Journal of Polymer Science Part B: Polymer Physics, Vol.37, No.16, 2229-2238, 1999
Non-equilibrium phase behavior of diblock copolymer melts and binary blends in the intermediate segregation regime
The phase behavior of intermediately segregated (chi N = 45) poly(ethylene)poly(ethylethylene) (PE-PEE) diblock copolymers and PE-PEE binary blends are characterized using transmission electron microscopy and small-angle X-ray scattering. Surprisingly, the preparation-dependent, nonequilibrium phase behavior can be overwhelming even at this degree of segregation. A pure diblock with a poly(ethylene) volume fraction of f(PE) = 0.46 exhibited coexisting lamellae and perforated layers when prepared using a precipitation technique, but contained only the lamellar morphology when solvent cast. This preparation dependence was more dramatic in binary diblock copolymer blends with average compositions of [f(PE)] = 0.44, 0.46, and 0.48. Precipitated blends exhibited a microphase separated structure that was disordered and bicontinuous; however, solvent cast samples exhibited either a cylindrical, coexisting cylindrical and lamellar, or lamellar morphology. This nonequilibrium behavior is attributed to the high degree of segregation and the proximity to the cylinder/lamellae phase boundary.
Keywords:transmission electron microscopy;small angle X-ray scattering;solvent casting;precipitation;preparation dependence;blends