Effect of heating rate on thermo-induced aggregation of poly(ethylene oxide)-b-poly(N-isopropylacrylamide) in aqueous solutions

The effects of heating rate on the aggregate behavior of poly(ethylene oxide)-b-poly(N-isopropylacrylamide) in aqueous solutions were investigated in detail by laser light scattering and TEM. By employing two separate heating protocols, step-by-step heating at < 5 K/step and one-step jump, to heat the sample from 15°C to the selected temperature, we found that the heating rate only showed significant effect on the aggregates above the cloud point. The aggregate formed by step-by-step heating exhibited a much larger size and a broader size distribution than those formed by one-step jump heating. Moreover, neither of the aggregates were ideal micellar structures as indicated by the size and the Rg/Rh values. On the contrary, at temperatures below the cloud point where the block copolymer formed core-shelled micelles, the heating rate showed negligible effect on the size and size distribution of the micelles. Since the system underwent a phase separation above the cloud point, the heating rate effect could be reasonably explained by the phase separation mechanisms: the nucleation-and-growth mechanism in the metastable region and the spinodal decomposition mechanism in the unstable region.