Rheological analysis of core-stabilized Pluronic F127 by semi-interpenetrating network (sIPN) in aqueous solution

Abstract

A poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer (Pluronic F127) micelle system was stabilized using an ultraviolet-induced semi-interpenetrating network (sIPN). The sIPN structure within the micelle cores was found to stabilize the micelles against low temperatures, but affected the resulting material properties. In this study, the rheological properties of Pluronic F127 with sIPN (F127-sIPN) and without sIPN (F127) were compared. The presence of the sIPN structure increased the gelation temperature (Tgel) at the same concentration, and unlike F127, F127-sIPN exhibited strong heating rate dependent and thermodynamically irreversible behaviors. Hard gels containing various concentrations of F127-sIPN and F127 were investigated at 40 °C. At concentrations above 18 wt. %, both F127-sIPN and F127 exhibited similar linear viscoelastic properties due to the tight, ordered core–shell micelles packing, but the two systems exhibited different behaviors below 18 wt. % concentration. To investigate this difference, hard gels with 16 wt. % F127-sIPN and F127 were selected, and two types of nonlinear rheological tests were conducted, i.e., large amplitude oscillatory shear (LAOS) and strain-rate frequency superposition (SRFS) tests. The cage modulus of F127-sIPN obtained from LAOS testing showed it maintained its elastic contribution over the large deformation region meaning that a loose core network still existed. The relaxation time spectrum of F127-sIPN obtained by SRFS testing indicated it had two relaxation modes (fast and slow) whereas that for F127 had only a fast mode. The slow relaxation mode of F127-sIPN is associated with crosslinking of the sIPN. Since these behaviors were not observed in linear rheological tests, it was concluded that nonlinear rheological tests provide more structural information about hard gels.