Properties of confinedpNIPAM-co-AAC microgels
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Tunable nanostructures have many important uses in thin film applications. Tunability can be achieved by creating a film that has features that respond to external stimuli, such as temperature, humidity, or pH. However, the response can vary greatly between a confined and unconfined case. In the case of confined materials, this response can be greatly reduced, even completely suppressed, which indicates that separate studies must be conducted on confined states in order to better understand their use for real applications. Microgels have been previously shown to have exceptional responsive properties that depend on their chemical structure and synthesis. Unlike solid thin hydrogel films that respond on the order of hours, microgels arrange on a surface with no external force and create a highly porous layer which responds rapidly, on the order of minutes, to outside stimuli. These properties make microgels a promising candidate for use in tunable thin films. Although the responsive properties of microgels have been extensively studied in solution and unconfined films, this is not indicative of conditions that would most likely have the microgels placed between two stiffer layers of material. Microgels have been shown to respond to glucose concentration, temperature, pH, and light. One well-studied microgel is poly-N-isopropylacrylamide copolymerized with Acrylic Acid (pNIPAM-co-AAC). These microgels use the thermal response of pNIPAM combined with the pH sensitivity of pAAC to create a dually-responsive material. To study the effects of confinement on pNIPAM-co-AAC microgels, we encapsulated these particles within bi-layers of poly(allylamine hydrochloride)-poly(sodium 4-styrenesulfonate) (PAH-PSS) in order to simulate their response within a polyelectrolyte material. Our samples were prepared with a method called tilt-drying, which creates a microgel concentration gradient. This allowed us to study both the confinement caused by the multi-layered film as well as the effects of microgels on each other. Our results have shown that the change in particle height is unaffected by the concentration of the film, but the thermal response of pNIPAM-co-AAC microgels is significantly suppressed by the encapsulation of microgels into nanoscale layers.