Deformation and orientation behavior of polystyrene-b-polybutadiene-b-poly(methyl methacrylate) triblock terpolymers: Influence of polybutadiene microstructures and the molar masses

Abstract

Morphological changes caused by deformation and orientation of different domains of polystyrene-b-polybutadiene-b-poly(methyl methacrylate), SBM, triblock terpolymers were investigated using in-situ small angle X-ray scattering (SAXS), tensile testing, and transmission electron microscopy (TEM). Two sets of SBM triblock terpolymers with similar weight fractions of the three blocks were studied. The two sets differ in terms of their molecular weights. Each set contained two SBM differing in their polybutadiene isomers (1,2- and 1,4-B). Results showed that for 1,2-B based SBMs the polybutadiene block forms cylindrical domains which coalesce in the glassy lamellar matrix of the two glassy outer blocks whereas the lower molar mass 1,4-B based SBM forms mixed S/M and the higher one forms well segregated long range ordered lamellae. These morphological differences indicate that the deformation and the orientation behavior of the polymers' domains differ. In 1,2-B based SBMs yielding at high stresses was followed by a stress drop after the yield point. The other polymer type showed homogeneous deformation of the lamellar domains at their yield point. 2D-SAXS during deformation of the triblock terpolymers showed an anisotropic deformation pattern in the 1,2-B SBMs, whereas four point SAXS patterns were found for the 1,4-B SBMs. Further studies showed that the fragmented lamellar planes of the lower molar mass 1,2-SBM oriented randomly whereas the orientation of the lamellar planes of the higher molar mass 1,2-B SBM was parallel to the strain direction. The alignment of the lamellar planes of 1,4-B SBMs were randomly distributed in the unstretched state.