Nanostructure in block copolymer solutions: Rheology and small-angle neutron scattering

Triblock copolymers composed of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) present an amphiphilic character in aqueous solutions. Since PPO is less hydrophilic than PEO and since their solubilities decrease when the temperature increases, the copolymers self-assemble spontaneously, forming micelles at moderate temperatures. For higher temperatures or concentrations, the copolymers or the micelles are ordered because of repulsive interactions and form lyotropic liquid crystalline phases. These are phases of very great viscosity with the aspect of gels, and transitions between different crystalline phases can occur at fixed concentration during an increase of temperature. We studied solutions of three different copolymers. The first two have a star structure. They are both composed of four branches (EO)(x)(PO)(y) fixed on an ethylene diamine, but differ by the values of x and y. Their commercial name is Tetronic 908 (x=114, y=21) and Tetronic 704 (x=16, y=18). The third copolymer (EO)(37)(PO)(56)(EO)(37) is linear and is known under the name of Pluronic P105. The measurements of the shear complex elastic modulus according to the temperature is used to determine the temperatures of the different transitions. Then, small-angle neutron scattering on samples under flow and true crystallographic arguments make it possible to identify the nature of the crystalline phases. For the systems studied, we show that the branched copolymers form only one type of liquid crystalline phase, which is bcc for the T908 and lamellar for the T704. For the linear copolymer, it is possible to identify three transitions: micellar solution to hexagonal phase, hexagonal phase to body-centered cubic phase, and finally body-centered cubic phase to lamellar phase.