Effect of water-soluble polymers, polyethylene glycol and poly(vinylpyrrolidone), on the gelation of aqueous micellar solutions of Pluronic copolymer F127.

The micellization of F127 (E(98)P(67)E(98)) in dilute aqueous solutions of polyethylene glycol (PEG6000 and PEG35000) and poly(vinylpyrrolidone) (PVP K30 and PVP K90) is studied. The average hydrodynamic radius (r(h,app)) obtained from the dynamic light scattering technique increased with increase in PEG concentration but decreased on addition of PVP, results which are consistent with interaction of the micelles with PEG and the formation of micelles clusters, but no such interaction occurs with PVP. Tube inversion was used to determine the onset of gelation. The critical concentration of F127 for gelation increased on addition of PEG and of PVP K30 but decreased on addition of PVP K90. Small-angle X-ray scattering (SAXS) was used to show that the 30 wt% F127 gel structure (fcc) was independent of polymer type and concentration, as was the d-spacing and so the micelle hard-sphere radius. The maximum elastic modulus (G(max)(')) of 30 wt% F127 decreased from its value for water alone as PEG was added, but was little changed by adding PVP. These results are consistent with the packed-micelles in the 30 wt% F127 gel being effectively isolated from the polymer solution on the microscale while, especially for the PEG, being mixed on the macroscale.

The effect of n-, s- and t-butanol on the micellization and gelation of Pluronic P123 in aqueous solution.

In dilute aqueous solution unimers of copolymer P123 (E(21)P(67)E(21)) associate to form micelles, and in more concentrated solution micelles pack to form high-modulus gels. We are interested in the use of the system as a templating agent in the synthesis of mesoporous materials, and the possibility of determining gel structure, hence mesoporosity, by use of n-, s- or t-butanol. Dynamic light scattering from clear dilute solutions has been used to confirm micellization, visual observation of mobility (tube inversion) to detect gel formation in concentrated solutions, oscillatory rheometry to confirm gel formation and provide values of elastic moduli over a wide temperature range, and small-angle X-ray scattering to determine gel structure. As expected, clear cubic gels (fcc) formed at moderate concentrations and temperatures, e.g. 30 wt.% P123, 20°C, and clear hexagonal gels at higher concentrations and temperatures. The transition on heating from cubic to hexagonal gel involved an intermediate turbid phase in which cubic and hex structures coexisted. Considering cubic gels of 35 wt.% P123 in 5 wt.% butanol/water, those in n-butanol/water had the lowest critical temperatures for gel formation and the highest maximum values for the dynamic elastic modulus (G') of the gels, a result consistent with n-butanol/water being the poorest solvent for P123.

Effect of ethanol on the gelation of aqueous solutions of Pluronic F127.

In dilute aqueous solution unimers of copolymer F127 (E(98)P(67)E(98)) associate to form micelles, and in more concentrated solution micelles pack to form high-modulus gels. Cosolvents are known to affect these processes, and ethanol/water mixtures have been of particular interest. Dynamic light scattering from dilute solutions was used to confirm micellization, but major attention was directed towards the gels. Visual observation of mobility (tube inversion) was used to detect gel formation, oscillatory rheometry to confirm gel formation and provide values of the elastic moduli over a wide temperature range, and small-angle X-ray scattering to determine gel structure. The solvents were limited to 10, 20 and 30 wt.% ethanol/water. Critical concentrations for gel formation were similar for 10 and 20 wt.% ethanol/water but were significantly increased for 30 wt.% ethanol/water, e.g. at T=45 degrees C from c approximately 15 wt.% to c approximately 28 wt.%. The elastic moduli reached maximum values at T approximately 50 degrees C: e.g. G' approximately 25 kPa for 25 wt.% F127 in 10 and 20 wt.% ethanol/water and a similar value for 30 wt.% F127 in 30 wt.% ethanol/water. Hard gels of 30 and 35 wt.% F127 in ethanol/water at 25 and 40 degrees C had the body-centered cubic (bcc) structure.

Aqueous gels of mixtures of ionic surfactant SDS with pluronic copolymers P123 or F127.

Gel diagrams based on tube inversion and oscillatory rheometry are reported for Pluronic copolymers F127 (E(98)P(67)E(98)) and P123 (E(21)P(67)E(21)) in mixtures with anionic surfactant sodium dodecyl sulfate (SDS). Total concentrations (c, SDS+copolymer) were as high as 50 wt % with mole ratios SDS/copolymer (mr) in the ranges 1-5 (F127) and 1-7 (P123). Temperatures were as high as 90 degrees C. Determination of the temperature dependences of the dynamic moduli served to confirm the gel boundaries from tube inversion and to reveal the high elastic moduli of the gels, e.g., compared at comparable positions in the gel phase, a 50 wt % SDS/P123 with mr = 7 had G' three times that of a corresponding gel of P123 alone. Small-angle X-ray scattering (SAXS) was used to show that the structures of all the SDS/F127 gels were bcc and that the structures of the SDS/P123 gels with mr = 1 were either fcc (c = 30 wt %) or hex (c = 40 wt %). Assignment of structures to SDS/P123 gels with values of mr in the range 3-7 was more difficult, as high-order scattering peaks could be very weak, and at the higher values of c and mr, the SAXS peaks included multiple reflections.

Effect of ethanol on the micellization and gelation of pluronic p123.

In certain applications copolymer P123 (E21P67E21) is dissolved in water-ethanol mixtures, initially to form micellar solutions and eventually to gel. For P123 in 10, 20, and 30 wt % aqueous ethanol we used dynamic light scattering from dilute solutions to confirm micellization, oscillatory rheometry, and visual observation of mobility (tube inversion) to determine gel formation in concentrated solutions and small-angle X-ray scattering (SAXS) to determine gel structure. Except for solutions in 30 wt % aqueous ethanol, a clear-turbid transition was encountered on heating dilute and concentrated micellar solutions alike, and as for solutions in water alone (Chaibundit et al. Langmuir 2007, 23, 9229) this could be ascribed to formation of wormlike micelles. Dense clouding, typical of phase separation, was observed at higher temperatures. Regions of isotropic and birefringent gel were defined for concentrated solutions and shown (by SAXS) to have cubic (fcc and hcp) and hexagonal structures, consistent with packed spherical and elongated micelles, respectively. The cubic gels (0, 10, and 20 wt % ethanol) were clear, while the hex gels were either turbid (0 and 10 wt % ethanol), turbid enclosing a clear region (20 wt % ethanol), or entirely clear (30 wt % ethanol). The SAXS profile was unchanged between turbid and clear regions of the 20 wt % ethanol gel. Temperature scans of dynamic moduli showed (as expected) a clear distinction between high-modulus cubic gels (G'max approximately 20-30 kPa) and lower modulus hex gels (G'max<10 kPa).