High Pressure Phase Diagram of an Aqueous PEO-PPO-PEO Triblock Copolymer System via Probe Diffusion Measurements

Phase diagrams of soft fragile materials are typically determined via static structural methods, such as small angle neutron scattering (SANS; Mortensen, K.; Pedersen, J. S. Macromolecules 1993, 26 (4), 805−812), small-angle X-ray scattering (Lodge, T. P.; Pudil, B.; Hanley, K. J. Macromolecules 2002, 35 (12), 4707−4717), or light scattering (Brown, W.; Schillen, K.; Almgren, M.; Hvidt, S.; Bahadur, P. J. Phys. Chem. 1991, 95 (4), 1850−1858). Dynamical methods, such as rheometry, can also be employed since the relaxation spectrum varies greatly from one phase to another. Unfortunately, mechanically disturbing these systems can alter the underlying fragile structures, precluding quiescent state determination. Here, a method for determining soft matter phase diagrams utilizing high-frequency tracer microrheology measurements is demonstrated for an aqueous PEO-PPO-PEO triblock copolymer system over a full range of temperatures and hydrostatic pressures. Since the tracer particle thermal motion reflects the underlying suspending media dynamics, the delicate fluid structure is preserved. Readily discernible changes in the tracer particle thermal motion are observed to be associated with morphological phase transitions, and the determined phase boundaries compare favorably with SANS data found in the literature.