Reversible photorheological fluids based on spiropyran-doped reverse micelles.

We describe a new class of photorheological (PR) fluids whose rheological properties can be reversibly tuned by light. The fluids were obtained by doping lecithin/sodium deoxycholate (SDC) reverse micelles with a photochromic spiropyran (SP) compound. Initially, the lecithin/SDC/SP mixtures formed highly viscoelastic fluids, reflecting the presence of long, wormlike reverse micelles. Under UV irradiation, the SP was isomerized to the open merocyanine (MC) form, causing the fluid viscosity to decrease 10-fold. When the UV irradiation was switched off, the MC reverted to the SP form, and the viscosity recovered its initial value. This cycle could be repeated several times without loss of response. The rheological transitions are believed to reflect changes in the lengths of the reverse worms. To our knowledge, this is the first example of a simple, reversible PR fluid that can be made entirely from commercially available components.

Thermogelling aqueous fluids containing low concentrations of Pluronic F127 and laponite nanoparticles.

The triblock copolymer Pluronic F127 (PF127) is frequently used in colloidal and pharmaceutical formulations. Concentrated aqueous solutions of PF127 (>15 wt %) are known to undergo thermogelling (i.e., a sol-to-gel transition upon heating), which is attributed to the formation of a volume-filling cubic array of micelles. Here, we report that thermogelling can occur at much lower PF127 concentrations (1.2 to 8 wt %) if nanoparticles of laponite (25-nm-diameter disks) are also present in the formulation. Thermogelling in laponite/PF127 mixtures requires each component to be present above a minimum level. The gels have moduli around 100 Pa, and they can be reversibly liquefied to sols upon cooling. Rheological techniques, small-angle neutron scattering (SANS), and transmission electron microscopy (TEM) are used to characterize the thermogels. We attribute the onset of thermogelling to depletion flocculation of the laponite particles into a network by spherical micelles of PF127.

Photogelling colloidal dispersions based on light-activated assembly of nanoparticles.

Photorheological (PR) fluids, i.e., fluids whose rheology can be tuned by light, have been a recent focus for our laboratory. We are interested in low-cost approaches to PR fluids using molecules or materials that are readily available. Toward this end, we report a new concept for such fluids based on light-activated assembly of nanoparticles into a physical network (gel). Our system consists of disk-like nanoparticles of laponite along with a surfactant stabilizer (Pluronic F127) and the photoacid generator (PAG), diphenyliodonium-2-carboxylate monohydrate. Initially, the nanoparticles are sterically stabilized by the surfactant, and the result is a stable, low-viscosity dispersion. Upon UV irradiation, the PAG gets photolyzed, lowering the pH by approximately 3 units. In turn, the stabilizing surfactant is displaced from the negatively charged faces of the nanoparticle disks while the edges of the disks become positively charged. The particles are thereby induced to assemble into a three-dimensional "house-of-cards" network that extends through the sample volume. The net result is a light-induced sol to gel transition, i.e., from a low, water-like viscosity to an infinite viscosity and yield stress. The yield stress of the photogel is sufficiently high to support the weight of small objects. The gel can be converted back to a sol by increasing either the pH or the surfactant content.