Perpendicular Deformation of a Near-Single-Crystal Triblock Copolymer with a Cylindrical Morphology. 1. Synchrotron SAXS

• Published in: Macromolecules 2000-12, Vol.33 (25), p.9395-9406
• Main Authors: Honeker, Christian C, Thomas, Edwin L, Albalak, Ramon J, Hajduk, Damian A, Gruner, Sol M, Capel, Malcolm C
• Format: Article
• Language: English
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Properties and characterization; Structure, morphology and analysis
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma000593y

A poly(styrene-block-isoprene-block-styrene) (SIS) triblock copolymer with a polystyrene (PS) cylinder morphology was processed via roll-casting to produce a near single-crystal texture. Deformation experiments normal to the cylinder axis were carried out using synchrotron small-angle X-ray scattering (SAXS) with the beam both parallel and perpendicular to the cylinder axis. In situ measurement of load and displacement enabled morphological information to be mapped to the stress−strain curve. Results indicate that the deformation proceeds in two stages. Deformation to strains of approximately 100−130% is nearly affine. The rubber matrix extends along the stretching direction (SD) while contraction occurs almost exclusively along the neutral direction due to the constraint imposed by the aligned PS cylinders. A measured Poisson's ratio of 0.9 compares favorably with a value of 1 expected for a perfect composite. At deformations beyond 130% an X-pattern is observed at perpendicular incidence. The angle between the arms of the X increases asymptotically, while the intercylinder spacing remains fairly constant. The initial hexagonal pattern undergoes a continuous distortion and provides further evidence for the deformation discontinuity in the rate of lateral contraction. The morphological observations in reciprocal space are interpreted in terms of a kinking instability in which the plane strain state imposed by the oriented cylinders is relieved by their kinking into a chevron pattern. The kinking transition strain is expected to be dependent on the degree of cylinder misorientation, the shear resistance of the rubber matrix, and the bending resistance of the PS cylinders.