Physical Gels of Atactic Poly(N-isopropylacrylamide) in Water: Rheological Properties and As-Derived Spinodal Temperature

Aqueous solutions of atactic poly(N-isopropylacrylamide) (a-PNIPAM) undergo complex phase transitions at 20–33 °C. In this temperature range, the a-PNIPAM solution exhibits a phase behavior of lower critical solution temperature at the binodal temperature (T(b)) and physical gel formation at the gel temperature (T(gel)). On slow heating of the one-phase solution containing linear a-PNIPAM chains, branched chains are gradually developed to proceed with the physical gelation before phase separation considering that T(gel) < T(b). Thus, the phase separation temperature determined from the conventional approaches, either by turbidity to derive the T(b) or by scattering to derive the spindal temperature (T(s)) from the Ornstein–Zernike analysis, is strictly the transition temperature associated with the a-PNIPAM hydrogel (or highly branched chains newly developed at elevated temperatures), rather than the initial a-PNIPAM solution prepared. Herein, the spinodal temperatures of a-PNIPAM hydrogels (T(s,gel)) of various concentrations were determined from rheological measurements at a heating rate of 0.2 °C/min. Analyses of the temperature dependence of loss modulus G″ and storage modulus G′ give rise to the T(s,gel), based on the Fredrickson–Larson–Ajji–Choplin mean field theory. In addition, the specific temperature (T(1)) above which the one-phase solution starts to dramatically form the aggregated structure (e.g., branched chains) was also derived from the onset temperature of G′ increase; this is because as solution temperature approaches the spinodal point, the concentration fluctuations become significant, which is manifested with the elastic response to enhance G′ at T > T(1). Depending on the solution concentration, the measured T(s,gel) is approximately 5–10 °C higher than the derived T(1). On the other hand, T(s,gel) is independent of solution concentration to be constant at 32.8 °C. A phase diagram of the a-PNIPAM/H(2)O mixture is thoroughly constructed together with the previous data of T(gel) and T(b).