Viscoelastic Response of Photo-Cross-Linked Poly(N-isopropylacrylamide) Coatings by QCM-D

The viscoelastic behavior of surface-tethered poly(N-isopropylacrylamide), or poly(NIPAAm), networks in contact with aqueous solutions was characterized by the quartz crystal microbalance with dissipation (QCM-D). To avoid ambiguities in the data analysis, four integer multiples of the dry thickness (h = k x 36 nm, where k = 1, 2, 3, 4) were analyzed at the third through ninth overtones of the QCM-D signal. At the third overtone, the networks resembled rigid films and the viscoelastic behavior could not be ascertained. With increasing overtones, however, the films showed deviation from the rigid film limit, allowing for analysis of the viscoelastic parameters. As the network collapsed over the temperature range of 15-40 degrees C, the shear modulus of the network increased by a factor of 24 (from 5 to 120 MPa); the shear viscosity, on the other hand, increased only by a factor of 2 (from 40 to 80 cP). The high values of the shear modulus suggest the QCM-D probes a regime where the polymer mesh does not adequately relax, and the high values of the shear viscosity suggest significant polymer-polymer coil overlap above and below the demixing temperature. Finally, the influence of NaCl on the viscoelastic response was measured. Interestingly, NaCl affects the shear modulus of the networks but not the dynamics.