Self-Assembled Photoresponsive and Thermoresponsive Fluids with Tunable Rheology

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Fluids whose rheological properties can be tuned by light or heat (termed as photorheological (PR) or thermorheological (TR) fluids, respectively) have attracted a lot of attention as they can be useful in numerous applications such as drug delivery, coatings, sensors, and valves for microfluidic devices. However, current formulations of these fluids suffer from several limitations: in particular, they often require synthesis of complex organic molecules by elaborate procedures, and this limits the widespread use of these fluids. In this dissertation, we seek to develop and investigate new classes of PR and TR fluids based on organic molecules that are readily available and quite inexpensive. Since no new synthesis is required, these systems could prove to be more attractive for a variety of applications.

In the first part of this study, we describe a new aqueous photorheological (PR) fluid based on the zwitterionic surfactant, erucyl dimethyl amidopropyl betaine (EDAB) and the photosensitive molecule, ortho-methoxy cinnamic acid (OMCA). EDAB/OMCA fluids exhibit photogelling, i.e., a large (~ 10,000 fold) increase in viscosity upon exposure to UV radiation. We show that this photogelling is caused by the growth of long wormlike micelles in the sample. This structural change, in turn, is induced by the UV-induced isomerization of OMCA molecules from their trans to cis form. Evidence from zeta-potential studies, small-angle neutron scattering (SANS), and rheology are used to systematically reveal the molecular and microstructural mechanism for our results.

In the second part of this study, we turn our attention to non-aqueous solvents and demonstrate a new class of PR fluids using such solvents. The PR effect here relies on transformations of "reverse" micellar structures formed by a well-known lipid (lecithin) in conjunction with para-coumaric acid (PCA). Lecithin/PCA fluids exhibit a substantial decrease in viscosity upon exposure to UV light (i.e., photothinning). Initially, the molecules self-assemble into long wormlike micelles, leading to highly viscoelastic fluids. Upon UV irradiation, PCA is photo-isomerized from trans to cis. This change in geometry induces a transition from long to short micelles. In turn, the solution viscosity is decreased by more than three orders of magnitude. Small-angle neutron scattering (SANS) is used to confirm the dramatic reduction in micellar length.

In the last study, we report a class of aqueous fluids whose viscosity increases upon heating (i.e., thermo-thickening). These fluids are mixtures of telechelic associating polymers (HEURs) and a type of supramolecules called cyclodextrins (CDs) in water. Interestingly, we observe this behavior only with a particular type of CDs, called alpha-CDs, and not with the other common CD types, i.e., beta- and gamma-CDs. These results are explained in terms of a competition between the hydrophobic end-caps and the hydrophilic backbone of the polymer for complexation with alpha-CD molecules. We have also investigated the effect of amphiphiles (single-tailed surfactants and double-tailed lipids) on the thermo-thickening. The addition of lipids substantially enhances the thermo-thickening behavior, which is explained to be due to an enhancement of the connectivity of hydrophobic junctions by lipid vesicles.