SUMMARY

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 networks of polymer and water, spontaneously expelling the bound water molecules to shrink as temperature increases beyond LCST.

This thesis seeks to examine applications in which PNIPAM hydrogels can be utilized for control of bulk fluid motion. The focus 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. The nature of these interactions is explored, and a model is proposed for explaining how these swelling hydrogel layers act to pin contact lines.

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.