Temperature and concentration dependent viscosity and gelation temperature of ABA triblock copolymer solutions

In solutions of ABA-triblock copolymers in a poor solvent for A thermoreversible gelation can occur. A three-dimensional dynamic network may form and, given the polymer and the solvent, its structure will depend on temperature and polymer mass fraction. The zero-shear rate viscosity of solutions of the triblock-copolymer polystyrene-polyisoprene-polystyrene in n-tetradecane was measured as a function of temperature and polymer mass fraction, and analyzed; the polystyrene blocks contained about 100 monomers, the polyisoprene blocks about 2000 monomers. Empirically, in the viscosity at constant mass fraction plotted versus inverse temperature, two contributions could be discerned; one contribution dominating at high and the other one dominating at low temperatures. In a comparison with theory, the contribution dominating at low temperatures was identified with the Lodge transient network viscosity; some questions remain to be answered, however. An earlier proposal for defining the gelation temperature Tgel is specified for the systems considered, and leads to a gelation curve; Tgel as a function of polymer mass fraction.