Temperature- and strain-dependent transient microstructure and rheological responses of endblock-associated triblock gels of different block lengths in a midblock selective solvent.

Endblock associative ABA gels in midblock selective solvents are attractive due to their easily tunable mechanical properties. Here, we present the effects of A- and B-block lengths on the rheological properties and microstructure of ABA gels by considering three low and one high polymer concentrations. The triblock polymer considered is poly(methyl methacrylate)-poly(-butyl acrylate)-poly(methyl methacrylate) [PMMA-PBA-PMMA] and the midblock solvent is 2-ethyl-1-hexanol. The gelation temperature has been found to be strongly dependent on the B-block (PBA) length, as longer B-blocks facilitate network formation resulting in higher gelation temperature even with lower polymer chain density. Longer A-blocks (PMMA chains) make the endblock association stronger and significantly increase the relaxation time of gels. Temperature-dependent microstructure evolution for the gels with high polymer concentration reveals that the gel microstructure does not change significantly after the gel formation takes place. The dynamic change of microstructure in an applied strain cycle was captured using RheoSAXS experiments. The microstructure orients with the applied strain and the process is reversible in nature, indicating no significant A-block pullout. Our results provide new understandings regarding the temperature and strain-dependent microstructural change of ABA gels in midblock selective solvents.