how the evolving gel interface pins the contact line. Additionally, an exploratory segment of this work examines the ways in which PNIPAM hydrogel nanoarrays can be synthesized via scalable template methods. Nanostructured PNIPAM films exhibit dramatic changes in surface properties with temperature, characterized by very low contact angles (~10°) below LCST, and very high ones (~160°) above LCST. Results for several methods are presented with lessons learned to guide future development of surfaces with temperature-responsive wetting properties.